APCChE 2019

All Abstracts

Plenary lectures

A200 [Plenary] Can biotechnology deliver cost effective fuels for transportation with reduced carbon footprint?
MIT, Cambridge, Massachusetts 02139, USA

Producing liquid fuels for transportation with reduced carbon footprint has been the focus of many laboratories around the world. To succeed, this effort must utilize low cost aggregated feedstocks that can be converted efficiently to liquid fuels. Lignocellulosic biomass, has attracted much attention during the past 50 years, however, its conversion still presents many challenges stemming from its relatively high cost, broad distribution and recalcitrance to biological or chemical methods of conversion. These difficulties have prevented the widespread use of this abundant resource. On the other hand, with the cost of renewable electricity in continuous decline, an era of inexpensive electrons, (or hydrogen), is envisioned, when focus is shifted away from the supply of cheap electrons (energy) to the cost effective utilization of carbon. In such Carbon-, instead of energy-constrained world, processes that most efficiently utilize carbon will take priority over processes that emphasize optimal energy use. This vision alters dramatically the parameters of the landscape of energy research. In this talk, I will provide evidence of low cost electrons and discuss processes that have the potential to compete with fossil fuels. These processes are based on CO2 fixation by acetogenic bacteria and provide a promising scheme for the production of liquid fuels in combination with biological methods for producing lipids and hydrocarbons from volatile fatty acids.

A300 [Plenary] Chemical Engineering: Relevance in a changing world
Jonathan SEVILLE
The University of Birmingham

Chemical engineering has been of immense value to mankind in the last 100 years but it needs to keep changing if it is to be of equal value to future generations. We need to recognise where its value really lies – not just as a collection of facts and a set of skills but in ways of thinking about problems. The discipline grew largely on the back of the oil and gas industry, but global concerns about sustainability have caused us to think about energy in completely different ways, in which chemical engineering needs to compete with other disciplines to maintain its relevance. Current concerns about our discipline’s over-concentration on supplying the needs of the fossil fuel industries are not new; a crisis of confidence in Europe from 2000 onwards has led to growth in activity in teaching and research which is aimed at sustainability and at “formulation engineering”. The latter is concerned with the manufacture of chemical and biochemical products that are sold by function or effect and are usually both chemically complex and physically ‘structured’. If chemical engineering is to maintain its relevance it needs strong institutions and professional organisations to grow and promote the discipline, and - crucially – to ensure that society has confidence in our professionalism, particularly in the area of safety. International collaboration between these organisations will ensure that global development priorities are met with rational and responsible solutions.

A400 [Plenary] Preparing chemical engineers for Industry 4.0
The University of Melbourne, Victoria 3010, Australia

Over the next two decades the potential exists to transform the process industries through the use of large data sets, machine learning and artificial intelligence. Adoption of these emerging technologies should lead to increases in efficiencies, productivity and safety. Integrating process plant data with market data will allow improved agility, allowing companies to respond to changing market demands more rapidly, and profitably.
In the coming decades new processing facilities will be more highly instrumented than they are today. Artificial intelligence and machine learning coupled with data analytics tools will allow the development of semi-autonomous systems which will aid in plant operation. These systems will be able to provide management and operators with advice on a range of issues including system inspections, maintenance scheduling and troubleshooting. The most appropriate data will be provided to operators in the field allowing more informed decision to be made.
Presently, advances are occurring in a range of areas including improved sensors for process control, connectivity, simulation and training. At the same time that all these advances are taking place, the risk of cyber attacks through the unauthorised access into data centres and control systems will increase. The vulnerabilities of processing facilities will not only be through internet-based resources, but also through the interception of plant-based communications systems such as wifi.
This digital revolution is currently not reflected in our chemical engineering programs at either the undergraduate or graduate level. The majority of workers in the process industries are simply unprepared for taking advantage of the current advances in digital technologies. This therefore opens up significant opportunities for education and training in both the short term and the long term.
This presentation will look at the challenges and opportunities in preparing chemical engineers to work in Industry 4.0.

A509 [Plenary] Chemical engineering for SDGs
Tohoku University, Sendai, Miyagi 980-8577, Japan

Today, the Asia-Pacific region is at the center of the world economy, but having this responsibility means that there will be many challenges and responsibilities for all of us. Production volume is growing in response to the continuous increase of global demand that is driving new innovations and businesses at unprecedented rates of growth that are thriving and being created almost simultaneously as new areas are discovered. Along with this remarkable economic growth and prosperity, our responsibility to the environment is also increasing; material intensity, which is the use of resources to produce products, is driving development of society with such large projections of consumption and production, that they can be considered to be unsustainable. We have to rethink some aspects of our growth and motivation.
As the result of a United Nations Conference on Sustainable Development in Rio de Janeiro in 2012, a new set of 17 sustainable development goals (SDGs) were formulated for 2030, which gives 17 Sustainable Development Goals (SDGs) in areas of People, Planet, Prosperity, Peace, and Partnership. While the Asia-Pacific region has the greatest growth in the World, its material intensity is also the greatest, which means that Earth's resources are increasingly being used inefficiently without regard to their environmental or social impact. One of the most important goals of the 18th Asian Pacific Confederation of Chemical Engineering Congress is to introduce innovative methods and techniques for reducing material intensity without degrading environmental and social conditions. The critical step in achieving the SDGs is philosophy for decoupling economic growth and environmental issues. So far, chemical engineering has contributed to the society through development and implementation of innovative chemical technologies and maximizing efficiency in process systems. However, to achieve sustainability, we have to embrace a completely new philosophy to include, as paramount, the well-being of society, Earth's environment and respect for nature. We propose to call this new philosophy “Sufficiency,” which has the goal of not only lowering material intensity and increasing process efficiency, but also, at the same time and with paramount importance, improving the well-being of people, their living and working conditions and the Earth's environment.
The theme of APCChE 2019 Congress is “Chemical Engineering for Sustainable Development Goals.” APCChE is an opportunity for all of us in the Asia-Pacific region to promote ideas to achieve the SDG 17 “Strengthen the means of implementation and revitalize the Global Partnership for Sustainable Development.” The Congress will provide many opportunities to discuss how chemical engineering will contribute to the SDGs in the world and will be a landmark event for promoting cooperation in the region.

Session SP. Student program (contest):— Research proposal for SDGs from youth (Open to the public)

A104 [Keynote] Science, technology and innovation for SDGs
Yamaguchi University
A106 [Keynote] Energy transition from diesel to renewables in off-grid islands: Techno-economics and its implication to the food-energy-water nexus
Joey D. OCON
The University of the Philippines - Diliman
(Proposals from University Teams)
SP01 Characterization of expanded perlite from Albay, Bicol, Philippines with chitosan as adsorbent medium and the design of a fixed-bed column for the adsorption of Ni(II), Cu(II) from synthetic rainwater
Hazil MAGPAYO1,2, Sam Denielle TUGAOEN1,2, Sheralyn FUERTE1,2, Michael Anthony CASTILLO1,2, Jerica DEOCAREZA1,2, Jeanelle IGNACIO1,2, and Lola Domnina PESTAŇO1,2
1 Department of Chemical Engineering, Faculty of Engineering, University of Santo Tomas, Manila
2 Research Center for the Natural and Applied Sciences, University of Santo Tomas, Manila

SP01 abstract PDF file <299001-1>
SP02 Development of an improved packing material using perlite from Albay, Bicol, Philippines and the design of a packed-column for the absorption of SO2 gas
Julian Sam ANTONIO1,2, Maritoni BUENVIAJE1,2, Fracheska CRUZ1,2, Jervin VALOROSO1,2, Allan Paolo L. ALMAJOSE1, Lola Domnina PESTAŇO1,2
1 Department of Chemical Engineering, Faculty of Engineering, University of Santo Tomas, Manila
2 Research Center for the Natural and Applied Sciences, University of Santo Tomas, Manila

SP02 abstract PDF file <299002-1>
SP03 Biomass-based biodegradable materials
Haijia SU, Zhaonan SUN, Daihui ZHU, Jiye GE, Ziwei LIU, Chengfeng TAN
Bioresources Group, School of Life Science and Technology, Beijing University of Chemical Technology, Beijing

SP03 abstract PDF file <299003-1>
SP04 A three-tier evaluation approach for chemical industry: how does it contribute to SDG globally, industrially and locally
Meng JIANG, Minghao XU, Xin CHEN, Zijian REN
Department of Chemical Engineering, Tsinghua University, Beijing

SP04 abstract PDF file <299004-1>
SP05 Natural wallpaper imitating the wax layer of plants
Yongjae NA, Jinyoung KIM, Eunha CHO, Hyunmin KIM
School of Chemical Engineering, Chonnam National University, Buk-gu Gwangju

SP05 abstract PDF file <299005-1>
SP06 The feasibility of solar-power-based hydrogen economy in Indonesia
Department of Chemical Science and Engineering, Tokyo Institute of Technology, Tokyo

SP06 abstract PDF file <299006-1>
SP07 Effect of different treatment of clay soil and its application to the removal of ammonium, nitrite and nitrate ion during phytoremediation
Nurul Solehah MOHD ZAINI1,2, Mohd Nazli NAIM1, Wuled LENGGORO2
1 Department of Process and Food Engineering, Faculty of Engineering, Universiti Malaysa, Serdang
2 Graduate School of Bio-Applications and Systems Engineering, Faculty of Engineering, Tokyo University of Agriculture and Engineering, Tokyo

SP07 abstract PDF file <299007-1>
SP08 Hydrothermal carbonization of bamboo waste as a cathode electrocatalyst support for oxygen reduction reaction
Mark Ian S. CASTILLANO, Larra Gene L. FERNANDO, Ir-shad M. JAUJOHN
Laboratory of Electrochemical Engineering, Department of Chemical Engineering, College of Engineering, University of the Philippines, Diliman, Quezon City

SP08 abstract PDF file <299008-1>
SP09 Genome-writing using big data and artificial intelligence for mass production of plastic-decomposing bacterium
HAO Yingquan, Nattanai KUNANUSONT, Peany HOUNG, Yuya MURAKAMI
School of Materials and Chemical Technology, Tokyo Institute of Technology, Tokyo

SP09 abstract PDF file <299009-1>
SP10 Development of a self-powered cyclone system using thermoelectrical power generation for a sustainable energy industry
Sion YU, Seong Beom PARK, Ga Ram YANG
Department of Energy and Chemical Engineering, Incheon National University, Incheon

SP10 abstract PDF file <299010-1>
SP11 Advancing current approaches to diabetes management: a framework to improve the stability of insulin
Vidya Sundaram, Chien Wei Ooi, Ramakrishnan Nagasundara Ramanan
Chemical Engineering Discipline, School of Engineering, Monash University Malaysia, Jalan Lagoon Selatan

SP11 abstract PDF file <299011-1>
SP12 Analysis of packing structure of fiber-reinforced asphalt compact
Department of Chemical Engineering, Nazarbayev University, Nur-Sultan

SP12 abstract PDF file <299012-1>
SP13 Fuzzy optimization of rice straw utilization in the Philippines based on carbon and nitrogen footprints
Iliana Benice TAN
Department of Chemical Engineering, De La Salle University, Manila

SP13 abstract PDF file <299013-1>
SP14 Process Design for Sustainable Production of Value Chemicals from Agricultural Wastes Instead of Fossil Resources
Ryu SATO1,2, Hiromu SASAKI1, Ryuta X. SUZUKI1, Kentaro ATSUKAWA1, Ryota MIYAMOTO1, Chinatsu UKAWA1,2
1 Department of Chemical Engineering, Tokyo University of Agriculture and Technology, Tokyo
2 Department of Food and Energy Systems Science, Tokyo University of Agriculture and Technology, Tokyo

SP14 abstract PDF file <299014-1>
SP15 Edu(A)ction
Ericha Indriani MARJUKI, Deri IRYAWAN, Nur Adry YANSAH, Muhammad Reza HUSEIN
Chemical Engineering Department, University of Muhammadiyah Jakarta, Jakarta Pusat

SP15 abstract PDF file <299015-1>
SP16 A sustainable solution to provide 100 % electricity to least developed countries: Case of Mozambique
Mayu ASAKA, Kaisheng FENG, Zihao ZHANG
Department of Applied Chemistry, Waseda University, Tokyo

SP16 abstract PDF file <299016-1>
SP17 Development of an eco-friendly agricultural product storage system using adsorption cooling
Soeun KIM, Sunhae SHIN, Jungmin AHN, Hyemin JUNG, Haeji HONG
Department of Chemical Engineering and Materials Science, EWHA Womans University, Seoul

SP17 abstract PDF file <299017-1>
SP18 Satoyama conservation to consider from state of bamboo forest
Ren ABE1, Yuhei TAKAMORI1, Sayaka NISHITANI1, Takashi MIYAZAKI2, Naoki MAEDA3, Kousuke HIROMORI3
1 School of Engineering, Tohoku University, Sendai
2 Faculty of agriculture, Tohoku University, Sendai
3 Department of Chemical Engineering, Tohoku University, Sendai

SP18 abstract PDF file <299018-1>
SP19 Interconnection between material synthesis and recycling process for enhanced sustainability of platinum
Graduate School of Environmental Studies, Tohoku University, Sendai

SP19 abstract PDF file <299019-1>
SP20 Life cycle assessment of Na-Y zeolite membrane for water/IPA separation in Japan
Department of Applied Chemistry, School of Advanced Science and Engineering, Waseda University, Tokyo

SP20 abstract PDF file <299020-1>
SP21 Improvement of in-vivo absorption of nutrient by advanced processing of bioencapsulation
Bowen FANG1, Noriaki SANO2, Kyuya NAKAGAWA2
1 Division of Food Science and Biotechnology, Graduate School of Agriculture, Kyoto University, Kyoto
2 Department of Chemical Engineering, Faculty of Engineering, Kyoto University, Kyoto

SP21 abstract PDF file <299021-1>
SP22 Energy harvesting device driven by transpiration for sensor power supply
Ryohei AOKI, Yusuke NOGUCHI, Risa NISHIO
School of Science for Open and Environmental Systems, Graduate School of Science and Technology, Keio University, Yokohama

SP22 abstract PDF file <299022-1>
SP23 Application of “Chemical Leasing” to shipbuilding industry for reducing a negative impact on marine environment
1 Graduate School of Public Policy, The University of Tokyo, Tokyo
2 Graduate School of Agricultural and Life Sciences, The University of Tokyo, Tokyo
3 Graduate School of Frontier Sciences, Atmosphere and Ocean Research Institute, The University of Tokyo, Kashiwa

SP23 abstract PDF file <299023-1>
SP24 Solutions to the global energy crisis: Development of extremely fast preparation method for hydrogen storage materials from plastic waste and biomass using microwave-induced plasma
Purichaya KUPTAJIT, Kyuya NAKAGAWA, Noriaki SANO
Department of Chemical Engineering, Kyoto University, Kyoto

SP24 abstract PDF file <299024-1>
SP25 Expanding the boundary of chemical engineering to the primary industry: Sustainable development in Tohoku
Kakeru OUCHI1, Jingwei ZHOU1, Yuki KATO2
1 Graduate School of Engineering, Tohoku University, Sendai
2 Faculty of Engineering, Tohoku University, Sendai

SP25 abstract PDF file <299025-1>
SP26 NEXUS: A simulation and optimization tool for productive use of renewable energy and water access planning in island communities
Michael CASTRO, Wilbert James FUTALAN
Laboratory of Electrochemical Engineering, University of the Philippines, Diliman, Quezon City

SP26 abstract PDF file <299026-1>
(Proposals from High-School Teams)
SP31 The power of sawdust to support the future of the Earth
Misaki IMAMURA, Syuka CHIBA, Ayaka HORII, Toshihiro KITSUI
Sapporo Nihon University Senior High School, Kitahiroshima

SP31 abstract PDF file <299031-1>
SP32 How to improve usefulness of biodegradable plastics?
Haruka UEHARA, Chinatsu NARAOKA, Manato TAKEDA, Taiga ARAI
Sapporo Kaisei Secondary School, Sapporo

SP32 abstract PDF file <299032-1>
SP33 To prevent sick house syndrome using peanut shell
Sapporo Kaisei Secondary School, Sapporo

SP33 abstract PDF file <299033-1>
SP34 How we can utilize lignin?
Sapporo Kaisei Secondary School, Sapporo

SP34 abstract PDF file <299034-1>
SP35 The problem of plastic pollution and future prospects
Sapporo Kaisei Secondary School, Sapporo

SP35 abstract PDF file <299035-1>
(Contributions to SDGs from Small-Medium Enterprises)
SP41 Sustainable management of mercury waste
Chiayu WU
Nomura Kosan Co., Ltd., Tokyo
SP42 Wastewater treatment: SDGs & HINODE SANGYO
Kaori FUJITA, Mahomadou TOURE
Hinode Sangyo Co., Ltd., Yokohama
SP43 How to stop ocean plastic waste? ∼Plastic waste to energy in house consumption bases∼
Takahisa SOMA
ELCOM Co., Ltd., Sapporo

Session S1. APCChE–UNIDO Special Symposium (Open to the public)

A202 [Keynote] UNIDO's technology transfer and realization of SDGs in developing countries
Fukuya IINO
United Nations Industrial Development Organization, Vienna 1190 Austria / UNIDO ITPO Tokyo, UNU HQs Bldg. 8F, 5-53-70, Jingumae, Shibuya-Ku, Tokyo 150-0001 Japan

UNIDO is the specialized agency of the United Nations that promotes inclusive and sustainable industrial development (ISID) for poverty reduction, inclusive globalization and environmental sustainability. Technology transfer and business management capacity building are one of the UNIDO's mainstream activities in promoting ISID involving various industrial activities related to chemical engineering. The refrigeration sector, which includes air conditioning, is currently responsible for around 17% of global electricity consumption. For some developing countries this percentage even exceeds 40% of total national electricity demand. Environmentally friendly manufacturing of refrigeration equipment and energy efficient cold supply chain are crucial for achieving the Sustainable Development Goals by 2030 and beyond. This presentation will share UNIDO's technology transfer examples in contributing to the achievement of the SDGs. In addition, it touches on the scope and share the expected output of this symposium.

A204 [Keynote] Enlighten the next generation on a diverse Chemical Engineering for sustainable development
–Practices in a Chemical Engineering introductory course for first-year undergraduates

Bing ZHU
Director and Professor, Institute for Circular Economy, Tsinghua University, Beijing 100084, P. R. China

Chemical engineering is uniquely placed to drive positive impact across the full spectrum of the SDG agenda. The UN pointed out ‘education is critical for promoting sustainable development and improving the capacity of the people to address sustainable development issues’. We, as the educators in chemical engineering, should enlighten the next generation on a diverse Chemical Engineering for sustainable development.
Diverse dimensions of sustainable development are embodied in the subjects of chemical engineering, yet the profound relations and representations are to be dug out and elucidated. The academia is obliged to explore the potential and boundary of how chemical engineering can make a more sustainable world. As the UN set up the roadmap of SDGs to 2030, people in the chemical engineering community shall contemplate and act proactively on how the instruction activities can be consistent with this process.
Among all the efforts, enhancing the next generation's recognitions of chemical engineering and guiding them to face the challenges matters most. Take my introductory course at Tsinghua University as a case. A group of professors, alumni and experts in the chemical industry are invited to share their understanding of chemical engineering to first-year undergraduates. Extracurricular activities such as practices, voices-from-young-professionals and demonstration videos also help them to draw a big picture. The integration of diverse information from the introductory class presents a wide range of SDG concepts and highlights some of them (e.g. SDG 5-gender; 6-water; 7-energy; 8-work; 9-innovation, 12-consumption and production, 13-climate change etc.), which allows us to think how to integrate SDG into teaching, starting from the freshmen. Inspired by APCChE-UNIDO Symposium, we will further upgrade the course with a systematic outlook of SDG. Hopefully, the discipline of chemical engineering could be enriched with more sustainability by our efforts at least starting from education.

A206 Mapping an undergraduate ChE Curriculum using an SDG-based CDIO Approach at the University of Santo Tomas, Manila Philippines
University of Santo Tomas, Manila, Philippines; Philippine Institute of Chemical Engineers, Manila, Philippines

The academic year 2018-2019 marks the introduction of a new 4-year B.S. Chemical Engineering curriculum to the first batch of K-12 graduates in the Philippines. The Commission on Higher Education (CHED), through its Technical Panel for Engineering and Technology (TPET) is tasked with monitoring the implementation of the 2018 Policies, Standards and Guidelines (PSG) on all higher Educational Institutions (HEIs) offering B.S. Engineering Programs to ensure that the attributes of our future graduates are comparable with global standards.
Apart from complying with the CHED-TPET guidelines, the Chemical Engineering Department at the University of Santo Tomas is re-engineering its 4-year undergraduate curriculum based on a localized Conceive, Design, Implement, Operate (CDIO) approach that integrates the Sustainable Development Goals (SDGs). The objective is to not only to integrate sustainability principles but also provide an action-oriented, transformative pedagogy, which supports self-directed learning, participative and interdisciplinary collaboration, creative problem-solving, and the linking of formal and informal learning.
An SDG map in the shape of a periodic table addresses specific targets for each SDG across the curriculum and identifies courses or modules where such target can be imparted to students. Similarly, a syllabus map is created for specific courses in order to allow faculty and students to merge awareness of the SDGs with a CDIO approach that will apply innovative solutions to sustainable development issues.
This presentation shall discuss the SDG-based CDIO approach in the preparation of the curriculum and syllabus map as well as issues and lessons learned from the endeavor.

A213 [Invited] Overview of trends and efforts towards achieving SDGs in Japan and Sapporo
Akihiro SATAKE
City of Sapporo, Sapporo, Hokkaido 060-8611 Japan

Sapporo City is the central city in Hokkaido with a population of about 1.96 million people. Roughly 13 million tourists a year from Japan and other countries visit us for our abundant nature and attractive cuisine. This city is promoting environmental policies on its “second basic environment plan” as a mean to achieve the SDGs and making connections with various bodies. Sustainable consumption activity by residents in an urban city as Sapporo, that consumes a large amount of resources and energy, is vital to achieving SDGs. We introduce the efforts for sustainable consumption of citizens in Sapporo city and trends for achieving SDGs in Japan.

A214 [Invited] Challenges of chemical engineering for SDGs
Masahiko HIRAO
The University of Tokyo, Tokyo 113-8656, Japan

The Asia-Pacific region is the cradle of production and the center stage of the world economy today. At the same time, the region is a flourishing arena of new socio-economic development driven by digital innovation. In light of these trends, it is necessary to examine and practice emerging opportunities for ensuring sustainable society, in which socioeconomic development and increases in environmental loads are decoupled from the real sense of securing people's well-being and happiness. Sustainability is not one-dimensional issue such as the prevention of global warming but is a multifaceted challenge, as the 2030 Agenda for Sustainable development indicates 17 goals and 169 targets in areas of People, Planet, Prosperity, Peace, and Partnership,
Chemical engineers have been responding to social demands by developing and implementing innovative technologies since chemical engineering inherently pursues a problem-oriented approach. However, we have to expand our focus from increasing the efficiency of existing products and systems to aiming at the well-being of society by improving people's sufficiency in the SDGs era. For this purpose, the Society of Chemical Engineers, Japan launched many activities to extend chemical engineer's scope from efficiency to sufficiency: a study group on diversifying technology implementation, the Committee on Future Energy and Social Systems, the Gender Equality Committee and the SDGs Committee, and so forth. Likewise, APCChE can be a good place in the Asia-Pacific region to achieve Goal 17 “Strengthen the means of implementation and revitalize the Global Partnership for Sustainable Development.”
By integrating these activities, we will be able to live up to paragraph 67 of the 2030 Agenda that states “We call upon all businesses to apply their creativity and innovation to solving sustainable development challenges.”

PA201 Life cycle assessment of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) characterized by bio-based content and biodegradability
Tomoki YAMANISHI1, Eri AMASAWA1, Jun NAKATANI1, Masahiko HIRAO1, Shunsuke SATO2
1 The University of Tokyo, Tokyo, Japan
2 Kaneka Corporation, Takasago, Japan

In this work, we performed a life cycle assessment of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH), which is made from biomass resources and has a characteristic of biodegradability in both soil and seawater. To reduce the dependency on petroleum resources and decrease marine plastics, increasing attention has been paid to bio-based and biodegradable polymers. Until now, many papers about the environmental impacts of these biopolymers have been reported. However, the environmental impact of a biodegradable polymer that dissolves in an aquatic environment has not been clearly investigated yet. To discuss the effect of bio-plastics introduction to the society, it is necessary to elucidate its impacts through its entire life cycle.
We applied a life cycle assessment to PHBH products from the cultivation of biomass resource to the end-of-life, and we considered their environmental benefit to the society. The selected target is PHBH products and comparable conventional plastic products with the same function. Their resource extraction, production processes and end-of-life are different from each other. Unlike the fossil-derived plastics, PHBH is biologically synthesized from plant oil and refined for pellets. We set a system boundary including biomass cultivation, microorganism fermentation, polymer extraction, product manufacture, use and end-of-life. The end-of-life was generated as several scenarios such as incineration, landfilling, recycling and dumping depending on local waste systems and consumer behaviors. To construct the inventory data, we investigated the actual production processes in Japan. Finally, we targeted global warming for the impact category to discuss whether PHBH can become a possible measure for climate change.
Through the assessments, we will discuss which process within life cycle has a significant environmental impact and which end-of-life scenario can contribute to reducing greenhouse gas emission. Our results will help design and construct a better social system for biopolymers and provide deep insights for utilizing PHBH.

PA202 Life cycle cost analysis of cooling of apartment building by stored snow
Yamagata University, Yonezawa, Japan

Promotion of cooling of building by snow is important in regions with heavy snowfall in terms of not only energy saving for cooling in summer, but also workload reduction of snow removal in winter because most of these regions in Japan now fases decrease of labor population. In the present study, life cycle cost (LCC) of cooling of apartment building by snow was calculated for three types of snow strage: open-air snow mound, half-underground storage, aboveground strage. Initial amount of snow storage, cooling area per household and annual cooling time were 100 t, 80 m2, 502 h, respectively. Number of households which shared the cooling energy from snow was modified from 1 to 20. Each household had 4 rooms with equivalent area. In case the amount of snow was not sufficient for cooling during the season, some of the rooms were cooled by electric air-conditioner.
Annually averaged value of the LCC (ALCC) per household showed convex dependence on number of households sharing the snow strage and there were optimum number of the households which minimized the ALCC. Snow strage of half-underground type and aboveground type had disadvantage especially smaller number of households because of high cost of construction.
Cost reduction potential in snow removal by the snow strage was also calculated. It was estimated as 160,000 Yen for 10 households for 40 years of operation period as shown in Fig. 1. It was mainly attributed to reduction of transportation of snow to dumping site.

PA203 Effectiveness of internship at international organizations for developing human resources contributing to the Sustainable Development Goals
Mitsuo YAMAMOTO1, Shingo KIMURA2
1 The University of Tokyo, Tokyo, Japan
2 The University of Tokyo, Chiba, Japan

Developing international human resources that possess a high level of expertise in many fields including chemical engineering and that show leadership at the global stage is important for establishing a sustainable society and achieving the Sustainable Development Goals (SDGs). The University of Tokyo Ocean Alliance conducts educational initiatives for fostering individuals who can succeed worldwide in ocean related areas. We started an overseas internship project from the 2014 academic year (AY 2014) and built collaborative relationships among nine international organizations and research institutions, such as the United Nations Industrial Development Organization (UNIDO), the Food and Agriculture Organization of the United Nations (FAO) and the International Atomic Energy Agency (IAEA). In particular, we have a strong relationship with UNIDO. Forty five graduate students have been sent to these international organizations from AY 2014 to AY 2018 (Table 1), and have undergone internships for two to six months. They could engage in actual projects related to their own research fields including environmental and energy issues. The objective of this study is to investigate the effectiveness of the internship at the international organizations mainly by analyzing students' internship reports. Their impressions for internship were classified into three categories. The first one is the description related to students' future and their career paths, the second one is the influence of internship on their master and doctor researches, and the third one is related to the construction of human networks and all the rest of it. The analyses of the reports for five years show that the internship was considered to be effective in establishing students' career paths through work experiences and formation of interpersonal relationships in the international organizations. It is expected that this internship system can contribute to achieving the SDGs in the long term.

Session S2. SDGs forum (Invited talks only. Open to the public)

A501 Sumitomo Chemical's challenge for sustainability ~Sumika Sustainable Solutions&sim~
Sumitomo Chemical Co., Ltd.
A502 The challenge of bioenergy in Indonesia for SDGs
Eniya Listiani Dewi
Technology of Information, Energy and Material- BPPT
A503 SDGs and Science Council of Japan
Science Council of Japan / Japan Science and Technology Agency
A504 AIChE and sustainability education
Kimberly OGDEN
American Institute of Chemical Engineers(AIChE) / The University of Arizona
A505 Report from Student program: —Research proposal for SDGs from youth—
Keio University
A506 Report from APCChE–UNIDO special symposium
Suguru NODA
Waseda University
A507 Report from Diversity in chemical engineering
The University of Tokyo
A508 Report from East Asian joint session: Critical SDGs in highly industrialized economies
Tohoku University
A509 [Plenary] Chemical engineering for SDGs
Tohoku University, Sendai, Miyagi 980-8577, Japan

Session S3. East Asian joint session: Critical SDGs in highly industrialized economies

Sustainable Circular Economy
L401 [Keynote] Taking the East Asian Chemical Industry into the circular economy
Department of Chemical Engineering, National Central University

The last few years have been quite challenging for the chemical industry in Asia. Vibration of oil prices, regulatory pressures, global climate plans and competition, and changing demographics have a huge impact on chemical industry. In the last years chemical industry companies are working on two major production concepts to further improve their production of chemicals, materials or bio-technology products: cyclic economy and modularized production. The general goal of these activities is to produce faster, with a higher quality and in a less wasteful manner. The chemical industry is facing an increasing demand from fast growing and vibrant markets in Asia and a trend to customized specialty and fine chemicals. Asian chemical companies face different challenge from those in US, Europe and Middle East, such as energy-deficiency, high cost of energy and raw materials, strengthening environmental regulations, increasing labor-cost, etc.
The circular economy in developing countries can increase productivity and economic growth, improving the quality and quantity of employment, and save lives, by reducing environmental impacts such as water and air pollution. For most Asian countries there is huge potential to improve productivity by using resources more efficiently. However, many chemical plants in East Asia are old and need renovate to achieve new standard. With efficient technologies, there are huge business opportunities for companies.

L404 Devising a circular economy strategy with bottom-up modeling: a lithium-ion battery example
I-Ching CHEN1, Hajime OHNO1, Chiharu TOKORO2, Yasuhiro FUKUSHIMA1
1 Tohoku University, Sendai, Japan
2 Waseda University, Tokyo, Japan

The demand for lithium-ion batteries (LIBs) is expected to increase dramatically in the next decades because of the growing EV market. As a result, a large volume of batteries will reach their end-of-primary-life in the near future. However, the spent battery may still retain their capacity, which could be serviceable in its second-life, e.g. for the stationary energy system, or remanufactured to be used again in EVs. The LIB supply chain might benefit from reducing raw material consumption, if LIBs are reused through refurbishing, remanufacturing, or recycled. The reuse and recycle of LIB will also facilitate waste management by the recovery of all valued battery components to contribute to a circular economy. To devise a circular economy strategy for the LIB system, the material flows and the environmental impacts associated with their life cycle including manufacturing, use, and end-of-life phases should be assessed. Although numerous studies on the environmental impact of LIB production are available, the existing primary life cycle inventory data is often difficult to trace back, which is inflexible to discuss the different properties of LIB and energy demand related to the manufacturing process. The different LIB chemistries that have different combinations of metals, will make the material and energy consumption in production process vary. In this study, a bottom-up inventory model of LIB production, which enables to estimate the material requirements, energy demands and the associated environmental impacts such as greenhouse gas (GHG) emission, is developed. Here, we demonstrate that with this modeling approach, it becomes possible to assist devising a circular economy strategy from environmental impact perspective, reflecting envisioned future circumstances e.g. decarbonization of electricity generation, by coupling with a material flow analysis model.

L405 Production of glycerol carbonate from transesterification of glycerol and dimethyl carbonate over MgO@ZIF-8
Zi-Jie GONG1,2, Cheng-Wei CHANG3, Nai-Chieh HUANG1,2, Cheng-Yu WANG3, Wen-Yueh YU1,2
1 Department of Chemical Engineering, National Taiwan University, Taipei, Taiwan
2 Advanced Research Center for Green Materials Science and Technology, Taipei, Taiwan
3 Department of Materials Science and Engineering, National Chiao Tung University, Hsinchu, Taiwan

MgO@ZIF-8 catalysts with various MgO loadings (10-50 wt%) were prepared through a wet-impregnation and calcination process. The physicochemical properties of MgO@ZIF-8 catalysts were characterized using atomic absorption spectroscopy, X-ray diffraction, , nitrogen sorption isotherms, field-emission transmission electron microscopy, and thermogravimetric analysis. It is found that MgO nanoparticles could deposit onto the ZIF-8 surface with high atom efficiency and little influence on the ZIF-8 structure. It is suggested that the surface sites and microporosity of ZIF-8 support facilitate the deposition of Mg precursor and subsequent formation of MgO nanoparticles. MgO@ZIF-8 catalysts were tested for catalytic transesterification of glycerol and dimethyl carbonate. It is found that the 50 wt% MgO@ZIF-8 catalyst display an improved catalytic activity on glycerol carbonate production than those of MgO and ZIF-8. Furthermore, the MgO@ZIF-8 catalysts showed higher catalytic activities than their physically-mixed counterparts. These results suggest a synergistic effect between MgO and ZIF-8, which is explained by an acid-base bifunctional catalysis mechanism.

Utilization of locally available resources
L413 Chemical systems synthesis with a rank-ordered optimization approach
Tohoku University, Sendai, Japan

Inclusivity is a vital aspect of sustainable development which has been emerging as a challenge in economically developed, matured societies. In Japan, the rural areas are suffering from lagged economic development, the aging society, and declining population. Tackling sustainability challenges without leaving out problems in these areas are essential, but requires a new approach in industrial development. Creating sufficiently productive and profitable systems that utilize locally-available resources are seen as a potential key to vitalize the rural areas while tackling the SGDs.
Attempts to collect and study all the relevant information can lead to an excessive requirement on time and effort in the early stages of a design project. Because some of the unknowns are more important than others, prioritization of the unknown factors that requires a closer investigation can potentially reduce the time and cost for the initial design. In this study, a system synthesis method that generates combinations of resources, technology, and products, ranked in order, formulated as a MILP is applied to indirectly prioritize the unknowns, while comprehensively exploring the combinations of the known options.
The higher ranked systems will include some designs that are impractical due to missing practical constraints. The ranked list of the systems will help to identify overlooked constraints, starting from more important ones. The unknowns that are related to the identified constraints are then studied and added in the systems synthesis model. After several iterations, all the critical unknowns are studied to describe the key constraints and the most promising systems can be proposed.
Features added to existing studies, i.e., 1) consideration of the combinations at its suboptimal capacity of processing, 2) incorporation of material storage equipment and efficiency in order to overcome the seasonal variations in availability of resources and the demand of products, will be introduced with simple examples.

L414 Conversion of woody biomass into MTHF (methyltetrahydrofuran) using chemical, thermal, and catalytic (CTC) conversion
Tae Hyun KIM1, Jun Seok KIM2, Jeong Gil SEO3, Yang Soo LEE4
1 Hanyang University, Ansan, Gyeonggi-do 15588, Republic of Korea
2 Kyonggi University, Suwon, Gyeonggi-do 16227, Republic of Korea
3 Myungji University, Yongin, Gyeonggi-do 17058, Republic of Korea
4 Samwon Industrial Co., Ltd., Ansan, Gyeonggi-do, 15612, Republic of Korea

Methyltetrahydrofuran (MTHF) have received great attention for combustion system applications, because it can be readily used in blends with gasoline and diesel without major engine modifications. In this study, as a sustainable platform chemical for the biofuels and biochemicals, conversion of MTHF from lignocellulosic biomass was studied. For the conversion of MTHF, domestic grown woody biomass such as pine and oak in Korea were firstly treated by chemical and thermal treatment for the production of C6 substrate and further production of levulinic acid (LA) via 5-hydroxymethylfurfural (HMF) intermediate, which was then subjected to the catalytic conversion for the conversion of MTHF.
At the beginning of the conversion process, alkaline reagents (ex. sodium hydroxide and ammonium hydroxide) were applied to produce C6-rich substrate (>70%), which was then converted by de-hydration and re-hydration reactions into LA using sulfuric acid (1~5 wt%) at high temperature (121~190 °C). For the conversion of MTHF via gamma-valero lactone (GVL) intermediate using de-hydration and hydrogenation reactions under high temperature and pressure conditions, high-efficiency heterogeneous bimetal catalyst was synthesized and attempted for precious metal replacement in the presence of the effective CTH (catalytic transfer hydrogenation) solutions.
In this paper, conversion yields of C6, LA, and MTHF were evaluated and reported under various reaction conditions. For the increased MTHF production, various catalytic reaction conditions pertinent to effective and viable process were explored and discussed.

L415 Demonstration the large-scaled (0.1 ton/d) continuous twin screw-driven reactor (CTSR) for thermo-mechanical biomass pretreatment
Hun Jin RYU1, Kyeong Keun OH1,2
1 SugarEn Co., Ltd., Yongin, Gyeonggi-do, 16890, Republic of Korea
2 Dankook University, Youngin, Gyeonggi-do, 16890, Republic of Korea

A continuous twin screw-driven reactor (CTSR) can provide a unique and efficient reaction environment for the pretreatment of lignocellulosic biomass. CTSR has the ability to provide high shear, rapid heat transfer, effective mixing. The thermo-mechanical energy provided by the continuously stirred screws in CTSR, which causes the shear forces, can be applied to the continuous pulverization of biomass, thus improving the overall rate of biomass conversion. Considering the high labor intensity and energy requirement of batch pretreatment, a CTSR process has great potential for increasing the efficiency of biomass pretreatment.
CTSR for the pretreatment of biomass would be practicable and useful for large scale production because it affords high-efficiency pulverization by a high shearing force, and adaptability to many different process modifications, such as application of simultaneous physical and chemical treatments using other catalysts. The performance of biomass pretreatment through CTSR is a complex function of screw rotational speed, throughput, and screw configuration etc. The interaction between different processing parameters leads to complex functions of shear conditions and reaction severities, both of which affect pretreatment performance.
With the aim to provide a further insight into CTSR pretreatment, enlarged CTSR to 100 kg/day scaled was developed and demonstrated. Mathematical modelling for fluid dynamics and heat transfer were developed by a set of ordinary differential equations (ODE) based on first-principle models. The resulting ODE set was experimentally validated using model biomass (sawdust) as feedstock. The kinetic parameters of biomass pretreatment performance were estimated from experimental results.
These results will contribute to improved reactor design and scale-up tasks, and in turn, to the successful deployment of novel industrial-scale technologies for biomass pretreatment.

L416 Planning support of biomass-based industrial symbiosis toward sustainable agriculture and forestry
Yuichiro KANEMATSU, Tatsuya OKUBO, Yasunori KIKUCHI
The University of Tokyo, Tokyo, Japan

Industrial symbiosis with unused local biomass can be one of a key approach from the viewpoint of sustainability of agriculture, forestry and the regions. Planning biomass-based industrial symbiosis necessitates hard decisions including long-term visioning of the regions and consensus building among various stakeholders such as agriculture, forestry, energy supplier, local government, and technology researchers. Chemical engineering approach with modeling and simulation can strongly support such planning process. The planning process of the symbiosis to be supported has not been well established nor systematized in previous studies. In this study, systematic planning process for biomass-based industrial symbiosis was proposed and the requirements of its supporting mechanisms were defined. The planning process was structured as the series of sub-activities based on the re-analysis of the case studies for planning industrial symbiosis integrating cane sugar industry and local forestry on a specific region. Modeling and simulation of regional energy systems with multiple co-generation plants fueled by local biomass from the industries were performed in the case studies. The planning process was defined that consists of the activities of planning tasks, i.e., <Examine present system>, <Generate alternatives>, <Simulate flows> and <Evaluate>. Additionally, these tasks are controlled by <Manage>, and the proposal of the symbiosis plan as the product by the tasks are checked by <Review>. These activities of planning tasks can be supported by the mechanisms, such as IoT monitoring system, technology matching tool, flow simulator and evaluation tool. The applicability of the planning process and the supporting mechanisms is to be discussed through new case studies in other regions. Human networks among region, academia and industries have significant roles to implement the symbiosis plans toward the regional sustainable visions even if the supporting tools highly developed in future.

Sufficiently low carbon and clean energy
L417 [Keynote] Multi-criteria technology roadmapping towards sustainable energy use: The case of photovoltaics
Hajime OHNO
Tohoku University

To effectively mobilize the limited time and resources for the accomplishment of a transition towards sustainability, efforts on a technology development must be made in a manner coherent with other efforts under a vision on the sustainable society. Technology Roadmapping (TR) is amongst the several approaches that may cross-link a technology development with a future vision. Here, I provide an example of assisting TR by exploring the balances between technology performances with other exogenous variables in the future society with a dynamic Material Flow Analysis (dMFA).
In Japan, a future target of the power supply configuration (energy mix) based on the massive introduction of renewable energy has been advocated, in which Photovoltaics (PV) accounts for ~7% of the total power generation capacity, i.e., approximately 30% of the renewable power sources. On the other hand, a substantial amount of Si type PV (Si-PV) would reach their End of Life (EoL) soon. Therefore, the development of a technology recovering Si from EoL Si-PV may effectively respond to the demand to achieve the target without spending a massive amount of energy for Si purification from Silica sand. To consider such technology, a long-term evaluation of benefits and impacts on both economy and environment is required to invite stakeholders to jointly materialize the reasonable and comprehensive roadmap. Here, our team conducted a time series quantification of flows and stocks in an envisioned Si-circulation system. Then, we deduce the development directions as a roadmap with respect to various design variables (ex. an average lifetime of product) on the basis of multiple criteria (e.g., the net-energy acquisition and net-CO2 avoidance). With this example, I aim to highlight the potentials and challenges of vision-oriented technology development for the achievement of SDGs 9: Industry, Innovations and Infrastructure and SDGs 7: Affordable and Clean Energy.

L421 Optimization of hydrogen supply chain: From production to distribution
Chul-Jin LEE
Chung-Ang University

A hydrogen supply chain consists of the production, transportation, storage, and distribution of hydrogen as an energy source. A variety of decision variables should be determined along the supply chain including technological options of producing hydrogen, phase of hydrogen, location and capacity of treating facility, and the amount of transportation between the regions. The optimization problem can be effectively formulated and solved for this complex systems. In this presentation, we have investigated for the optimal strategy for hydrogen supply chain and present the optimal solution to the case of South Korea.

L422 Improving solar-to-fuel conversion of CuInS2 thin film electrode
Bo-Cheng CHEN1, Kai-Yu YANG1, Meng-Chi LI2, Cheng-Chung LEE2, Cheng-Liang LIU1, Tai-Chou LEE1
1 Department of Chemical and Materials Engineering, National Central University, Taoyuan, Taiwan
2 Thin Film Technology Center / Department of Optics and Photons, National Central University, Taoyuan, Taiwan

CuInS2 (CIS) is a solar absorber with the energy band gap of 1.5 eV, suitable for hydrogen production from water splitting. The types of conductivity (n- or p-type) of CIS photoelectrode can be tuned as a function of Cu/In concentration ratio. In this report, CIS films were deposited using spray deposition onto ITO-coated glass substrates from aqueous solutions consisted of copper (II) chloride, indium chloride and thiourea. First, the ratios of the precursor solutions were varied and the transition from n- to p-type conductivity was observed. Next, Zn-doped CuInS2 (Zn-CIS) thin films exhibited p-type conductivity from electrochemical measurements. XRD results reveal the cubic-structured Zn-CIS films. The successive shift of XRD patterns toward higher angles with zinc molar fraction is evident of the formation of Cu-In-Zn-S solid solution. LSV results shows that the photocurrent density of Zn-CIS film reached 2.5 mA/cm2, higher than the bare CIS (0.3 mA/cm2). Finally, n-type ITO thin film was deposited onto the p-type CIS. Here, we want to demonstrate that suitable match of the p-n junction can create a high efficient photoelectrode for hydrogen production from water.

L423 General techno-economic analysis for electrochemical coproduction of CO2 reduction and anodic oxidation
Jonggeol NA1, Bora SEO1, Jeongnam KIM1,2, Hyung-Suk OH1, Ung LEE1
1 Clean Energy Research Center, Korea Institute of Science and Technology, Republic of Korea
2 Chemical and Biological Engineering, Seoul National University, Republic of Korea

The electrochemical reduction of CO2 recently draws great attention because of its sustainable capability of producing fuels and chemicals. However, the high over potential of CO2 reduction reaction-oxygen evolution reaction (CO2RR-OER) have been pointed out as an obstacle of commercialization. Herein, we propose electrochemical co-production of CO2RR and oxidative reforming of organic materials. The oxidative reforming of organic materials not only potentially reduces operating cell voltages but also improves system economic feasibility by producing more valuable chemicals than oxygen. We introduces an automated and generalized platform for the techno- economic alanysis (TEA) of electrochemical coproduction system and investigate the 16 candidates of CO2RR for cathode and 18 candidates of organic oxidation reaction for anode. The TES platform generates a product oriented process systems design including reaction, separation, and recycle. Global sensitivity analysis of Faraday efficiency, current density, and overpotential for the levelized cost of each product to understand which index should be improved first. Hydrogen, carbon monoxide, formic acid, glycoladehyde, ally alcohol, ethylene glycol, acetic acid, and propanol can be the promising candidate for the CO2RR and 2,5-Furandicarboxylic acid (FDCA), oxalic acid, acrylic acid, glycolic acid, lactic acid, 2-furoic acid, and ethyl acetate can be the promising candidate for the anodic oxidation.

Session S4+S5. Bioseparations and bionanotechnology & Next generation downstream processing of biologics

B126 Continuous downstream processing R&D in Europe
University of Natural Resources and Life Sciences, Vienna
B128 Continuous downstream processing R&D in Japan
Yamaguchi University, Ube

Session S4. SCEJ–AIChE joint session: Bioseparations and bionanotechnology

F201 [Keynote] The study of surface chemistry to enhance viral bioprocessing
Caryn L. HELDT, Xue MI, Pratik U. JOSHI, Seth KRIZ, Emily BROMLEY
Michigan Technological University, USA

Virus surface chemistry plays a key role in virus sorption and partitioning processes, however there is very limited information on viral surface chemical properties. To enhance the toolbox of available characterization tools, chemical force microscopy (CFM) is being pioneered for viral particle characterization. CFM measures the adhesion force between a particle, in this case a virus particle, and a functionalized atomic force microscopy (AFM) tip. CFM reduces many of the difficulties of bulk characterization techniques by measuring adhesion of individual virus particles, likely reducing purification affects that can change surface properties. Two important surface characteristic that can dominate separation processes are isoelectric point (pI) and hydrophobicity. The surface charge of virus particles is pH dependent, which dictates the mobility and controls the colloidal behavior in virus sorption processes. While traditional characterization methods, including zeta potential and viral adsorption to a charged surface chemistry, have been used to study viral surface charges and determine the pI of virus, they are bulk measurements that can change when the studied particle has a different purification method. Hydrophobic interactions are known to be strong for virus particles and are implicated to be important in virus entry into cells. The single particle method of CFM allows not only the quantitation of the virus surface chemistry, but could be used to understand and better design purification processes. The adhesion of a viral particle to any chemical moiety in any solution condition can be tested with this method. The model non-enveloped porcine parvovirus (PPV) and enveloped bovine viral diarrhea virus (BVDV) were used to demonstrate the use of CFM to determine the hydrophobicity and pI for viral particles. This information is being used to determine the binding and elution conditions of a virus to a chromatographic column. With a thorough understanding of virus surface characteristics, virus sorption and desorption processes could be significantly improved and designed to specifically target viral particles using minimal viral material during development.

F203 [Keynote] Rapid development of orthogonal, integrated downstream bioprocesses
Rensselaer Polytechnic Institute, Troy, NY

Designing integrated non-affinity downstream processes for biologics poses a significant challenge due to the broad range of design space available for resin selection and buffer conditions. To address this challenge, we developed an in silico-based approach to quickly design and rank a fully inclusive list of integrated downstream processes for their ability to remove impurities using only orthogonally selective multimodal and ion exchange resins. This approach involves the one-time characterization of an impurity database and considers both impurity profiles patterns and product retention behavior to generate and score all possible integrated purification trains. This database was then employed in concert with an in silico process development tool which generates and ranks all possible integrated chromatographic sequences for their ability to remove orthogonal impurities. Top-ranking outputs are then used to guide the experimental development and refinement of purification processes, significantly expediting the development of downstream processes. For Pichia pastoris, this approach was used for two non-mAb products, hGH and G-CSF, which were successfully purified from cell culture fluid process impurities in a process that resulted in high purity and product recovery. We also performed modifications to our process design approach in order to account for both process-related impurities and product-related impurities. This modified strategy was first shown to be successful for purifying IFN produced in Pichia pastoris, and was then applied to the non-affinity-based purification of a mAb-aggregate challenge in CHO, an expression system with a much higher HCP burden. Finally, results are presented on a mathematical framework to characterize and quantify orthogonality in multimodal systems. Using this, we observed several interesting and unexpected results including the existence of a highly orthogonal pair of resins belonging to the same class/family.

F205 Chromatographic Behavior of Bivalent Bispecific Antibodies
Giorgio CARTA
Department of Chemical Engineering, University of Virginia, Charlottesville, Virginia, USA

Bivalent bispecific antibodies (BiS) are produced by recombinantly expressing a whole monoclonal antibody (mAb) with two single chain variable fragments (scFv) using flexible polypeptide linkers. Three homologous BiS samples varying only by scFv attachment location show reversible, three-peak elution profiles on ProPac WCX-10 and Source 15S cation exchange columns. Collection and reinjection of any of the three peaks results in the same three-peak elution profile. This behavior is seen at pH values in the range 5–8.5. In-line DLS showed that all peaks have a monomer-sized hydrodynamic radius of 6.2 nm. Unlike the normal chromatographic behavior, decreasing flow rate decreased resolution. At the lowest flow rate tested, only a single symmetric peak was observed eluting between the first and second peak of the higher flow rate elution profiles. A hold step at strong binding conditions followed by gradient elution with high flow rate enriched the third, most retained, peak. Biophysical measurements including in-line fluorescence, chemical cross-linking, enzyme digestion to determine domain contributions, and a mechanistic model reveals that the three-peak elution is caused by conformational interconversion occurring on time sales comparable with chromatographic separation. From the peptide sequence, the scFvs carry a net positive charge. When the scFv is folded onto the base mAb weaker bind to the resin occurs whereas if the scFv is outstretched more favorable interaction and stronger binding occurs on the resin surface. The three peaks from weakest to strongest retention are: both scFvs interacting with base mAb, one scFv interacting with base mAb and one outstretched, and both scFvs outstretched. Equilibrium favors the tight conformation in solution and outstretched while adsorbed. The highly flexible linkers allow slow changes in tertiary structure responsible for reversible, three-peak elution behavior. Analogous results are observed on HIC columns suggesting that similar molecular interactions are responsible for the multi-peak elution behavior.

F206 Affinity separation of exosomal vesicles utilizing TIM-immobilized solid supports
Kyoto Institute of Technology, Kyoto, Japan

Recently, exosomal vesicles are known as a next generation of biomarkers for molecular diagnosis, and their separation methods has been studied last decades. T-cell Immunoglobulin and Mucin domain (TIM) which is Ca-dependent membrane protein has an ability to interact phosphatidyl serine (PS) clusters on inner cell membrane, and thus it is considered that TIM fragment is one of ligand candidates to separate exosomal vesicles from serum as well as culture supernatant. Also, Exosome can be released from the resin.
Here, we designed and characterized TIM fragments genetically-fused with Avi-tag and PMMA-tag for site-direct immobilization to solid supports.
Avi-tag-fused TIM fragments were successfully produced by HEK293T cells with co-expression with Biotin ligase BirA. Consequently, site-specific biotinylation at the C-terminal region of TIM fragments could be achieved. Mono-biotinylated TIM fragment (ABT-TIM-VM) could be immobilized on the surface of streptavidin-coated plate, and could recover 10-times lower concentration of exosomes, compared with the plate with randomly-biotinylated TIM (RBT-TIM-VM). These results indicated that orientation control of TIM on the surface of solid support is more important to improve recovery of exosomes. Furthermore, biotinylation yields of ABT-TIM-VM could be controllable by changing the ratio of expression vectors for TIM and BirA.
Another candidate, PMMA-tag was introduced at the C-terminal region of TIM fragments. TIM-VM-PM could also be produced by 293T cells, and purified by Ni-NTA chromatography. The optimal buffer condition for TIM-VM-PM was screened from 96 conditions with different pH and NaCl concentrations. Consequently, 25-times higher signal intensity of sandwich ELISA for detection of exosome was detected, compared with the plate with tagless TIM-VM. These results indicated that PMMA-tag introduced was functional and preferentially adsorbed the surface of PMMA plate.
Thus, both TIM fragments developed in this study, namely, ABT-TIM-VM and TIM-VM-PM are useful ligand proteins to separate exosomal vesicles from biological samples.

PF201 Developments of new DNA oligonucleotides with site-specific methyl-phosphotriester linkages for molecular detections and precision medicine
Wen-Yih CHEN*, Meng-Wei WU, Chih-Chin TSAI, Tsai-Ling LI, Yu-Hsuan CHANG, Wei-Chen LIN, Wei-Cheng CHOU
Department of Chemical and Materials Engineering, National Central University, Taoyuan City, TAIWAN

The synthetic DNA containing modified nucleotides comprise a powerful toolbox of manipulating the formation of nucleic acid duplexes for diagnosis and therapeutic purposes. We are interested in the DNA oligonucleotides containing site-specific neutral internucleoside methyl phosphotriester (MPTE) linkages, nDNA in short (n for neutral). nDNA is interesting because the electrostatic repulsion between nDNA and its complementary strand would decrease and the duplex formation could be enhanced. However, the methyl group of MPTEs may sterically hinder duplex formation and destabilize the duplexes. Therefore, the uses of nDNA may offer additional elements of maneuvering the stability of nucleic acid duplexes formation. The structural information and hybridization thermodynamics were reported in this study. Based on the structural and thermodynamics information of nDNA with natural DNA, successful results in the molecular detection method such as PCR and qPCR will be reported. The applications of nDNA on the in-situ hybridization will be discussed as well. Most importantly, using nDNA on the semi-conductor based biochip and biosensor, such as field effect transistor, has generated wide avenue for the precision medicine, which also will be highlighted in this report.
Keywords: methyl-phosphotriester linkage of DNA (nDNA); molecular detections; PCR and qPCR; In-situ hybridization; field effect transistor

Session S5. SCEJ–ESBES joint session: Next generation downstream processing of biologics

F213 Chromatography beads, monoliths, or membrane adsorbers or continuous ultracentrifuges for purification of enveloped virus-like particles and gene-therapy vehicles
1 University of Natural Resources and Life Sciences, Vienna, Austria
2 Austrian Centre of Industrial Biotechnology, Vienna, Austria

The challenge for applications of viruses, virus-like particles, or other extra cellular bionanoparticles in gene-therapy or in cancer therapy is the high dose with up to 1014 particles per dose. Downstream processing is one bottleneck in the production of these bionanoparticles. It has been often overlooked that a heterogenous population of bionanoparticles is present and they must be separated from the product. The heterogeneous populations of bionanoparticles are released from the cells, carrying different host cell proteins, DNA and RNA fragments. Additionally, cells produce extracellular vesicles (microvesicles and exosomes) with similar size and surface properties. The biological activity of these different particle populations is not fully understood. Particle characterization and biological activity assays require the separation of these populations with high purity. Here we compare the results obtained for the purification, as well as particle populations' separation, of HIV-1 gag VLPs produced in CHO cell culture using different downstream processing approaches. These approaches include polymer grafted anion exchangers, monoliths (anion exchange and hydrophobic interaction), a combination of flow-through and heparin affinity chromatography, and membrane adsorbers. Several analytical tools including Nanoparticle Tracking Analysis and Mass Spectrometry were used for VLP characterization. An outlook will be given how continuous ultracentrifuges will complement these purification approaches.

F214 Analysis of PEGylated DNAs Retention in Electrostatic Interaction Chromatography
Noriko YOSHIMOTO, Yoshiatsu ONO, Shuichi YAMAMOTO
Yamaguchi University, Ube, Japan

PEGylation is a well-known technique to develop biopharmaceuticals, such as proteins and DNAs. It can increase the hydrodynamic radius to reduce their kidney excretion and prolong their in vivo half-life. On the other hand, the control of PEGylation reaction is difficult because of the formation of heterogeneous mixtures of target PEGylated product, its isomers, unreacted proteins and PEG reagents. As the differences in the sizes and the surface properties such as charge and hydrophobicity of the isomers are sometimes small, several purification steps are always combined to obtain the target product from the reaction mixture. Among the purification method, ion exchange chromatography has an advantage for the separation of isomers on the basis of their difference in size and charge with a single operation. However the separation mechanism is not fully understood. In this study, synthetic PEGylated DNAs were used as a model of well-defined structure isomers to investigate the charge shielding effect of PEG on the charged biomolecules. Poly T possessing 9 to 95 thymine bases, an amine group for conjugation and middle base was reacted with NHS-activated PEG reagents. The retention factors on anionic exchange chromatography, Q sepharose HP and QA monolith, were determined by liner salt gradient experiment. Elution salt concentration of PEGylated DNA was decreased depending on the molecular weight of PEG. However, the decrease was not pronounced when the number of bases increased. On the other hand, the number of binding site was practically unaffected by the PEGylation which means that the conjugated PEG chain did not disturb the interaction of DNA with cationic ligand while the interaction was weakened by the conjugated chain.

F215 Protein A Affinity Chromatography: Mass transfer enhancement upon alkaline treatment
Rainer HAHN, Desiree Womser, Andreas DAXBACHER
Department of Biotechnology, BOKU Vienna; Vienna, Austria

Protein A affinity chromatography is still the preferred option for antibody capture. In the past years, significant improvements have been made with respect to alkaline stability of the recombinant Protein A ligands, with resistance to 1 M NaOH over extended time periods as the latest milestone. We have investigated how exposure to alkaline conditions can alter antibody binding kinetics of Protein A resins. Break-through curves of fresh resins and resins after different time periods of alkaline exposure were compared using mAb and polyclonal IgG. As expected, equilibrium binding capacity dropped to some degree at long incubation times. In contrast, mass transfer of IgG was enhanced which was reflected by steeper break-through curves. Fitting of the break-through profiles with a pore diffusion model revealed effective pore diffusion coefficients which were increased by a factor of 2-3. Adsorption isotherm measurements showed that even after alkaline exposure, typical highly favorable isotherms were obtained, albeit with association constants that were reduced to some extent. Based on these altered binding properties we could identify a narrow window of specific operating conditions, where the alkaline treatment eventually led to an increase of the dynamic binding capacity. These conditions varied for different resins and strongly depended on the NaOH concentration and incubation time. Confocal laser scanning microscopy measurement showed that the accelerated mass transfer involved a transition from a shrinking core behavior with sharp fronts to a situation with more diffuse profiles typical for solid diffusion or pore diffusion with lower binding strength. Linear pH gradient elution studies showed that the desorption behavior was not changed significantly, as pH values at the peak maximum were almost the same as for fresh resin. The results of this study will contribute to a deeper understanding of phenomena associated with performance change of affinity media upon alkaline regeneration.

F216 Highly efficient purification of lysozyme from chicken egg white by dyed nanofiber membrane chromatography
Yu-Han LEE, Yu-Kaung CHANG
Department of Chemical Engineering, Graduate School of Biochemical Engineering, Ming Chi University of Technology, New Taipei City, Taiwan

Polyacrylonitrile (PAN) nanofibrous membrane was prepared by electro-spinning technique. After heat treatment, alkaline hydrolysis and neutralization reaction, the ion exchange membrane (namely P-COOH) was further chemically grafted with chitosan molecule. The obtained P-Chitosan membrane (namely P-CS) was then covalently immobilized with Procion orange MX-2R dye from simulated textile wastewater to be used as a dye-ligand membrane. Fiber diameter, porosity, pore size, immobilized dye-ligand concentration, and protein binding capacity were characterized. Furthermore, the membrane was applied to evaluate the binding capacity of lysozyme under various operating parameters (e.g., pH, chitosan mass per volume ratio, immobilized dye concentration, ionic strength, and temperature) in batch mode. The experimental results were directly applied to purify lysozyme from chicken egg white by newly designed membrane chromatography module. The results showed that the recovery yield and purification factor were 98.9 % and 56.9-fold, respectively, in a single step. The binding capacity remained consistent after five repeated cycles of adsorption-desorption operations. This work demonstrates that the dye-ligand nanofibrous membrane holds great potential for purification of lysozyme from real feedstock.

F217 Fractal dimension of antibody PEG-precipitate: An engineering parameter for comparison of batch and continuous operation.
Peter Satzer1,2, Daniel BURGSTALLER1, Walpurga Krepper1, Alois JUNGBAUER1,2
1 University of Natural Resources and Life Sciences, Vienna
2 Austrian Center of Industrial Biotechnology

Protein precipitation by polyethylenglycol is a simple, robust and cost effective first capture step for purification. The resulting structure of the precipitate particles has a significant impact on process design and process performance like recovery and dissolution kinetics. Current technologies for visualizing and reconstructing 3D precipitate structures are either very time consuming and expensive (Cryo-TEM) or generate a single average value (a fractal dimension) for a population of precipitate particles (light scattering). We developed a new method using light microscopy to reconstruct the complete three dimensional structure of individual precipitate particles with a resolution of 0.1-0.2 μm. This methods was then used to reconstruct and characterize the three-dimensional structure of particles generated by batch precipitation by PEG as well as continuous precipitation in different shear stress environments. Both methods, batch and continuous precipitation, generate particle structures of very diverse nature, while the average fractal dimension is significantly different between the two (2.40 for batch in low shear environment and 2.52 for continuous in high shear environment). Besides the overall average, when investigating both populations in detail, the distributions of fractal dimensions of individual particles overlap significantly. We could also confirm that the generation of PEG-precipitated particles is diffusion limited, as simulations predict a fractal dimension of 2.4 for diffusion limited precipitation and 1.7 for reaction limited precipitation. A close inspection of the 3D structure of the precipitate also shows monofractality of the particles from micro to nano scale visualized by light microscopy. We showed that the fractal dimension and 3D reconstruction is a valuable tool for characterization of different shear stress conditions and mode of operation. The current switch from batch manufacturing to continuous manufacturing has to take the 3D structure and population of different protein precipitates into account in their design, engineering and scale up.

F223 Chromatographic analysis of a Break-Through Curve on a Single Akta System
1 University of Ljubljana, Faculty of Chemistry and Chemical Technology, Večna pot 113, 1000 Ljubljana, Slovenia
2 Lek d.d., Technical Development Biologics Mengeš, Kolodvorska 27, 1234 Mengeš, Slovenia
3 COBIK, Tovarniška 26, 5270 Ajdovščina, Slovenia

A preparative high-performance liquid chromatography is an extensively used technique for a purification of commercially important bio macromolecules, such as proteins and polynucleotides. Since process time is becoming more and more critical, fast and effective chromatographic methods are widely required. In this context, target molecule breakthrough point determination is of a great interest for optimization of downstream processing. Ideally, continuous analysis is preferred, such as UV absorbance or fluorescence monitoring, which in some cases however lack sufficient selectivity. An alternative is to perform fast analysis of column outlet fraction via chromatography providing equal or greater selectivity than purification step. This can be done using UPLC that however requires specialized equipment. On the other hand, fast analysis of macromolecules can also be achieved using convective chromatographic media at much lower pressure drop. This opens possibility to combine purification step and chromatographic analytics on a single chromatographic system.
In our case we implemented äKTA Explorer system to test feasibility of proposed approach. On-line analysis of preparative column outflow was performed by sequentially injecting outlet on convection based analytical column operating on the same chromatographic system where target molecules were analyzed. Cationic and/or anionic exchangers were used as chromatographic supports (along with selective protein A membrane), depending on feed sample and its characteristics. Three different case studies were tested: monoclonal antibodies purification, aggregate content and plasmid DNA (pDNA). To adjust limit of detection an algorithm varying number of injections was used. This enabled accurate monitoring of an early breakthrough for concentration below 1%. Due to its simplicity and flexibility such methodology can easily be adopted also in pharmaceutical environments.

F224 Real-time monitoring and model-based prediction of purity and quantity during chromatographic purification of biopharmaceuticals
1 Austrian Centre of Industrial Biotechnology, Vienna, Austria
2 Institute for Applied statistics and computing, BOKU, Vienna, Austria
3 Boehringer Ingelheim, Vienna, Austria
4 Department of Biotechnology, BOKU, Vienna, Austria

To enhance product quality and process robustness in biomanuacturing regulatory agencies have encouraged the implementation of process analytical technology (PAT). This combination of process understanding and control with real-time monitoring of quality and performance attributes also increases process efficiency and productivity. Currently, process performance is monitored by laborious and time-delayed offline analysis after each process step. This conventional approach increases hold times and overall process duration as well as the risk for batch failure. We have equipped a commercial chromatographic workstation with additional online sensors based on multi-angle light scattering, refractive index, attenuated total reflection Fourier-transform infrared, and fluorescence spectroscopy. The combination of these derived online data enables the prediction of product quantity and various purity attributes such as high molecular weight impurities, HCP and dsDNA content simultaneously during the elution phase of a chromatographic purification step. Such predictive models based solely on online data have been established for capture, intermediate and polishing steps of a monoclonal antibody produced in CHO and for fibroblast growth factor 2 overexpressed in E. coli. Online signals and corresponding offline data for product quantity and co-eluting impurities were analyzed by the statistical tools partial least square regression and boosted structured additive regression. Also chromatographic runs with varied process parameters were conducted to determine the predictive power of the models. The established methodology using complimentary online sensors enables the prediction of product quality and process performance attributes simultaneously in biopharmaceutical purification processes within a feedback time below 5 sec. The application of such models allows online pooling decisions and decreases the number of off-line analysis and hold times significantly. The costs for in-process analytics are lowered and the risk for batch failure is reduced. These findings are fundamental for the successful implementation of continuous manufacturing and real-time release in biomanufacturing.

PF202 Isothermal titration calorimetry as a method for analyzing protein adsorption in ion exchange chromatography
Yamaguchi University, Ube, Japan

Ion exchange chromatography is a widely used method for purification in all types of biomolecules in current biotechnological downstream processes. Knowledge on the binding behavior of proteins provides valuable insight for understanding the molecular mechanisms of protein interactions in a biological context. However, thermodynamic parameters such as enthalpy and entropy changes accompanied by protein adsorption and desorption are still unknown in ion exchange chromatography. This work relates the change in molar adsorption enthalpy, Δh0, with the salt concentration needed to elute a model protein with a gradient elution, IR. Bovine serum albumin (BSA) was adsorbed on four anion exchanger solid phases possessing grafted ligands (Toyopearl GigaCap Q-650M, Toyopearl SuperQ-650M, Toyopearl Q-600C AR, Q Sepharose XL). A linear relation was observed between the Δh0 and IR. From the highest Δh0 to the most negative: Toyopearl SuperQ > Q Sepharose XL > Toyopearl Gigacap Q-650M > Toyopearl Q-600C AR. The same experiments were also done with a non-grafted conventional solid phase, Q Sepharose FF. However, it did not fit in the same trend due to the ligand disposition. Δh0 was found to be endothermic for Q Sepharose FF and Toyopearl SuperQ-650M and exothermic for the other solid phases. Endothermic Δh0 indicate that entropic effects play a major role on the adsorption of BSA on these two solid phases.

PF203 Scalability of OPUS® Pre-packed Disposable Columns from 1 mL Laboratory to 57L Production Scale
1 Austrian Centre of Industrial Biotechnology, Vienna, Austria
2 Repligen Corporation, Waltham, USA
3 Repligen GmbH, Ravensburg, Germany
4 BOKU, Vienna, Austria

Flexible adaptation to constantly changing market demand is getting increasingly important in the manufacturing workflow of biopharmaceuticals. Moreover, fast development times and reliable scale-up are required and are key to success.
Pre-packed chromatography columns have been commonly adapted in industry during the recent years and allow to reach these requirements, however data showing scalability throughout various column sizes applied in early stage process development up to commercial manufacturing has been not available so far. This presentation confirms the scalability of column performance throughout Repligen's OPUS® pre-packed column line including MiniChrom, ValiChrom and OPUS® Process Scale columns covering a range of 0.5 to 60 cm inner diameter.
Scalability has been demonstrated for various resin types and functionalities and has been proven for both column packing performance and protein separation under isocratic conditions.
Experimental data on OPUS® packing performance has been compared to traditional self-packed columns and found at least equal if not better.
Furthermore a statistical data analysis using advanced software tools has been performed for more than 30.000 pre-packed columns supplied into global industry over a time span of 10 years.

PF204 Extra-column effects in pilot scale chromatography
Jürgen BECK1, Eric VON LIERES2, Rainer HAHN1
1 University of Natural Resources and Life Sciences, Vienna, Austria
2 Forschungszentrum Jülich, Jülich, Germany

Extra-column effects can have significant influence on separation performance. These effects are caused by dead-volumes, valves, column hardware and tubings. For small scale chromatography systems, and especially with very small columns, the extra-column band broadening can be dominant over the actual broadening of the column that is used for separation. This issue has long been recognized and has been investigated extensively by many researchers. However, though it is often overlooked, also for preparative and pilot scale chromatography extra-column effects can be an important factor. This is particularly valid, if the column size is relatively small. We have investigated the Aekta Pilot system volume contribution to band-broadening by non-binding tracer experiments on columns of various sizes using columns packed by axial compression to ensure consistent packing performance. Additionally, the influence of non-standard mixing behavior occurring in the bubble trap during step elution was investigated using a simplified model of interconnected reactors. Other flow parts of the chromatography system were modelled by dispersed plug flow reactors and CSTRs for dead zones, e.g. column in- and outlet and mixers. Essentially, the effective mixing volume of the bubble trap is affected by the flow rate and the density difference of the two buffers. As a consequence, the influence on the separation in the column varies with these parameters. Experimentally, the band broadening effect of the bubble trap on the chromatographic separation was investigated by performing linear gradient elution and step elution experiments using bovine serum albumin at analytical loads. There was no observable band broadening effect in linear gradient elution. However, during step elution the salt transition profile was affected leading to significant peak broadening of the BSA elution profile.

PF205 Effect of single pass TFF on impurity removal of intensified chromatography for mAb processing
Takao ITO, AKAI Yusuke
Merck Ltd., Tokyo Japan

There is growing interest in mAb processing to improve individual unit operation performance and overall process train efficiency through linked processing. In the downstream process, several types of chromatography are typically performed to achieve the target of purity of therapeutic mAb. AEX chromatography is commonly operated under product flow-through conditions to bind negatively charged impurities such as HCP and virus. CEX chromatography focuses to separate the mAb related impurity. Ichihara et al., (mAbs J. 10-2, 325-334, 2018) reported the operating CEX chromatography in the flow-through mode for mAb aggregate removal. To intensified flow-through chromatography, controlling the feed concentration through single pass TFF (SPTFF) is one of the ideas to get the higher loadings from the isotherm binding condition, especially for AEX column. The use of SPTFF technology can help facilitate these process intensification efforts by modifying process intermediate volumes and concentrations without the need for recirculation. However, the impact of concentration change on other chromatography is not evaluated well on the fully combined in-series operation.
In this work, SPTFF by Pellicon® 3 30kD is used prior to a flow-through chromatography polishing step to boost chromatography resin loading. Then, Eshmuno® CP-FT resin was challenged with various concentrations of mAb feed and evaluated the difference of impurity removal. And results compared the performance of previously reported SPTFF-AEX results (Merck Application Note, AN5364EN00 2017), and evaluate the impact of connected flow-through polishing on feed concentration.

PF206 Innovative impurity reduction method for next generation mAb purification process
Fuminori KONOIKE1,2, Dai MURATA1,2, Masakatsu NISHIHACHIJO1,2, Kazunobu MINAKUCHI1,2
1 KANEKA Corporation., Takasago, Hyogo, Japan
2 Manufacturing Technology Association of Biologics

The biopharmaceutical downstream process is designed to achieve high product yield with efficient impurity removal. “Process derived impurities” such as host cell proteins (HCPs), lipid, DNA and fermentation ingredients and “Product related impurities” like aggregates and fragments should be reduced to meet each specification of drugs for quality and safely.
Economical pressure on biopharmaceuticals, especially monoclonal antibodies (mAb), has motivated to develop high capacity chromatography resins and new purification technologies including periodic counter-current chromatography and multi cycle batch chromatography using smaller particle size resins with high flow rate. Thus, load amount onto chromatography resins are tend to increase.
Higher amount loading of not only target proteins but also impurities on chromatography resins affect selectivity and life time of chromatography resins. Increased risk of fouling on chromatography resins by accumulation of impurities should be mitigated as much as possible to minimize burdens on each step to develop stable process with lower COGs.
We developed new impurity reduction method using co-precipitation of impurities without loss of target proteins. The method reduced HCPs and DNA in harvested cell culture fluid expressing mAb one third and one thousandth respectively. We also evaluated the effect on the quality of eluate from protein A chromatography and other benefits on the process.

PF207 Continuous capture step of a monoclonal antibody downstream process with Amsphere™ A3
Tomoyuki KAMIDE, Kaori ITAYA, Takashi MATSUDA, Satoshi NAKAMURA, Masaaki HANAMURA
JSR Corporation, Tsukuba, Ibaraki, Japan

1. Introduction
There is increased interest in continuous processing for monoclonal antibody (mAb) purification in bind and elute mode. This is because such continuous chromatography offers higher productivity and cost effectiveness than conventional batch mode. JSR developed and conducted a DoE for continuous chromatography process of mAb in bind and elute mode using a high-capacity Protein A resin, Amsphere™ A3.
2. Experimental
The mAb breakthrough was monitored by HPLC. The concentration of Protein A purified mAb was determined from the measured absorbance at 280 nm. Host cell protein (HCP) was quantified by CHO HCP ELISA kit, 3G (Cygnus Technologies). A harvested cell culture fluid (HCCF) contains IgG1 subclass mAb.
A three factor and three level DoE was designed using Minitab (Minitab, Inc.) to determine the impact of purification conditions on productivity (g/L/hr) and HCP concentration. The tested factors were IgG-loading, residence time for washing step and washing volume.
3. Results and discussion
Productivity of the continuous process with Amsphere A3 was calculated on various purification conditions. The results showed that the process time for sample loading and washing steps have significant effect on the productivity. The total amount of HCP in the eluates showed a positive correlation with the sample loading amount, especially when the flow rate for the loading step was relatively faster. That is, washing conditions have smaller effect on the HCP clearance performance with shorter residence time of sample loading step.
4. Conclusions
Amsphere A3 showed high productivity with continuous process because of its high DBC even for high linear flow velocity. Also, we found that the HCP clearance performance is independent from the residence time for washing step. This indicates that higher productivity and good HCP clearance can be achieved together by increasing flow rate and decreasing process time of washing step.

PF208 Development of efficient mAb purification in integrated FT-FT mode with cellulose based chromatography resins
Kojiro SOTA1,2, Yoshihiro MATSUMOTO1,2, Shigeyuki AOYAMA1,2
1 JNC Corp., Tokyo, Japan
2 Manufacturing Technology Association of Biologics, Tokyo, Japan

The development of efficient downstream processing plays an importance in therapeutic antibodies (mAb) purification. As an example, a continuous multicolumn chromatography technology in ProteinA capturing step has been attracted attention from biopharmaceutical companies. Recently an integrated flow-through (FT) process is considered to be one of effective approaches for mAb purification. FT mode has an advantage to increase loading amount of mAb per column volume. Further an integrated FT-FT process technology is expected to achieve much less installed chromatography resins, buffer and tanks to use in comparison with a conventional polishing step consisting of bind/elute (B/E) mode and FT mode. This technology will promise pool-less manufacturing for economical mAb process in near future.
Cellulose based chromatography resins are well-known to be stable to caustic condition for cleaning and less nonspecific adsorption properties. These unique properties are suitable to apply an integrated FT-FT process technology for mAb purification. In the past few years we succeeded in developing a unique cellulose based mixed mode resin, Cellufine MAX IB, which can remove impurities effectively in FT mode for mAb purification under high salt condition. The resin is further tested to use integrated FT-FT mode for mAb purification by examining mAb recovery and impurities removal. In this poster, we report development of efficient mAb polishing process by integrated FT-FT mode which consists of a combination of Cellufine MAX IB resin with other cellulose based cation exchange or hydrophobic chromatography resins.

PF209 Accelerated Process Design and Simulation of Protein Chromatography by Using Mechanistic Modeling
Chyi-Shin CHEN, Noriko YOSHIMOTO, Shuichi YAMAMOTO
Yamaguchi University, Ube, Japan

To accelerate process development and optimization of chromatography, it is essential to use mechanistic models to simulate and predict the implementation of such operation for certain products. The universal prerequisites for chromatography modeling involve adsorption isotherm and mass transfer mechanism, where users can choose the models based on the balance of predictability and calculation ability. Unfortunately, most software packages are still not user-friendly because of complexity of models and input parameters.
In the study, different mechanistic models for various simulation platforms that depend on the same isotherm and mass transfer coefficients were tested for linear gradient elution (LGE) of proteins. The model system was separation of basic proteins such as lysozyme and IgG by ion exchange chromatography (IEC). Our model (Yamamoto model) was used for determining the two parameters (A, B) needed for steric mass action (SMA) isotherm model from LGE experiments. As for mass transfer, lumped kinetic model and linear driving force model (LDF) were used as only one lumped mass transfer coefficient (km) is included, which reduces the computational burden in determining individual effect from axial dispersion and pore diffusion, and such. The km value was determined also from LGE experiments based on Yamamoto LGE-HETP model, which includes the compression factor for the peak sharpening effect in LGE.
By a set of LGE experiment, the major parameters (A, B, HETP) can be obtained, and thus the adsorption and mass transfer models for mechanistic modeling can be constructed. Different simulation platforms have given similar outputs in comparison, which demonstrates that modeling for protein chromatography can be achieved from limited LGE data in different computational tools, albeit the coefficients definition varies in the software.
Reference Yoshimoto, Yamamoto, Simplified methods based on mechanistic models for understanding and designing chromatography processes-Yamamoto Models and Approach-, in Preparative chromatography for separation of proteins, 2017

PF210 Economics and ecology: Modelling of primary recovery and capture scenarios of recombinant antibody production processes
Alessandro Luigi CATALDO1,2, Peter SATZER1,2, Alois JUNGBAUER1,2
1 Department of Biotechnology, University of Natural Resources and Life Sciences, 1190 Vienna, Austria
2 Austrian Centre of Industrial Biotechnology (ACIB), Muthgasse 18, 1190 Vienna, Austria

The changes from stainless steel equipment to single-use solutions as well as switching from batch to continuous operations are currently strong discussed topics in the field of downstream processing. Besides the product yields and the purity grades, the footprint reduction and higher productivities result in decreased cost of goods (CoGs). With these developments, not only economic but also ecological goals will be achieved through buffer and materials savings. In the course of the present evaluation, we compared continuous and single use solutions to conventional platform processes and quantified their economic and ecological impact. In detail, we have compared a cell culture antibody process consisting of conventional broth clarification by centrifugation and batch capture by protein A affinity chromatography with a continuous process consisting of continuous clarification by depth flocculation and continuous precipitation and/or periodic counter current chromatography (PCC). Our results show potential cost saving strategies and how ecological goals and improved costs of goods can be combined. Possible savings of 30 % can be achieved by combining novel technologies and buffer savings of 60 % can be realized by the use of precipitation or PCC. The scenarios were evaluated for an existing facility with a bioreactor scale of 1,000 L as well as for two theoretical facilities scaled for either an orphan drug production of 50 kg/year or a blockbuster production of 1,000 kg/year.

PF211 Antibody concentration measurement using optical rotation: toward Process Analytical Technology
1 Yamaguchi University, Ube, Japan
2 Astellas Pharma Inc., Tsukuba, Japan

The antibody manufacturing process is consisted of a cell culture process using animal cells and a purification process including several chromatography steps and filtration steps. The purification process is important to obtain high quality bio-pharmaceutical products by removing impurities, and measurement of antibody concentration is a fundamental and essential factor to control the manufacturing process and to confirm the yield of each purification step.
The concentration range in the purification process is wide, and over 100 mg/mL concentration can be observed for example in a final polishing step. In this study, optical rotation was applied for the first time to measure various concentrations of antibody and their accuracy was evaluated. Furthermore, the possibility of application to the process analytical technology was also discussed in the poster presentation.

PF212 Combination of Column Chromatography and Virus Filter for Continuous Bioprocessing
Hironobu SHIRATAKI1, Yoshihiro YOKOYAMA2, Ryota OGURI2
1 Asahi Kasei Medical, Tokyo, Japan
2 Asahi Kasei Medical, Nobeoka, Japan

Virus filter is essential step to eliminate viruses in the Bio-pharmaceutical products. Continuous bioprocessing is of great interest for bioprocess manufacturers because of the possibilities of reducing production time, cost and footprint. One important element of continuous bioprocess is tankless connection between the adjacent steps, however virus filtration is mostly batch process, in which the target protein solution is pooled in a tank and then loaded to the virus filter with constant pressure. One reason of the preference of batch process is the concern of possible flux decay during the loading process Especially if chromatography process is connected directly to virus filter, flux decay by the sudden pressure rising is fatal for the manufacturing process. In this concern, virus filters with multi-layer structure as shown in the figure having high robustness in the continuous loading are necessary for the manufacturing process
Chromatography process is located just in front of the virus filter step and it affects the permeability of virus filter significantly. Especially ion exchange chromatography (IEX, AEX or CEX) step is usually just before the virus filter in the IgG purification process and impurity removability of IEX step is essential for the virus filter permeability.
In this study, the effect on the virus filter permeability of different types of IEX chromatography resins, i.e., normal IEX and mixed-mode IEX, are compared by using IgG solution with spiking aggregates. Mixed-mode AEX shows much higher aggregate removal than normal AEX. The virus filter permeability is tested both for constant pressure and constant flow rate loading. The dependencies of IgG concentration and flow rate are also tested. These results indicate that appropriate combination of IEX resin, column volume, virus filter membrane area and flow rate is very important for high protein recovery and the cost effectiveness process in the continuous bioprocessing.

PF213 A simple method for determining the optimum temperature for polyphenol separation by reversed phase chromatography
Shinya NOZAKI, Chyii-Shin CHEN, Noriko YOSHIMOTO, Shuichi YAMAMOTO
Bio-Process Engineering Laboratory, Graduate School of Innovation and Science, Biomedical Engineering Center (YUBEC), Yamaguchi University, Tokiwadai, Ube 755-8611, Japan

Chromatography separation, which is essential in biopharmaceutical industry, is not widely used in food industry as food products are much less expensive than pharma products. However, as functional foods are highly anticipated, there is an increasing need for development of efficient and economically-feasible chromatography process for food separation.
In addition to the cost issues, food separations have many constraints and requirements, which make it difficult to use chromatography. As for the stationary phase (resins) and the mobile phase (liquid), they must be chosen based on the accepted materials by the regulatory agency. In addition, the resins must be cleaned and sanitized easily. Considering these requirements, polystyrene divinylbenzene (PS-DVB) resins-based chromatography with ethanol-water mobile phase is most attractive. The resins can be washed with sodium hydroxide. Ethanol is a very safe solvent, and can be recycled easily if needed.
In this study, a simple method for determining the optimum temperature for the above mentioned chromatography system was proposed based on the iso-resolution curve concept. The model samples were polyphenols (catechin and epigallocatechin gallate). PS-DVB resins were employed for the column stationary phase. The mobile phase was ethanol-water mixture. The distribution coefficient K was determined as a function of ethanol concentration,I , and temperature, T. A method for calculating the iso-resolution curve was developed with K, T, and mobile phase velocity, u. From the iso-resolution curve, the productivity was calculated as a function of I, T and u. It was found that there is an optimum T, where the highest productivity considering minimum mobile phase consumption.
From the industrial point of view, precise temperature control is costly. However, choosing the right temperature will result in more efficient separation processes.

PF214 Rational evaluation methods for pre-packed chromatography columns for protein separations
Noriko YOSHIMOTO, Shinya NOZAKI, Ayaka KIMURA, ChyiShin CHEN, Shuichi YAMAMOTO
Yamaguchi University, Ube, Japan

Various different sizes of pre-packed chromatography columns are needed for process design, pre-clinical trials and production. It is therefore needed to evaluate the quality of pre-packed columns properly. HETP and asymmetrical factor As measured at non-binding conditions are commonly employed to check the packed bed quality. In this study, for capture chromatography (protein A) columns E = DBC/SBC vs. F0 plots [1] were used for the evaluation. DBC is the dynamic binding capacity and SBC is the static binding capacity. F0 is the dimensionless group, which is given by the square of particle diameter divided by the molecular diffusion coefficient and the residence time. For polishing chromatography columns (ion-exchange chromatography), another dimensionless group, Ym was used for the evaluation. Ym is composed of column length, velocity, particle diameter and gradient slope [2].
[1] N. Yoshimoto, T. Yada, S. Yamamoto; A simple method for predicting the adsorption performance of capture chromatography of proteins. Jpn. J. Food Eng., 17, 95–98 (2016).
[2] N. Yoshimoto, S.Yamamoto; Simplified methods based on mechanistic models for understanding and designing chromatography processes for proteins and other biological products-Yamamoto models and Yamamoto approach-, in Preparative chromatography for separation of proteins, Chap 4, Wiley, New York, 2017, pp. 111–157.

PF215 Development of large-scale column packing technology for protein A affinity resins
Yasuhiro TADA, Masaru HIRANO
Kaneka Corporation

In antibody drug manufacturing, Protein A affinity chromatography is performed as separation and purification steps using its specific binding ability to antibodies. In the manufacturing process, two different packing systems, Axial compression (AX) and Pack in Place (PIP), are mainly used to pack Protein A chromatography resins into large-scale columns.
KANEKA KanCapATM (KanCapA), which is one of our commercially available Protein A resins, can be appropriately packed into both AX and PIP system columns. With PIP system column, however, it is important to select conditions because PIP packing is susceptible to various parameters.
<Experiment and Result>
Some parameters for PIP packing were investigated with 80cm I.D. Chromaflow column (PIP system column of GE HealthCare) in this study. Higher slurry concentration and higher slurry flow rate led to better column performance. In addition, pump pulsation at the feeding slurry had an influence on the performance and installation of pulsation dampener reduced the influence. Consequently, good column performance was realized by setting slurry concentration and its flow rate appropriately with pulsation dampener.
It is feasible to realize good column performance by packing KanCapA into PIP system column with proper slurry concentration and its flow rate. Even with pumps generating large pulsations, good column performance is also realizable using pulsation dampener.

PF216 Dispersion behavior in tubular reactors for continuous virus inactivation
Sachie FUJII, Hidenori INABA, Noriko YOSHIMOTO, Shuichi YAMAMOTO
Yamaguchi University, Ube, Japan

Continuous manufacturing is expected to be more efficient for production of biologic such as monoclonal antibodies (mAbs) compared with batch productions. Various unit operations are included in downstream processing (DSP) of mAbs such as chromatography and membrane separation. Virus inactivation is also required in DSP.
Tubular reactors are possible formats for continuous virus inactivation. It is important to know dispersion behavior in tubular reactors. For open tubular reactors, the dispersion is described by Taylor dispersion due to molecular diffusion. We carried out pulse response experiments to measure response curves (residence distribution curves). Various factors affecting the dispersion such as molecular diffusivity, tube diameter, tube diameter to coli diameter ratio, temperature and viscosity were examined.

PF217 Purification of peptides by twin-column countercurrent chromatography
Masatoshi TANIGUCHI1, Thomas MÜLLER-SPÄTH2, Michel BAVAND2, Noritaka KURODA1, Naohiro KURIYAMA1
1 YMC Co., Ltd. YMC Karasuma-Gojo Bldg., 284 Daigo-cho, Karasuma Nishiiru Gojo-dori, Shimogyo-ku, Kyoto 600-8106, Japan
2 ChromaCon AG, Technoparkstrasse 1, 8005 Zurich, Switzerland

Continuous countercurrent chromatography is a valuable tool for the purification of peptides produced by chemical synthesis. Using a process comprising two reverse-phase columns and internal recycling (MCSGP), peptides are purified on a preparative scale with high yield and purity simultaneously while the generation of side-fractions and re-chromatography is avoided. The poster introduces the process concept, lab- and production scale equipment, and recent results of an economic evaluation of MCSGP in comparison with batch chromatography, showing the large upside of employing the two-column process.

PF218 Modeling and Process Development for Protein Separation by Flow-Through Chromatography
Bio-Process Engineering Laboratory, Biomedical Engineering Center (YUBEC), Yamaguchi University, Ube 755-8611, Japan

Chromatography is considered as a critical part in antibody manufacturing process. To improve the productivity of the process, different strategies have been investigated. Flow-through chromatography (FTC) is being considered as one operation which can increase the efficiency in downstream process by adjusting the mobile phase environment that makes contaminants bind tighter to the column while the product elutes out as flow-through fraction.
A mechanistic model containing distribution coefficient and plate number to describe the start and the end of the protein elution fraction and contaminants is developed for FTC. From a set of linear gradient elution experiments in different gradients, the correlation between distribution coefficient and salt concentration can be determined. Combined with the particle diameter and diffusion coefficient, plate number under certain elution condition (e.g. pH, retention time, etc.) can be calculated. By setting the end of the product to be equal to the start of the contaminant, the optimal amount of sample loading and its productivity can be obtained.
In the study, samples containing bovine serum albumin monomer and dimer were selected for separation by ion exchange chromatography. Based on the mechanistic model, productivities under different mobile phase condition including pH, particle size, and retention time were determined for 100L of material with 100 minutes of operation time. A small scale of FTC experiment was conducted to verify the model predictability. Based on the result, separation process for proteins can be developed and simulated by adjusting the parameters involved in the model to achieve higher productivity.

PF219 A novel approach to diafiltration for intensified or continuous processing
Takao ITO1, Elizabeth GOODRICH2, Akshat GUPTA2, Herb LUTZ2
1 Merck Ltd., Tokyo
2 EMD Millipore Corporation, Burlington, MA

Diafiltration is a critical unit operation which is part of practically every downstream purification train of monoclonal antibody or bio therapeutic modality production. It is typically employed to provide an efficient and robust method for exchanging buffer matrix for the therapeutic modality and offers simultaneous clearance of small molecule and elemental impurities.
Continuous manufacturing and process intensification approaches has been an area of keen interest and various technologies are being investigated to make biotherapeutic manufacturing process more efficient in terms of facility utilization and capital cost reduction by reducing reliance on large scale facilities. Technologies like multi-column cycling, inline viral inactivation and single pass tangential flow filtration (SPTFF) for protein concentration have been developed in past few years, offering significant improvement over their existing batch equivalents. Ability to develop a similar technology for diafiltration suitable for GMP manufacturing has remain rather elusive.
Our approach here is based on a shift in perspective wherein the process design is based on membrane utilization and system footprint as opposed to flux and process time in a typical batch diafiltration process. This rather flexible technology offers 6-8-fold increased membrane utilization, up to 3-fold reduction in pump passes and system footprint can be substantially decreased. Buffer usage, extent of buffer exchange, and product yield are consistent with a constant volume diafiltration process.
In this presentation, we will present a system design for this concept and a 24-hour experimental data demonstrating operational robustness. Implementation into a fully continuous, or intensified process train and flexibility of the system to accommodate complex diafiltation schemes for challenging molecules will also be discussed.

PF220 Elution profiles of antibody-drug conjugates in preparative chromatography
Takuro TANAKA, Koichiro IKEDA, Noriko YOSHIMOTO, Shuichi YAMAMOTO
Yamaguchi University, Ube, Japan

Monoclonal antibodies conjugated with drugs (ADC) have received much attention as pharmaceutical agents for treating serious diseases such as cancer. However, it is difficult to separate them on the basis of the number of conjugated drugs. Hydrophobic chromatography (HIC) is commonly used for the analysis of the drug to antibody ratio, DAR. The retention of ADCs on HIC can be controlled by the hydrophobic nature of ADCs, depending on the mobile phase conditions. They are sometimes performed at the restricted conditions where the solubility is too low and thus one cannot archive high capacity. Ion exchange chromatography (IEC) using electrostatic interaction is an orthogonal method to HIC. IEC is widely used because of its higher capacity than HIC. We investigated the retention behavior of the protein conjugated surrogate drugs on IEC. The surrogate drugs employed are 7-diethylamino-3-(4'-maleimidylhenyl) 4-methylcoumarin (CPM), N-(1-pyrenyl)maleimide (NPM) and Cyanine5 mono NHS Ester (Cy5-NHS). Bovine serum albumin (BSA) and human immunoglobulin G (h-IgG) were used as a model protein. The molar ratio (CPM or NPM or Cy5-NHS to protein) was set to 3. The maleimide group of CPM and NPM reacts with the thiol group of the proteins, and the NHS ester group of Cy5-NHS reacts with the amino group of the protein. On the linear gradient elution experiments, the elution salt concentrations of the conjugated and non-conjugated proteins were measured to obtain chromatographic parameter of the number of binding site, B.

PF221 Thermodynamic analysis of bovine serum albumin adsorption onto grafted ion exchange ligands
Yamaguchi University, Ube, Yamaguchi, Japan

The graft-type ion exchange chromatography is expected to have a high binding capacity. However, in some cases, the steric hindrance needs to be considered in the pore fulfilled by the grafted ligand. It is difficult to visualize the structure in the pore, and it is not known how the adsorption reaction is progressing. In this study, the heat of adsorption reaction was measured by using isothermal titration calorimeter (ITC), the enthalpy and entropy changes associated with protein adsorption to the graft-type ligand were analyzed, and the relationship with the capacity and structure of pore was discussed. SuperQ 650M, GigaCapQ 650M and Q-600C AR were used as the resins with graft-type ligands, and bovine serum albumin (BSA) monomer was used as the model protein. The binding isotherm was obtained by varying the concentration of BSA from 0mg/mL to 20mg/mL incubated with 50% resin slurry. The equilibrated binding capacity of Super Q was only about 1/4 of that of Q-AR. For the measured enthalpies by ITC, GigaCapQ and Q-AR were negative and SuperQ was positive. From these, it can be seen that adsorption is exothermic and endothermic, respectively. Also, ΔS was calculated by ΔG from the adsoprtion isotherm and ΔH from ITC. As the result, it turned out that enthalpy contribution was large in GigaCapQ and Q-AR, entropy contribution was large in SuperQ. This indicates SuperQ needs the release of water and counter ions when electrostatic interaction occurs. There is less steric hindrance in GigaCapQ and Q-AR (=there is little entropy contribution), the adsorption mechanism is driven by electrostatic interactions.

PF222 Adsorption of immunoglobulin G in protein A resins studied by confocal laser scanning microscopy taking account of the optical hindrance inside a particle
Tomohisa KATSUDA, Tomoki YAMAGUCHI, Naruaki INOUE, Yuki KASE, Kou OTA, Hideki YAMAJI
Kobe University, Kobe, Japan

In the present work, we studied the adsorption behavior of immunoglobulin G (IgG) in commercially available protein A resins by use of confocal laser scanning microscopy (CLSM) together with the fluorescein isothiocyanate (FITC) conjugate, combining a newly proposed calibration method. CLSM provides the capability to collect serial optical sections from thick specimens, and thus applying to protein A resins taking up FITC-IgG it enables us to pursue the progress of adsorption front within a particle and furthermore to determine apparent diffusion coefficients through a model-based analysis. Although CLSM could count as powerful method to understand intraparticle mass transfer, there seems no availability of appropriate data without taking account of the optical hindrance inside a porous resin particle. The laser light penetrating a resin particle is likely to be attenuated with the scattering by particle matrix, absorption by fluorescent label, or both, and furthermore the fluorescent light emitted from the fluorescent label of adsorbed proteins could undergo these interactions, too. Therefore, the light attenuation of exciting and emitted light is necessary to be calibrated in determination of the distribution of protein amount adsorbed. For this purpose, we propose to adopt the attenuation ratio, determined from a negative image of the particle taken by use of the fluorescein solution with a concentration at which the solution itself can emit fluorescence with the laser light used. Though found a large difference in the light attenuation depending on resin, we concluded from the dependence of the attenuation ratio on the dye concentration that the scattering by particle matrix mainly contributed to the light attenuation but the absorption by fluorescent label did less. By combining this calibration method with CLSM it makes possible to compare the profile of protein amount adsorbed within a particle among different types of resins.

PF223 Diffusion behavior of biopolymer in ion exchange carrier with graft type ligand
Yamaguchi University, 2-16-1 Tokiwadai Ube, 755-8611 Japan

Antibody drugs have specificity and act only on the target site, so they have few side effects and are expected as therapeutic agents for cancer etc. In chromatography used for separation, purification, etc. of antibodies, there is graft type ligand chromatography where ligand is increased by introducing a graft chain for the purpose of increasing adsorption amount.
However, it is also feared that pore blockage may cause diffusion inhibition. Therefore, we used some grafted chromatography to investigate the actual adsorption mechanism.
In this study, two columns, graft type Super Q and Q Giga Cap, were used. The pore size was calculated using DNA. Q Giga Cap was 3.0 nm and Super Q was 4.6 nm. It was found that when the diffusion coefficient at that time was determined, the diffusion resistance increased as the pore size decreased. In particular, in the case of small pore size Q Giga Cap, the amount of decrease was large.
In addition, as a result of measuring the adsorption amount of BSA, Q Giga Cap showed higher DBC than Super Q. This is because the space volume of the graft chain layer is large.
From the above results, it was found that the introduction of the graft chain increases the diffusion resistance but increases the adsorption amount.

PF224 Retention behavior of Antibody-Drug Conjugation on ion exchange chromatography
Kouichirou IKEDA, Noriko YOSHIMOTO, Shuichi YAMAMOTO
Ymaguchi University, 2-16-1 Tokiwadai, Ube, 755-8611 Japan

Antibody-Drug Conjugation (ADC) is studied actively as future Drug. ADC has parameter called Drug-to-Antibody Ratio (DAR). DAR is number of drugs on antibody. Now, DAR is controlled by genetically modified cell, bad this is not simply. To control the DAR of ADC from normal antibodies is difficult by reaction of antibody and drug. DAR should be controlled without complicated procedure. Therefore, it is necessary to separate precisely. In this work, for the development of separation technology of ADC by Ion Exchange Chromatography (IEC), we analyze the ADC's adsorption system. There are many studies of separation by Hydrophobicity Interaction Chromatography (HIC). However, HIC is complicated by column selection. IEC is more simply procedure and higher recovery rate than HIC.
Result of analysis of the number of adsorption site B, model ADC A from Lysozyme is lower number than native Lysozyme. However, model ADC B from Bovine Serum Albumin (BSA) is higher number than native BSA. Therefore, ADC B is considered to be aggregated with the conjugated BSA as a core. Also, ADC conjugated charged drug is higher amount of change than ADC conjugated hydrophobicity drug. Therefore, ADC conjugated charged drug is higher effect than ADC conjugated hydrophobicity drug.

Session S6. Australia–China–Japan session for powder and nanotechnology

A313 [Keynote] Multiscale modelling and analysis of particle-fluid flow systems: Some examples
Shibo Kuang
Monash University
A315 [Invited] Shaping particles by chemical diffusion and reaction
Yongsheng HAN, Kai WANG, Yongxiu CHEN, Haoyang HUANG, Xiangyu DOU
Institute of Process Engineering, Chinese Academy of Sciences, 100190 Beijing, China

Chemical diffusion and reaction are generally involved in the formation of materials. These two processes are coupled together and play a role in the structure evolution of materials. Although the individual role of diffusion and reaction has been investigated, it is still unclear how these two factors work together to determine the materials structure and what is the mechanism behind. Firstly we used different approaches to regulate the diffusion and reaction rates in the synthesis of silver particles [1-3]. The role of diffusion and reaction in shaping particles was generalized. At a diffusion limitation, small silver particles were obtained and big polyhedral particles were formed at a reaction limitation. In the middle range of diffusion and reaction, dendritic structures were largely produced, which is independent on the preparation methods. In the following, the control on diffusion and reaction has been extended to synthesize other materials and the similar results were obtained [4-6], which further confirms the general role of diffusion and reaction in shaping materials. The Damkoehler number was employed to quantify the relative change of diffusion and reaction[7]. It was found that the morphology of materials is dependent on the relative strength of diffusion and reaction. Since the diffusion and reaction determine the chemical distribution around the growth front of materials, the local chemical gradient was proposed to be the mechanism of diffusion and reaction controlling materials structures, which was verified by measuring the local chemical distribution by laser interference as well as by conducting phase field simulation.
[1] Chemical Engineering Science 2018, 192, 254-263.
[2] Chemical Engineering Science 2015, 138, 457-464.
[3] Ind. Eng. Chem. Res. 2016, 55, 8319-8326.
[4] CrystEngComm 2017, 19, 72-79.
[5] Crystal Growth & Design 2013, 13, 1820-1825.
[6] Advanced Energy Materials, 2019, doi.org/10.1002/aenm.201900019.
[7] Crystal Growth & Design 2016, 16, 2850-2859.

A316 [Invited] Innovative granular flow modeling for industrial systems
The University of Tokyo, Tokyo, Japan

Numerical modeling plays a leading part for virtual manufacturing in industries. When numerical technologies are utilized in the general industrial systems, high-accuracy, simple operation and calculation efficiency are always required. The requirements are the same even in powder industries. In the author's group, innovative models such as coupled discrete element method (DEM) with volume-of-fluid (VOF), signed distance functions (SDF) and coarse graining DEM have been developed for the simulations of granular flows in industrial powder systems. The SDF makes it possible to create an arbitrary shape domain by simple operation. The SDF has been applied to various powder systems such as mixers, die filling and conveyers so far. Besides, calculation domain for simulations of industrial multi-phase flows including solid particles can be created easily by combining the SDF with immersed boundary method (IBM). The coarse graining DEM is a scaling law model and can simulate large-scale systems by smaller number of computational particles than actual ones. Efficiency of the coarse graining DEM has been examined through several industrial systems such as a spouted bed and a fluidized bed. The DEM-VOF method can simulate gas-solid-liquid flows in an arbitrary shape domain because the SDF and the IBM has been introduced as wall boundary model. The DEM-VOF has been applied to a complex gas-solid-liquid flow system such as a twin screw kneader. Adequacy of these models has been proven through verification and validation tests. Hence, in the future, usage and/or combination of these models will be useful for virtual manufacturing.
This study is financially supported by JSPS KAKENHI grants (17KK0110, 17H02825 and 17H03451).

A317 [Invited] Numerical and experimental investigation of particle deposition in the mouth-throat models with handihaler®
F. HUANG1,3, Z. B. TONG1,2*, Z. Y. ZHOU3, J. CHEN2, A. B. YU1,2,3
1 Key Laboratory of Energy Thermal Conversion and Control of Ministry of Education, School of Energy and Environment, Southeast University, Nanjing, China
2 Centre for Simulation and Modelling of Particulate Systems, Southeast University-Monash University Joint Research Institute, Suzhou, China
3 Department of Chemical Engineering, Monash University, Clayton, Vic 3800, Australia

The inhaled drugs are generated as aerosol in dry powder inhalers (DPIs) and then delivered into respiratory tract. The deposition in the target sites mainly depends on a number of factors related to anatomical structure variation, particle characteristics and inhalation conditions (inhaled angle and breathing pattern e.g.). This project aims to numerically and experimentally investigate the effects of inhalation parameters on fine particle deposition in the US pharmacopeia throat (USP), idealized mouth-throat (IMT) and realistic mouth-throat (RMT) models with a commercial inhaler (Handihaler®). In the numerical model, the flow-field equations are solved by computational fluid dynamics (CFD). The monodispersed and Rosin-Rammler distributed particles in the size range of 1-20 μm are tracked with discrete phase method (DPM). Corresponding physical experiments under the same inhalation conditions are designed to quantitatively and qualitatively characterize particle deposition in realistic mouth-throat as well as validate the numerical results. The results indicate that particle deposition fraction and spatial distribution are highly sensitive to the geometrical variation and respiratory conditions such as the inhalation airflow rate, particle size and inhalation angle. Moreover, the effect of geometrical variation on the particle deposition pattern is more dominant. In the RMT model, inhalation angle creates quite obvious effect on the aerosol delivery, especially for particles depositing in oral cavity. This study could be used to develop an in vitro method which aims to better predict in vivo lung deposition mechanisms of pharmaceutical aerosol.
Keywords: computational fluid dynamics, particle deposition, dry powder inhalers, mouth-throat geometry.

A321 [Invited] Modelling and optimisation of ironmaking processes: Some recent developments
Yansong SHEN
University of New South Wales, Sydney, Australia

Ironmaking blast furnace industry involves many complex thermochemical processes including, for example, multiphase flows, heat and mass transfers and chemical reactions. It is essential to understand, visualize and optimize the in-furnace phenomena for competitiveness and sustainability under increasing economic and environmental demanding conditions. Mathematical modelling, facilitated by physical modelling, provides a cost-effective way of achieving this goal. In particular, multiscale modelling is widely used in academia and industry for their proven effectiveness. This paper will review our recent CFD- and DEM-based process models and discuss their roles in the development of new technology for sustainable ironmaking. Some recent examples are used: 3D modelling of blast furnace with raceway, 3D modelling of pulverised coal injection, and 3D modelling of cokemaking. It is demonstrated that mathematical modelling indeed plays a significant role in process understanding and optimisation, vital to sustainable modern ironmaking.

A322 [Invited] Potential bridge towards green H2 from coal: Supercritical water gasification
Liejin GUO*, Youjun LU, Hui JIN
State Key Laboratory of Multiphase Flow in Power Engineering (SKLMF), Xi'an Jiaotong University, Xi'an, Shaanxi 710049, China

Hydrogen production by coal gasification in supercritical water is a promising way of coal utilization due to its clean, efficient and low-carbon characteristics. How to further lower the temperature for complete conversion of carbon in supercritical water is a hot topic. Extensive theoretical and experimental investigations were conducted in State Key Laboratory of Multiphase Flow in Power Engineering since 1997.
(1) The rate-determining steps for the supercritical water gasification of coal particles were obtained at different spatial scales. Experimental device such as supercritical water visual platform that combining Raman spectrometer was established to reveal the microscopic kinetic mechanisms. Density functional theory (DFT) and reactive empirical force fields (ReaxFF) were combined to investigate the rate-determining steps and its reaction enhancement strategy. The directional gasification characteristics can be obtained by coordination regulation and control method of temperature and pressure for chemical/transport properties of supercritical water.
(2) A fluidized reactor operating in supercritical water condition was invented. A series of theories of multiphase flow, heat/mass transfer, and chemical reaction gasification in supercritical water fluidized bed reactor were established. By the approach of the coordinated matching of mass flow and energy flow, the primary reactions were enhanced while the side reactions were suppressed.
(3) A demonstration plant was constructed to verify the above-mentioned theories. The carbon content in coal is completely gasified below 670 °C. The C, H, O content in typical coals can be converted to H2 and CO2, while other impurities are flushed off in clean, non-toxic and inert ashes. The demonstration plant operation has lasted continuously and stably for more than ten thousand hours, which lays a foundation for large scale industrialization and widespread application, so as to provide a new way for the solution of energy shortage problems, haze controlling and the realization of a clean and efficient utilization of coal.

A323 [Invited] Numerical simulation of a CH4 dehydroaromatization-catalyst regeneration fluidized bed system using multi-phase particle-in-cell methodology
Xiaoxun MA1, Ming GONG1,2
1 School of Chemical Engineering, Northwest University, Xi'an, Shaanxi, China
2 Beijing UNINSIM Tech Co., Ltd., Beijing, China

Non-oxidative dehydroaromatization can convert methane into important aromatic products, such as benzene toluene and naphthalene, and produce large amounts of hydrogen simultaneously. A pilot-scale methane dehydroaromatization—H2 regeneration fluidized bed system (MDARS) has been developed. The catalyst circulates between two fluidized beds which are methane dehydroaromatization reactor and catalyst H2 regeneration reactor. The fluidization and energy transportation including mechanism of catalytic reactions are modelled in the Eulerian-Lagrangian Multi-Phase Particle-in-Cell (MP-PIC) methodology, also called Computational Particle Fluid Dynamics (CPFD). MP-PIC model uses a stochastic particle method and an Eulerian method for the fluid phase to solve equations for dense particle flow.
The mechanisms of methane dehydroaromatization reaction and catalyst deactivation reaction were investigated by fixed bed reactor and agreed with the experiment data. The whole system with two reactors and one cyclone was simulated in one model so that the interaction between two fluidized beds and catalyst deactivation can be investigated. The simulation results indicated that the catalytic activity remain stable, and the optimal regeneration-reaction ratio is 8 which consistent with the experiment results. The influence of catalyst particle size and catalyst loading were also investigated. The results showed that the small catalyst particle size can increase the methane conversion and products formation rate. The suitable catalyst loading is between 20~30 gram in consideration of the conversion and formation rate per catalyst mass. More operating conditions can be varied over a wide range to optimize and scale-up the methane dehydroaromatization—H2 regeneration fluidized bed system.

A325 High-density operations in downers: Theoretical analysis and simulation
Guoqing GUAN1*, Wenhao LIAN2, Zhongkai ZHAO1, Xiaogang Hao2 Abuliti Abudula1, Chihiro FUSHIMI3, Atsushi TSUTSUMI4
1 Laboratory of Energy Conversion Engineering, Institute of Regional Innovation (IRI), Hirosaki University, 2-1-3 Matsubara, Aomori 030-0813, Japan
2 School of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024, China
3 Department of Chemical Engineering, Tokyo University of Agriculture and Technology, 2-24-16 Naka-cho, Koganei, Tokyo, 184-8588, Japan
4 Komaba Organization for Educational Excellence, Graduate School of Art and Sciences, The University of Tokyo, 3-8-1 Komaba, Meguro-ku, Tokyo 153-8902, Japan

The downer reactor, in which gas and solids move downward in a co-current way, has attracted many attentions in the past two decades due to its unique features such as shorter residence time, narrower residence time distribution, less solids back-mixing and lower pressure drop since gravity acts in the same direction with the flow direction of gas and solids when compared to the flow behaviors in riser. How to increase the solids holds-up in a downer is still an important issue. In this talk, solids volumetric flux (Vs), which is expected to replace the solids mass flux (Gs) as the key factor influencing solids holdup in circulating fluidized beds, was proposed to investigate the solids holdup variation and predict the extreme operation conditions in the downers. It is considered that using Vs to replace Gs to define high-density operation in the downer could be more suitable in this study To increase the solids-up in the downer, the flow behaviors in a series of novel gas-solids co-current downflow conical fluidized bed which is expected to realize a high-density solids holdup along a downer-type pyrolyzer to strengthen the heat transfer efficiency, were systematically investigated by means of a numerical approach. In addition, A Eulerian–Eulerian model incorporating the kinetic theory of granular flow was adopted to simulate the gas-solids flow behaviors in a dense downer below a conventional downer, which could be used for the further pyrolysis of coal and/or decomposition of tar on the generated char before the char and tar are completely separated in a triple-bed combined circulating fluidized bed (TBCFB) system.
(Acknowledgments:This work is supported by the JSPS KAKENHI Grant-in-Aid for Scientific Research B (Kiban B, 17H03451), Japan and the National Natural Science Foundation of China (U1710101)

A326 Three-dimensional modelling of biomass combustion in an industrial scale blast furnace
Yiran LIU, Yansong SHEN
School of Chemical Engineering, University of New South Wales, Sydney, NSW 2052, Australia

Biomass is a carbon-neutral fuel and has the potential to replace coal in ironmaking blast furnaces (BFs) under the carbon-constrained environmental policy conditions. However, the flow and thermochemical in-furnace phenomena related to biomass combustion are not clear at industrial scale BF conditions yet. In this study, a three-dimensional (3D) industrial scale computational fluid dynamics (CFD) model is developed for describing the flow and thermo-chemical behaviours related to charcoal injection into the lower part of a BF under the real BF conditions. The computational domain includes lance, blowpipe, tuyere, raceway and the surrounding coke bed regions. The model features characteristics of the industrial scale BF and charcoal materials, including the real dimensions, operating conditions, bird's nest within the raceway, coke bed around the raceway, non-spherical particle shape of charcoal particles, modified sub-models of charcoal chemical reactions. The simulation results show that the charcoal combustion process can be classified into 5 stages based on the evolutions of the gas species, burnout, fuel gas and gas temperature along the particle plume. The behaviour of different charcoal particle size groups varies considerably within the raceway. The combustion profiles of the charcoal and two typical PCI coals are then compared. It is indicated the burnout profiles comparable qualitatively, confirming the potential of charcoal utilization in PCI technology, whereas the temperature and gas species profiles are different from typical PCI operation quantitatively, indicating the charcoal injection and its control strategy should be redesigned in BF practice, for example, the use of finer mean particle size. This industrial scale model is useful for understanding the combustion behaviour of pulverized charcoal and optimising biomass injection operations.

PA321 Generation of local quantities of particle-fluid flows and formulation of constitutive relations
Qinfu HOU1, Yongli WU1, Zongyan ZHOU1, Jennifer S. CURTIS2, Aibing YU1,3
1 ARC Research Hub for Computational Particle Technology, Department of Chemical Engineering, Monash University, Clayton, VIC 3800, Australia
2 College of Engineering, University of California at Davis, One Shields Ave, Davis, CA 95616, USA
3 Centre for Simulation and Modelling of Particulate Systems, Southeast University - Monash University Joint Research Institute, Suzhou 215123, PR China

There are continuum and discrete approaches to describe granular flows. A continuum approach relies on local average quantities which can be derived through an averaging method based on a discrete approach. But the selection of averaging domain and the validity of local quantities for constitutive relations are not well established, particularly for transient particle-fluid flows. This presentation is about our recent study in this direction for non-cohesive and cohesive particles. Here, it is demonstrated that converged local quantities can be achieved on an averaging domain with proper spatial and temporal sizes. Furthermore, the relation between solid pressure and solid volume fraction is established, agreeing qualitatively to all the existing monotonic ones in the literature. But it is quantitatively different, showing a bifurcation at a high solid volume fraction, which is essentially linked to the variation of short and enduring contacts among particles with flow state and solid volume fraction. This bifurcation must be properly recognized in developing constitutive relations for granular materials. It is also demonstrated that there are different temporal scales in the fluidized bed and different averaged quantities can be obtained, showing the transient heterogeneous structures.

PA322 Development of a stable algorithm for drag force term in the DEM-CFD method
Yuki MORI, Mikio SAKAI
The University of Tokyo, Tokyo, Japan

Coupled method the discrete elements method (DEM) with the computational fluid dynamics (CFD) is widely used for numerical simulation of gas-solid two phase flows, such as fluidized beds. In the DEM-CFD method, the modeling of the arbitrary shaped boundaries and stable algorithm are essential for simulating engineering processes, as industrial systems often have complex shaped wall boundaries. To model arbitrary shaped boundaries, the SDF-IBM wall boundary modelling, where the signed distance function (SDF) are coupled with immersed boundary method (IBM), has been developed. The efficiency and accuracy of the SDF-IBM boundary modeling have been proved through verification and validation tests. On the other hand, when drag forces acting on solid particles becomes extremely high, numerical simulation cannot be performed stably. In order to solve the instability problem, the aim of this study is development of an implicit algorithm for stable calculation for the drag force term. In verification test in the fixed bed, it is revealed that the implicit algorithm solves the numerical instability problem in the drag force. Subsequently, a new robust implicit algorithm which combined the implicit algorithm to SDF-IBM wall boundary modeling is developed and the validation tests are performed in a fluidized bed with inserted tubes. Consequently, a robust implicit algorithm for DEM-CFD method is developed and adequacy of this algorithm is proved through validation tests.

PA323 Investigation of osmotic pressure generation and water sucking behavior for the dense sediment of well-dispersed slurry
Gaku TSUTSUI1, Takamasa MORI2,3, JunIchiro TSUBAKI4
1 Graduate School of Science and Engineering, Hosei University, Koganei, Tokyo, Japan
2 Department of Chemical Science and Technology, Faculty of Bioscience and Applied Chemistry, Hosei University, Koganei, Tokyo, Japan
3 Hosei University Research Institute for Slurry Engineering, Koganei, Tokyo, Japan
4 Nagoya Industrial Science Research Institute, Nagoya, Aichi, Japa

From our previous research, it was found that the sediment of well-dispersed slurry could act as a continuous osmotic pump and kept sucking water for long time. This means that the sediment of well dispersed slurry is expected to be a pump for irrigation and greening desert. In order to achieve this, it is important to increase the amount of sucking water flux, thus, the effects of slurry conditions on the water sucking behavior for the sediment of well dispersed slurry must be clarified. Therefore, in this study, we investigated the effects of slurry conditions such as particle size, particle concentration, slurry height, type of additives, on the water sucking flux of the sediment. In addition, the osmotic pressure generated by the sediment for various slurries were measured. It was shown that the sediment of the smaller particles could generate the larger osmotic pressure and show the higher water sucking flux, since the overlap of the electric double layer became remarkable for the slurry of smaller particles.

PA324 Effect of alkali metals for ash particle adhesion phenomena at high temperature
Ryosuke FUJII, Yuta BEPPU, Genki HORIGUCHI, Yohei OKADA, Hidehiro KAMIYA
Graduate school of Bio-Applications and Systems Engineering, Tokyo University of Agriculture and Technology, Koganei, Tokyo 184-8588 Japan

Ash adhesion and deposition phenomena on the surface of super heater and furnace wall has hindered the stable operation of coal, biomass and waste combustion and power generation plants. These phenomena also reduced the efficiency of power generation and heat transfer. Based on the measurement of tensile strength and shrinking behavior of various ash powder bed collected from the coal-fired power plant and waste incinerator at high temperature ranging from 773 to 1173 K, we estimated that a very few amount of liquid or slag phase formation of main component SiO2 with alkali metal, such as Na and K, contributed to the increase of adhesion force between ash particles. However, since many other chemical compounds were included in real combustion ash, it is difficult to discuss the quantitative influence of alkali component in ash on the adhesion behavior at high temperature. In this study, in order to clarify the influence of alkaline components on adhesion behavior, some kinds of synthesized model combustion ash particles with different alkali metal content were synthesized from pure silica particles. The tensile strength and shrinking behavior of each synthesized ash particle bed at high temperature was carried out and analyzed by thermodynamic calculation. Fig.1 shows tensile strength at 900°C of synthesized ashes with different contain of Na and K. By the few amounts of Na and K content (lower than several few %) in synthesized model ash, the adhesion force increased more than several 10 times compared with pure silica particles. Furthermore, alumina nanoparticles, which was useful to reduce adhesion force by the addition with real ash particles in our previous paper, were similarly added to synthesized model ash, and then the effect of adhesion behavior at high temperature were investigated.

PA325 Low-pH Stressed Cell Exosomes with Superior Cellular Uptake as Targeting Drug-carrier for Combined Chemotherapy and Photodynamic Anticancer Therapy
Changguo GONG1, Yugang WANG1, Min SHI1, Rongrong JIA1, Guanghui MA2, Wei WEI2
1 Shanghai Tongren Hospital, Shanghai, China
2 Institute of Process Engineering, Chinese Academy of Sciences, Beijing, China

As mediators for cell communication, exosomes are an emerging carrier for drug delivery. Cell communication is a dynamic process, will affected dramatically by the cell conditions, however, the present studies only focus on the normal condition. Inspired by this, we compared the cancer cell uptake of five different stressed and normal cancer cell originated exosomes, found that low-pH stressed cell secret exosomes have the highest uptake efficiency (2.9 times of normal exosomes). Lipidomics data and molecular-dynamics simulations indicated that the unique lipid composition played the key role for cancer cell membrane affinity which further affected cancer cell uptake efficiency. The homologous targeting was evidenced by the gastric cancer cell (MGC803) originated exosomes were only uptaken by cancer cells (MGC803, HGC27 and MKN45), the gastric epithelial cell (GES1) exosomes were only uptaken by GES1, the tumor targeting was further verified by the in vivo imaging of biodistribution. Using the low-pH stressed cancer cell exosomes, we loaded the hydrophobic doxorubicin (Dox) in the lipid membrane and a hydrophilic photosensitizer, Al (III) phthalocyanine chloride tetrasulfonic acid (AlPcS4) in the lumen to construct a combined anticancer therapy platform. The reactive oxygen species generated by AlPcS4 after irradiation destructed the exosomes for rapid released of Dox, at the same time, induced apoptosis with released Dox in a synergistic manner. The superior anticancer therapeutic effects were achieved both in vitro and in vivo. The successful utilizing of low-pH stressed cell exosomes for gastric cancer therapy in this study indicated that the efficient exosomes may have great potential for various anticancer drug delivery.

PA326 Dispersion of cellulose nanofibers in epoxy based resin assisted by surface modified SiO2 nanoparticles
Marina SAITO1, Tatsuya KUMADA2, Toshimitsu MORIYA2, Hiroyuki IZAWA2, Junichi TATAMI1, Motoyuki IIJIMA1
1 Yokohama National University, Yokohama, Japan
2 Hitachi Chemical Co., Ltd., Chikusei, Japan

Epoxy-based resin filled with SiO2 nanoparticles is one of useful composites applied as adhesives for electronic devices, as it provides reliable insulation resistance and improved mechanical properties. On processing SiO2/epoxy composites, a compound with lower viscosity which is favorable for shaping and those curable to a material with improved elastic modulus is required. However, since the disaggregation of SiO2 nanoparticles is essential for the former and network formation is necessary for the latter, the realization of both properties was a kind of contradiction and difficult to achieve. To overcome this issue, herein we report a processing route to fabricate epoxy-based composites co-filled with SiO2 nanoparticles and cellulose nanofibers (CNFs). First, the surface of SiO2 nanoparticles were modified to improve the compatibility with epoxy-based resin. Briefly, the adsorption of functional dispersant, polyethyleneimine partially complexed with oleic acid (PEI-OA), on SiO2 nanoparticles and further epoxy grafting from the free amine groups of PEI-OA was conducted simultaneously in toluene with bead milling. The disaggregated and surface modified SiO2 nanoparticles were collected by centrifugation and redispersed in ethyl acetate. Then, CNFs and epoxy based resins (a mixture of bisphenol-F type phenoxy resin and bisphenol-A type epoxy resin) was mixed with the epoxy-grafted SiO2 dispersion. While CNFs strongly aggregated in the solution of ethyl acetate/epoxy-based resin, CNFs found to disperse and flowable suspension was obtained when the epoxy grafted SiO2 nanoparticles were co-dispersed (>1 mg-CNF/g-SiO2). Furthermore, the cured epoxy-based resin filled with SiO2 nanoparticles (15 phr) and CNFs (1.0 mg-CNF/g-SiO2) showed improved storage elastic modulus above Tg compared to those without CNFs. We suspect that SiO2 nanoparticles having a surface compatible with epoxy resin adsorbed on CNFs and stabilized them in the resin/solvent solution. The existence of small amount of dispersed CNFs were effective to improve the mechanical properties of epoxy-based composites.

A413 [Keynote] Hollow multi-shelled structures particles: Synthesis and applications
State Key Laboratory of Biochemical Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing, China

Hollow multi-shelled structures (HoMSs) with hollow interior and multiple shells have been recognized as one type of promising material for applications in in energy conversion and storage, sensors, catalysis, electromagnetic absorption and drug delivery, etc. However, compared to their single- shelled counterparts, the synthesis of HoMSs is much more challenging due to the increased complexity of the structure.
Our group proposed a general and widely usable sequential templating approach (STA) to prepare HoMSs by utilizing carbonaceous spheres as templates to adsorb metal ions and heating them to remove the template and generate multiple shells. Numerous HoMSs of single metal oxides (such as α-Fe2O3, ZnO, Co3O4, SnO2, TiO2, Mn2O3 and V2O5), metal sulfides (Ni3S2, NiS, NiS2), binary metal oxides ((CO2/3Mn1/3)(Co5/6Mn1/6)2O4) and also heterogeneous mixed metal oxides (ZnO@ZnO/ZnFe2O4@ ZnO/ZnFe2O4) have been successfully prepared using STA. The concentration and radial distribution of metal ions can be adjusted by changing the corresponding experimental conditions, such as the metal salt concentration, the solvent, the adsorption temperature and duration, the heating temperature and rate, and so forth, thus controlling the geometric parameters of HoMSs.
The breakthrough of synthetic methodologies for HoMSs also provides opportunities to acquire unique physical or chemical properties and performance in specific applications by manipulating their geometric structures, such as shell numbers, shell thickness, inter-shell space as well as shell composition and morphology. Many successful examples have been well demonstrated in the specific fields, including dye-sensitized solar cells, lithium ion batteries, sodium-ion battery, alkaline rechargeable battery,[14,16, 19] photo detector, gas sensors, etc.

A415 (canceled) <506501-1>
A416 [Invited] Pickering Emulsion: Old Trees Blossom New Flowers
Guanghui MA, Jie WU, Yufei XIA
State Key Laboratory of Biochemical Engineering, Institute of Process Engineering, Chinese Academy of Sciences

Pickering emulsion is a special emulsion stabilized by nanoparticles instead of surfactant, it has been studied since 1903. Pickering emulsion has many advantages, for example: it is more stable than normal emulsion; its properties can be modulated by nanoparticles. However, conventionally SiO2 or polystyrene (PST) nanoparticle was used for preparing Pickering emulsion because uniform SiO2 and PST nanoparticles are easily prepared. The bio-application study of Pickering emulsion was limited due to the preparation difficulty of uniform biodegradable nanoparticles.
In this study, we prepared uniform alginate/chitosan and poly(lactide-glycolide) (PLGA) biodegradable nanoparticles by membrane emulsification technique and other technique, and used them to prepare Pickering emulsion for Insulin oral delivery and advanced engineered vaccine.
Firstly, we prepared alginate nanoparticle by rapid membrane emulsification technique, then we obtained alginate/chitosan nanoparticle by layer-by-layer process. Then, we prepared Pickering double emulsion (W/O/W) with insulin solution as inner water phase, PLGA/ethyl acetate (EA)/Arlacel 83 as oil phase, and nanoparticle aqueous phase as outer water phase. Then, after removing EA, we can obtain microcapsule with nanoparticle on its surface, it is called colloidosome. This colloidosome showed pH-sensitivity, it was stable at pH 1.2 (stomach), but released insulin quickly at pH 6.8 (Intestine), due to the pH-sensitivity of alginate/chitosan nanoparticle. Finally, the blood glucose level can be decreased apparently after oral administration.
Secondly, we prepared Pickering emulsion (O/W) by using squalene as oil phase, and PLGA nanoparticle aqueous phase as outer phase. Then we assembled antigen in the gap among nanoparticles to form engineered vaccine. We found that this vaccine mimic pathogen behavior, it showed force-dependent deformation, and antigen can move at oil/water interface. As a result, compared with conventional emulsion, it exerted potent immune protections against influenza virus challenge, and enhanced therapeutic anti-tumor efficiency, when we loaded H1N1 or MUC1 antigen on this Pickering emulsion, respectively.

A417 Direct increase of intracellular hydrogen peroxide and enhancement for radiosensitivity with polyacrylic acid-modified titanium peroxide nanoparticles
Chiaki OGINO1, Kenta MORITA1, Yuya NISHIMURA1, Chiya NUMAKO2, Masao NAKAYAMA1, Ryohei SASAKI1, Akihiko KONDO1
1 Kobe University
2 Chiba University

Polyacrylic acid–modified titanium peroxide nanoparticles (PAA-TiOx NPs) locally injected into tumors exhibit radiosensitizing activity in vivo, enhancing the therapeutic effect of X-ray irradiation. However, the underlying mechanism remains unclear except for the involvement of hydrogen peroxide (H2O2), which is continuously from the PAA-TiOx NPs. Thus, this study investigated the details of H2O2 release from PAA-TiOx NPs and the effect on radiosensitivity of cultured tumor cells in vitro using a clonogenic assay in comparison with H2O2 solution as a control. PAA-TiOx NPs were internalized by treated cells within 10 min and released H2O2 for at least 7 h. Interestingly, further experiments revealed a significant increase in the intracellular H2O2 concentration corresponding with PAA-TiOx NP internalization. Additional X-ray irradiation killed tumor cells that had internalized PAA-TiOx NPs more effectively than tumor cells treated only with H2O2. PAA-TiOx NPs represent a novel radiosensitizing system for generating H2O2 in tumor cells.

A421 [Invited] Biomimetic formulation engineering for anticancer therapy
Wei WEI, Guanghui MA
State Key Laboratory of Biochemical Engineering, Institute of Process Engineering, Chinese Academy of Sciences

Owing to the extreme complexity in vivo, the performance of elaborately designed anticancer formulation in the final clinical trials is often compromised from the previous experimental results. Such a inconsistency apparently reduces the druggability of the research objects and increases the risk of new drug development. Therefore, it is urgent to change traditional ideas of research and development for anticancer formulation.
In order to solve this problem, we have integrated the structure, function and program of biological systems into the design, and developed new preparation processes to construct a series of biomimetic anticancer formulations. For example, we developed in situ drug loading technology based on the unique hollow-porous structure of cage proteins. The high expression of corresponding receptors on the surface of tumor cells further enabled us to achieve targeted drug delivery. Meanwhile, a new hydrothermal process was developed to precisely regulate the bacterial structure for the accommodation of tumor antigen. Through natural infection, a large amount of antigen could be delivered to the dendritic cells, leading to a potent immune response. In addition, we also developed a new membrane emulsification process to coat the nanoparticles with cell membranes, thereby endowing them with excellent in vivo fate, such as long circulation and tumor penetration. Such a camouflage approach could significantly improve the performance for cancer imaging, diagnosis and chemotherapy.
As aforementioned, biomimetic formulation followed the intrinsic transport route in vivo, and precisely delivered drug, antigen or probe to the target site as expected. We believe these candidates will lead to the slightest adverse reaction, obtain the optimal application effects, reduce the risk of research and development, and promote the clinical conversion.

A422 [Invited] Design of functionalized polyethyleneimine as versatile surface modifier for processing nanoparticles in nonaqueous solvents
Motoyuki IIJIMA, Momoko KATAOKA, Junichi TATAMI
Yokohama National University, Yokohama 240-8501 Japan

Controlling dispersion stability and assembled structures of nanoparticles in solvents during processing nanoparticle-based composite materials is one of the most important key factors toward designing the material properties. Although various surface designs have been reported up to date to achieve the improvement of nanoparticle dispersion stability, most system suffers from limited conditions to have enhanced dispersion stability (i.e. limitation in dispersible solvents and nanoparticle species). Herein, we report a new class of polymer dispersants which can be applied to various combinations of particles and solvent species. The proposed dispersant design involves the partial complex formation of polyethyleneimine (PEI) with functional anionic surfactant, which branches into polyethylene glycol based hydrophilic chain and alkyl based hydrophobic chain near the head group. The designed PEI-complex found to effectively adsorb on various species of particles including metal oxides, metal nitrides, metals, and carbon related materials. The particles fully covered with the designed dispersant were able to be dispersed into various series of solvents such as methanol, methyl ethyl ketone, ethyl acetate and toluene. Due to the high versatility of the designed dispersants, nanoparticles were able to be stabilized though relatively complicated process, such as ligand exchanging process of oleylamine stabilized Ag nanoparticles and simultaneous surface modifications of gas phase synthesized SiO2 nanoparticles during bead milling treatments. As well as the dispersion properties of PEI-complex-stabilized nanoparticles, some of our achievements toward aligning the surface modified nanoparticles on template particles/nanofibers and micro-structural control of composite materials will be introduced.

A424 Manipulating cell transport for simultaneous systemic and gastrointestinal immune responses via oil-in-polymer particles
Yufei XIA, Guanghui MA
Institute of Process Engineering, Chinese Academy of Sciences

As peripheral lymphocytes are typically excluded from the gastrointestinal lymph tissues, current parenteral vaccinations failed to simultaneously induce systemic and mucosal responses. To break the natural barrier, we developed and heralded “immunoticket” capsules. Via internal phase separation, the capsules were formed with positive charged shells and oily core (oil-in-polymer particles) to spatiotemporally deliver antigens and all-trans retinoic acid (RA). After intramuscular vaccinations, these capsules functioned as immunoticket to cultivate the peripheral DCs with chemokine receptor 9 (CCR9). By hitchhiking on the concentration gradient of chemokine (C-C motif) ligand 25 (CCL25), the primed DCs would home to the gut associated lymphoid tissues (GALTs) and induced antigen-specific IgA secretion and T cell engagements. Compared with the currently employed RA-involved formulations, the immunoticket capsules stimulated enhanced RA-mediated gut-tropism by mounting the inflammatory innate immunity. Through controlling RA payloads, the potential regulatory T cell engagement was circumvented. In OVA and EV71 vaccinations, the immunoticket capsules induced potent serum IgG titer, antigen-specific cytotoxic T cells in the peripheral lymph tissues, as well as robust IgA secretion and T cell engagements on gastrointestinal sites. Our data suggested the potential of the immunotickets to serve as facile, effective and safe strategy to provide comprehensive immune responses against gastrointestinal infections and diseases.

A425 Exploration of 2D graphene oxide as advantageous biomedical delivery systems
Hua YUE, Wei WEI, Guanghui MA
State Key Laboratory of Biochemical Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing, China

Using delivery system shows promising signs on biobased therapy. However, there's a huge challenge for incorporating all the bioactive factors into one single carrier, leading to unsatisfied efficiency for present antigen/drug delivery system (A/DDS). To break this bottleneck, we uncover the cellular response that induced by graphene oxide (GO) and establish specific A/DDS based on this two dimensional material. On one hand, the flat micro GO exhibit unique properties, including extraordinarily high level of antigen adsorption, intracellular folding effect, and autophagy induction. Such a “One but All” vaccine delivery system induces high level of anti-tumor responses in a programmable way and finally results in the in vivo tumor regression. On the other hand, we evidence sandwiched graphene-cell membrane superstructures in different cells and reveal the transport of GO varies from Brownian to Lévy and even directional dynamics. In terms of above unique advantages, the applicability of sandwiched GOs in enhanced efficiency of membrane-specific drug delivery is thus demonstrated. Our findings inform approaches to program two-dimensional nanomaterials towards advantageous tumor vaccine delivery and intramembrane drug transport.
[1] Pengyu Chen#, Hua Yue#, Xiaobo Zhai, Zihan Huang, Guanghui Ma, Wei Wei, and Li-Tang Yan. Transport of graphene nanosheet sandwiched inside cell membranes. Sci Adv, 2019. Accepted (# Authors contributed equally)
[2] Hua Yue, Wei Wei, Zonglin Gu, Dezhi Ni, Nana Luo, Zaixing Yang, Lin Zhao, Jose-Antonio Garate, Ruhong Zhou, Zhiguo Su, Guanghui Ma. Exploration of graphene oxide as an intelligent platform for cancer vaccines. Nanoscale, 2015, 7, 19949-19957 (Back cover story)
[3] Hua Yue, Wei Wei, Zhanguo Yue, Bin Wang, Nana Luo, Yongjun Gao, Ding Ma, Guanghui Ma, Zhiguo Su. The role of the lateral dimension of graphene oxide in the regulation of cellular responses. Biomaterials, 2012, 33(16): 4013–4020

Session S7. Carbon capture, utilization, and storage (CCUS)

G321 [Keynote] Challenges and opportunities for carbon capture and utilisation in high CO2 content natural gas environment
CO2 Research Centre, Institute of Contaminant Management, Chemical Engineering Department, Universiti Technology PETRONAS, Bandar Seri Iskandar, Tronoh, 32610, Perak, Malaysia

Natural gas reserves available worldwide includes varying amounts of CO2 ranging from CO2-free in Siberia to as high as 90% CO2 content in the Platong and Erawan fields in Thailand. The Natuna field in the Greater Sarawak Basin in Indonesia is the largest gas field in south east Asia, with estimated 46 trillion cubic feet of recoverable reserved. Unfortunately, it remains unexplored due to high CO2 content up to 71%. In Malaysia, CO2 content from natural gas fields varies up to 87%. Over 13 trillion cubic feet of natural gas reserves are undeveloped due to the presence of high CO2 content. The high CO2 content in natural gas is a major issue to monetizing the gas reserves. Without the removal of its CO2 content, natural gas cannot be further processed, liquefied, transported or commercially sold. However, the release of bulk CO2 into environment aggravates global warming and violates the requirement of Kyoto Protocol. Hence, there is a need for the development of technologies for the effective capture and subsequent utilization of CO2 for its conversion into value added products. In this paper, the recent advances on the potential technologies to manage the CO2 rich natural gas fields is deliberated. Challenges for gas treatment including capturing systems (from common technologies such as absorption, adsorption, cryogenic and membrane to novel technologies such as CUAS) and their applications towards a wide range of CO2 concentrations are presented. Additionally, the opportunities of separating huge amount of CO2 from such environments to produce added values products (bio fuel, synthetic-fuel, CO2-EOR, power production, etc.) are discussed.

G323 Carbon Dioxide Capture by Sodium Hydroxide-Methanol Solution in a Rotating Packed Bed
Chia-Ying CHIANG1, Yuk-Man TANG2, Hwai-Shen LIU2
1 Department of Chemical Engineering, National Taiwan University of Science and Technology, Taipei, Taiwan
2 Department of Chemical Engineering, National Taiwan University, Taipei, Taiwan

In a well-known efficient CO2 absorption process, Rectisol, chilled and pressured methanol is used as the absorbent to capture of CO2 physically. Unfortunately, because of higher solubility of CO2 in methanol under lower temperature and higher pressure, this process requires strict conditions (-40 ~ -60 oC and 3~8 MPa) and this leads in high demand of both operating and equipment costs. Therefore, a rotating packed bed (RPB) was evaluated to capture CO2 with NaOH in aqueous methanol as well as pure methanol solution under ambient conditions to relax low-temperature and high-pressure constraints. The experimental results suggest that with the NaOH-methanol solution, the absorption could be almost completed (~100%) within one gas/liquid pass in an RPB at room temperature and atmospheric pressure. Furthermore, the apparent overall mass transfer coefficient could be elevated to almost 5 s-1, which is one of the highest values among the RPB-related chemical absorption processes. Under this intensified centrifugal field, it is clear that CO2 capture can be highly enhanced with this good combination of physical-chemical absorbent, NaOH-methanol solution.

G324 CO2 separation membrane modules for high purity CO2 recovery
Kyushu University, Fukuoka, Japan

High purity CO2 recovery with lower energy consumption is required for effective CO2 Capture and Utilization/Storage (CCUS), and membrane separation would be suitable for the CO2 separation. Our research group has investigated and developed amine-containing polymeric membranes for effective CO2 capture. For example, amine-immobilized poly(vinyl alcohol) (PVA) membranes show excellent CO2 separation properties even over smaller H2. It was found recently that alkanolamines, such as 2-(2-aminoethylamino)ethanol (AEAE), elevated the CO2 separation properties, and mechanism of the preferential CO2 transportation was elucidated. Under humidified conditions, carbamate formed by an interaction between CO2 and the secondary amino group of AEAE was hydrolyzed to give bicarbonate ion, which was the major migrating species through the membrane. The hydroxyl group of alkanolamines facilitate the interaction to enhance bicarbonate production upon hydrolysis of the carbamate.
For pilot-scale demonstration, a hollow membrane module was prepared by in-situ modification (IM) method (Duan S., J. Membr. Sci., 2006). An aqueous solution of amines and PVA was circulated in a commercial hollow-fiber membrane module, and a CO2-selective layer was formed on the inner surface of hollow fiber membrane (Fig. 1). The thickness of the active layer was determined by circulation period, concentration of the solutes, and flow rate of the solution. The optimization of the IM method explained that 5 min circulation was enough to obtain higher CO2 permeability and CO2 selectivity. While the amines were physically immobilized in a polymer matrix, decrease in the CO2 separation performance was not found at all under 90 % relative humidity at 50 °C for about 300 h, which was triggered by the leakage of the amines. The IM method is preferable for mass production, and the scale-up is also feasible. The membrane modules developed would be suitable for biogas upgrading and air capture to obtain high purity CO2 in the permeate.

G325 [Keynote] Manufacturing advanced structured contactors with integrated heat management capabilities
School of Chemical and Biomolecular Engineering, Georgia Institute of Technology, Atlanta, GA, USA

CO2 capture from dilute sources (e.g., flue gases, air) and subsequent storage or conversion will play a key role in the carbon-constrained future. The low driving force for CO2 capture from these dilute streams has positioned adsorbent materials and adsorption technology as a leading approach for addressing this global challenge. The creation of robust materials-enabled advanced adsorption separators and their manufacturing into low-cost, energy-efficient devices will be the focus of the talk. Engineering novel materials—such as solid-supported amines, metal-organic frameworks, and polymers of intrinsic microporosity—into structured contactor adsorption devices shows promise for these CO2 capture applications. Structured sorbent contactors can help manage kinetic and engineering factors associated with the separation, including pressure drop, sorption enthalpy effects, and external heat integration (for temperature swing adsorption). Monoliths, fiber sorbents, and 3D printed materials will be discussed as the three main classes of existing or emerging structured sorbent contactors. Recent developments in their manufacture; advantages and disadvantages of each structure relative to each other and to pellet packed beds; recent developments in system modeling; and finally, critical needs in this area of research will all be discussed.

G401 [Keynote] Chinese CCUS overview and CO2 mineralization research for concrete curing
State Key Laboratory of Clean Energy Utilization, Zhejiang University, China

CCUS (Carbon Capture, Utilization and Storage) is an important choice for a sustainable low-carbon development in China. The Chinese government attaches great importance to guiding the development of CCUS technology and has taken a series of measures to reduce CO2 emission in the past decade. This speech provides an overview of CCUS technology development which contained specific details about supported program from National Key R&D Program of China. The speech will also introduce several leading large-scale CCUS industrial demonstrations in China, by summarizing the technical characteristics, reactivity, and procedural scheme of each demonstration. An outlook on future development will be provided according to the 13th Five-Year Plan of China (2016-2020), which is focused on promoting large-scale industrial demonstration in the coal-based industry and oil and gas exploration industry.
One of the promising CO2 utilization demonstration projects is carbonation curing of concrete. CO2 curing technology has two major benefits: (i) rapid strength gain of cementitious materials, and (ii) large-scale CO2 sequestration in concrete. The gas-solid reaction kinetics between CO2 and cement-based materials were studied. According to the fitting results of different kinetic models, the carbonation curing of concrete showed a progressive product-layer-diffusion limited kinetics despite different factors. Our group also evaluated the feasibility of blending calcium silicate (CS) as intensified addition, which was found to significantly enhance the reaction rate and CO2 uptake capacity. In terms of practical feasibility, carbonation curing also improved the compressive performance of cement paste with CS. In addition, three typical industrial solid wastes - fly ash, blast furnace slag, and red mud - were studied to replace part of the cement materials to reduce CO2 emissions. The effects of carbonation curing time, pressure, and water-to-solids ratio on the CO2 uptake and compressive strength were comprehensively studied.

G403 Application of DDR-type zeolite membrane for CO2-EOR
Shogo TERATANI1, Mizuki YOSHIDA1, Tomoya NONOUE1, Junya OKAZAKI1, Hiroaki HASEGAWA1, Katsuya SHIMIZU2, Kenji YAJIMA2, Makiko NIINO2
1 JGC Corporation, Yokohama, Japan
2 NGK Insulators, Ltd., Nagoya, Aichi, Japan

As one of the most important technologies for Carbon dioxide (CO2) Capture, Utilization and Storage (CCUS), the practical application of CO2 enhanced oil recovery (CO2-EOR) has been growing rapidly. Since the profitability of CO2-EOR project can be improved by the re-use of CO2 contained in the associated gas, superior CO2 separation technology is essential. JGC Corporation (JGC) and NGK Insulators, Ltd. (NGK) have developed CO2 separation system with DDR-type zeolite membrane. In many cases, the associated gas also contains hydrocarbons in which predominant constituent is methane (CH4). Since DDR-type zeolite has subnano-size pores which are desirable for CO2/CH4 separation, this membrane achieves excellent CO2 permselectivity. In addition, this system can be operated under high CO2 partial pressure conditions (~ 8 MPa) which is suitable for CO2 recovery process from associated gas with high pressure and high concentration of CO2. Recently, JGC has launched the first field test with laboratory scale DDR-type zeolite membrane at a CO2-EOR oil field. The membrane was prepared onto the inner surface of 30 channels in a cylindrical monolithic alumina substrate (diameter: 30 mm, length: 160 mm). In this field test, it has been confirmed that this membrane performed well for CO2 separation from the associated gas. It's of note that the performance observed using the associated gas was substantially equivalent to that of obtained using a simulated gas consisting of CO2 and light hydrocarbons in laboratory tests. In this presentation, the features of the DDR-type zeolite membrane as well as the summary of the first field test at a CO2-EOR oil field are addressed. In addition, the outline of the ongoing demonstration project with commercial scale DDR-type zeolite membrane (diameter: 180 mm, length: 1,000 mm) is introduced.

G404 Performance evaluation of DDR type zeolite membrane under high pressure condition
Mizuki YOSHIDA1, Shogo TERATANI1, Tomoya NONOUE1, Junya OKAZAKI1, Hiroaki HASEGAWA1, Katsuya SHIMIZU2, Kenji YAJIMA2, Makiko NIINO2
1 JGC Corporation, Yokohama, Japan
2 NGK Insulators, Ltd., Nagoya, Aichi, Japan

Along with the growth of CO2 enhanced oil recovery (CO2-EOR) industries, demand of CO2 separation technologies has been increasing to recover CO2 from associated gas which contains not only CO2 but also hydrocarbons mainly CH4. DDR-type zeolite membrane has the subnano-size pores which are preferable for CO2/CH4 separation, resulting in the excellent CO2 permselectivity. In this study, CO2 permeance and selectivity of the DDR-type zeolite membrane were examined under high pressure conditions using CO2/CH4 binary gas mixture to evaluate the potential applicability for CO2 recovery process in CO2-EOR industries. The membrane was prepared onto the inner surface of multi channels in a cylindrical monolithic alumina substrate (diameter: 30 mm, length: 160 mm). The membrane properties are investigated using one channel of the substrate. The test pressure was increased up to 8 MPaG with the temperature range of 90 - 150 deg. C. The CO2 concentration in the gas mixtures were varied from 50 to 100 %. From these experiments, CO2 permeance decreased with increasing pressure and temperature. In addition, CO2 permeance and selectivity decreased with decreasing CO2 partial pressure in the experiments with CO2/CH4 binary gas mixture. CO2 permeance obtained in experiments was correlated by the surface diffusion model coupled with adsorption isotherm equations (Langmuir equation and Dubinin-Astakhov equation). The surface diffusion model could correlate CO2 permeances well against the wide range of CO2 partial pressure. The comparison of CO2 adsorption curves estimated by the correlation was implied that the competitive adsorption between CO2 and CH4 was occurred in this system and it affected to CO2 permeability of the DDR-type zeolite membrane. As mentioned above, the amount of adsorbed CO2 decreased as CH4 concentration in binary gas increased because of competitive adsorption. In contrast, gas diffusion constant and equilibrium constant were not changed.

G405 Alkali nitrate modified flash calcined MgO for the in-situ CO2 capture in the water-gas shift reaction
Dan Allen Zamora1, Jacinto Lamud1, Qian Shun Yong1, Thomas HANH1, Hongzhe LI1, Nicholas BEDFORD1, Jason SCOTT1,2, May LIM1
1 School of Chemical Engineering, The University of New South Wales, Sydney 2052 NSW, Australia
2 Particle Catalysis Research Group, The University of New South Wales, Sydney 2052 NSW, Australia

High surface area magnesium oxide (MgO) has garnered interest as an in-situ CO2 sorbent for the water-gas shift reaction (WGSR) for its low regeneration temperature and uptake of CO2 gas at intermediate temperatures of 300 °C upon modification with alkali nitrate salts. Semi-industrial scale production of these high surface area MgO sorbents (>200 m2·g-1) can be achieved via Calix's flash calcination process. Upon modification with NaNO3, the CO2 uptake of MgO in a pure CO2 environment after 1 h improved by a factor of 27 to 11.1 mmol CO2·g-1. The sorbent retained 60% of its CO2 capacity after 40 adsorption-desorption cycles, outperforming a commercial MgO control. The higher uptake of the NaNO3 modified high surface area MgO is attributed to a higher ratio of NaNO3 to MgO, resulting in larger and more similarly sized crystallites of MgO and NaNO3. This improves the extent of interphase boundaries between the molten salt and gaseous CO2, improving the rate of adsorption of CO2 into the sorbent. The molten salt also influences the sintering of MgO and NaNO3, which further increased the crystallite size and surface area in the first few cycles. When applied as a sorbent in the Cu catalysed WGSR, the NaNO3 modified MgO sorbent exhibited a CO conversion of 27% at 300 °C, while CO2 output remained relatively high. The high CO2 output is attributed to the loss of basic sites when the NaNO3-MgO sorbents are mixed with the Cu catalyst, which lowers the retention of CO2 at 300 °C, and impedes the effect of NaNO3 in capturing CO2 in the WGSR.

G406 Auto-methanation of carbon dioxide with oxidation: a novel route for CO2 transformation over supported metal catalyst
Choji FUKUHARA1, Sakhon Ratchahat2, Masao SUDOH3, Ryo WATANABE1
1 Graduate School of Engineering, Shizuoka University
2 Faculty of Engineering, Mahidol University
3 Amano Institute of Technology

The CO2 methanation has received attention as a reaction converting CO2 into a useful resource such as methane (PtG technology). When assuming that methanation is used as a reaction to process CO2 emitted from an industrial process, the presence of oxygen may have a negative influence, such as an oxidation of the active site. In this study, to examine the influence of O2 on the catalytic function, the methanation performance of a Ni/CeO2 catalyst was evaluated using a raw material gas containing oxygen of 1–10 vol%. As a result, the methanation activity at a lower temperature was greatly improved, and the ability to produce a high methanation performance was realized even in a region at room temperature. We found a novel route of CO2 methanation that can be driven with no heating, even in ambient, which we named as auto-methanation. No one in the World has reported such transformation route yet.
A granular Ni/CeO2 catalyst was prepared using evaporation to dryness of Ni(NO3)2·6H2O on CeO2 support. The CO2 methanation was investigated using conventional flow-type reactor by introducing feed-gas at setting temperature of 350 °C down to room-temperature. The raw gas contained CO2, H2, O2, N2. The CO2 concentration was fixed at 10 vol% with 400 ml/min.
Figures 1(a) and 1(b) show CO2 conversion and product-selectivity. When supplying oxygen of 1 vol% and 3 vol%, the drastic change in conversion shifted to the lower side, which was near room temperature. At oxygen of 5 vol% and 7 vol%, about 65 and 70% conversions were obtained even at room temperature without external heating. Methane selectivity was almost 100% at lower temperature. Figure 1(c) is snapshot of the auto-methanation state. A combination of methanation and combustion might offer a novel CO2 transformation technique, which will open a new process.

G413 [Keynote] IHI PCC technologies demonstration at a coal-fired power plant
Takumi ENDO
IHI Corporation, Toyosu IHI Building, 1-1, Toyosu 3-chome, Koto, Tokyo 135-8710 Japan

The CO2 separation technology is considered to play a key role to reduce or control the CO2 emission from the fossil fuel, especially from coal in the world. Australia, rich in coal resources, is also facing “De-carbonization trend” and thus technical solutions are needed.
In Australia, we launched an internationally collaborative PCC (Post Combustion Capture) demonstration project in 2014. The name of the project is the abbreviation of PCC, and IHI (Japanese engineering company), CSIRO (Australian research institute), AGL (Australian power company), the partners of the project.
Prior to the project, we had developed IHI advanced CO2 captured system with 20 ton CO2/day scale pilot plant in Japan, which mainly consists of the IHI Solution No.162 (ISOL-162), the advanced packing material and the advanced process enabling to significantly reduce the solvent regeneration energy.
Through the long term operation at this demonstration project under the practical conditions, i.e., using the flue gas of an operating brown coal-fired power plant, we have evaluated our integrated PCC technologies. During the operation, 90 % CO2 capture ratio was achieved stably and other measured values were also kept stable. The results indicate that the PICA plant and the ISOL-162 solvent have sufficient stability and robustness to enable long term operation.
IHI has improved the design and refined operation to provide a robust and environmentally friendly PCC system based on the knowledge and technologies obtained through the ISOL-162 long-term operation using the PICA pilot plant and parallel research activities.
Over the long term operation, practical studies of the emission evaluation were carried out. The emissions of amine and its derivatives from the outlet of the washing tower were measured on various wash-type conditions. The result clearly demonstrated that the amine emission from the system was considerably reduced and minimized by the application of the washing technologies. The demonstration results are explained in detail in the presentation.

G415 Determination of the properties of mixed dump serpentinites from Nickel mine site through leaching process for indirect CO2 mineral carbonation
Bernard Jomari B. Razote1, Ramon Christian P. EUSEBIO2, Mark Kenneth MARANAN2, Richard D. ALORRO3, Arnel B. BELTRAN1, Aileen H. ORBECIDO1
1 Chemical Engineering Department, Gokongwei College of Engineering, De La Salle University, 2401 Taft Avenue, Manila 1004, Philippines
2 Chemical Engineering Department, College of Engineering and Agro-Industrial Technology, University of the Philippines-Los Baños, Los Baños, Laguna, Philippines
3 Western Australian School of Mines: Minerals, Energy and Chemical Engineering, Faculty of Science and Engineering, Curtin University, Kargoorlie, Australia

Indirect carbon sequestration via mineralization has been perceived as an alternative solution to address increasing anthropogenic emissions. Ex situ mineralization, in contrast with the in situ counterpart, has been the focus of recent studies as it provides a faster and more efficient carbon capture process due to the addition of a leaching step that releases the ions available for intimate contact with carbon dioxide. Mixed dump serpentenite samples from a Nickel mine site in Mindanao, Philippines were characterized through leaching tests to determine their viability in carbon sequestration. Ground samples of 75-150 microns particle size were leached with hydrochloric acid concentrations of 1 M, 2.5 M, and 4 M, at temperatures of 50C, 75C and 100C. The reaction time was also set at 1 hr, 2.5 hrs, and 4 hrs, respectively. The optimum set of conditions were then determined by analyzing the extraction efficiencies of Mg, Fe, Si, Ca, and Al ions from the aforementioned set of parameters, using the Face-Centered Cube model for Response Surface Methodology. Prior to leaching, XRD, XRF, and ICP-MS analyses were performed to determine the dominant minerals and elemental composition of the sample. The morphology and crystal structure of the optimum and non-optimum samples were also confirmed by BET and SEM analyses to establish the relationship of the crystal structure of the media to the ion extraction efficiencies.

G416 Chemical kinetics of oxygen carriers for chemical looping combustion technology producing CO2 rich flue gas from coal fired power plant
National Institute of Advanced Industrial Science and Technology, Research Institute of Energy Frontier, Non-conventional Carbon Resources Group, 16-1, Onogawa, Tsukuba, Japan

Efficient and economical CO2 capture from coal-fired power plants is a major challenge for the application of CCS concept as this step incurs primary cost and energy penalty. Oxy-fuel combustion and post-combustion CO2 capture using Amine process are few approaches but are energy intensive. Chemical Looping Combustion (CLC) technology where oxygen for combustion is supplied by metal oxygen carriers instead of air is finding application in coal fired power plants for its economical CO2 capture. The oxygen carrier is circulated between the two reactors, Fuel reactor and Air reactor which usually operate under fluidized bed conditions. The flue gases from Fuel reactor contain CO2 and H2O which can be easily separated leading to nearly pure CO2 and thus reducing the energy requirement for CO2 separation. Therefore, development of a robust, effective and economical metal oxygen carrier is of primary research interest. This study reports and compares the reduction-oxidation characteristics of several oxygen carriers. Basic reduction-oxidation experiments were carried out in a small fluidized bed reactor by switching gases. Effect of reduction temperature, gas residence time, and type of oxygen carrier on conversion efficiency was investigated. Results were discussed in terms of their physical characteristics, oxygen capacity, oxygen release rate and stability after repeated redox cycles. A first order reaction was applied to analyse the reduction kinetics. The study also reports long run performance results of a 100kW scale circulating fluidized bed bench scale CLC unit developed at AIST under NEDO project.

G417 Influence of amine-based absorbents on CO2 desorption in membrane flash process using alumina porous hollow fiber membranes
Faculty of Textile Science and Technology, Shinshu University, Japan

A novel process named a membrane flash process was studied to realize an energy-saving technology and to substitute it for a conventional process using steam for regeneration of the CO2 absorbent liquids in CCS. In this study, four different amine-based absorbents (MEA, DEA, MDEA, MDEA and piperazine (PZ)) were tested to find an absorbent favorable for the membrane flash process using an alumina microporous hollow fiber membrane.
CO2 rich solution of each absorbent was supplied into the tube side of the hollow fiber and the pressure on the shell side was reduced so that the pressure difference between the tube and shell sides was 45, 65, 85 and 95 kPa. The absorbent liquid was forced to permeate through the pores of the membrane and CO2 was released during and after permeation. MEA showed the highest liquid permeation rate while MDEA+PZ showed the lowest permeation rate. DEA and MDEA had the similar permeation rates. On the other hand, the highest CO2 desorption rate was obtained with MDEA+PZ and the second was obtained with MEA. As a result, the CO2 release ratio, which was defined as the ratio of actually desorbed CO2 amount to the potentially releasable CO2 amount, was highest with MDEA+PZ while MEA showed the lowest CO2 release ratio. The energy requirement for CO2 desorption consisting of the energy items required for liquid permeation, gas discharge and reaction heat was estimated based on the experimental results for each absorbent. The results indicated that the energy requirement was smallest in the case of MDEA+PZ. From these results, it has been found out that MDEA+PZ was most suitable for the membrane flash process.

G418 Effect of wash-coated metal oxides over synthesized carbon nanofibers coated monolith substrates
Mohamad Rasool Malekbala, Suraya Abdul Rashid, Luqman Chuah Abdullah, Thomas Shean Yaw Choong, Soroush Soltani
Universiti Putra Malaysia, 43400 Selangor, Malaysia

In this research work, carbon nanofibers (CNFs) were initially synthesized and then post-coated on honeycomb monolith substrates using injection chemical vapor deposition (ICVD) technique. The synthesized CNF monolith was intended for CO2 adsorption study. The effect of various wash-coated materials and catalyst promoter on the growth rate of CNFs on monolith substrates were examined. The characteristics of the synthesized CNFs-coated monolith composites were examined using Raman spectroscopy, Brunauer–Emmett–Teller (BET), thermogravimetric analysis (TGA), field emission scanning electron microscopy (FE-SEM), and Transmission electron microscopy (TEM) techniques. According to the textural characterization study, the specific surface area and pore volume of CNFs-coated monolith composites were significantly improved as compared to bare monolith which might be attributed to the growth of highly pure and aligned CNFs over monolith substrate. Besides that, the synthesized CNFs-coated monolith possessed extremely well thermal stability up to the temperature of 550 °C which was corresponded to the strong attachment of highly graphitized CNFs over monolith substrates.

G421 Mineral carbonation of steel-making waste: A green approach
Mohamed H. Ibrahim1, Muftah H. El-Naas1, Abdelbaki BENAMOR1, Saad Al-Sobhi2
1 Gas Processing Centre, College of Engineering, Qatar University, 2713, Doha, Qatar
2 Department of Chemical Engineering, College of Engineering, Qatar University, 2713, Doha

Mineral carbonation (MC) is the only recognized form of permanent CO2 storage options with no concerns regarding its long term stability. Industrial waste alkaline residues are utilized in mineral carbonation transforming them into useful products. The waste usually requires at least one pre-treatment step to make it more reactive. Pre-treatment is usually an energy-intensive process and involves the use of extraction agents which are not environmentally friendly. This translates into numerous environmental and economic concerns that hider the applicability of MC using industrial wastes. In this study, steel-making waste has been mineralized by CO2 to produce valuable calcium and magnesium carbonates and capture CO2 as illustrated in Figure 1. The study investigates an environmentally friendly and economical approach for MC by reacting electric arc furnace (EAF) baghouse dust (BHD) in a reject brine medium with CO2 in a novel reactor system, specially designed for contacting gases and liquids. This approach eliminates the need for pre-treatment chemicals and its associated cost which is estimated to be 0.4 €/kg of steel waste. Response surface methodology was used to optimize the MC process. At optimum operating parameters, the optimum CO2 uptake was 0.22 g CO2 /g BHD. A higher CO2 uptake performance of 0.98 g CO2/g BHD was achieved at ambient temperature and pressure of 5 bar. In addition, the concentration of the dissolved solids in the reject brine was reduced hence reducing its salinity. Thermal gravimetric analysis (TGA) of the solid products revealed that a variety of carbonate products being produced, particularly, calcium and magnesium carbonates.

G422 Energy-saving CO2 capture process by integrating separation and conversion process
Hiroshi MACHIDA1, Takehiro ESAKI2, Tsuyoshi YAMAGUCHI1, Koyo NORINAGA1
1 Nagoya University, Nagoya, Aichi, Japan
2 Fukuoka University, Fukuoka, Japan

A technology for converting CO2 recovered from a power plant into fuels or chemicals like methane or methanol is attracting attention as a CO2 effective utilization technology. We have been developing phase separation solvent for the purpose of energy saving of CO2 recovery. The absorbent consists of amine / ether / water and is characterized by low temperature regeneration. In this presentation, we will report on the prospect of significant energy savings by integrating CO2 recovery in the first stage and conversion in the second stage.

G423 [Keynote] CCS demonstration projects in Japan and Tomakomai CCS Demonstration Project
Yoshihiro SAWADA, Jiro TANAKA, Chiyoko SUZUKI
Japan CCS Co., Ltd., Chiyoda, Tokyo 100-0005 Japan

The following carbon capture, storage and investigation of potential CO2 storage sites projects are being conducted in Japan.
1. Tomakomai CCS Demonstration Project
Full-chain CCS demonstration Project
2. Investigation of Potential CO2 Storage Sites
Identify potential CO2 storage sites in waters surrounding Japan by 2021.
3. Sustainable CCS Project
Demonstration of capture facilities and comprehensive studies to introduce CCS
4. Osaki Coolgen Demonstration Project
Step 1: Oxygen-blown IGCC, Step 2: IGCC+CO2 Capture, Step 3: IGFC+CO2 Capture
The description of Tomakomai CCS Demonstration Project is as follows.
CO2 Capture Facility: The CO2 source is a hydrogen production unit (HPU) of an adjacent oil refinery, which supplies off gas containing approximately 50% CO2 from a Pressure Swing Adsorption (PSA) hydrogen purification unit. In the capture facility, gaseous CO2 of 99% purity is recovered by a commercially proven amine scrubbing process. A two-stage absorption system reduces the amine reboiler duty in the capture system.
CO2 Injection Wells: The CO2 is compressed and injected into shallow and deep offshore reservoirs by two separate deviated wells. The cumulative injected CO2 volume is 230,000 tonnes as of March 20, 2019.
Monitoring Facilities: An important objective of the project is to confirm the safety and stability of CO2 injection. As Japan is highly susceptible to earthquakes, natural earthquakes and micro-seismicity are also monitored to verify that natural earthquakes do not affect the stored CO2, and that CO2 injection does not cause any noticeable tremors. An extensive monitoring system comprising 3 observation wells with bottomhole temperature & pressure sensors and seismometers, 4 ocean bottom seismometers (OBSs), 1 ocean bottom cable (OBC) and 1 onshore seismometer was established. Monitoring was commenced one year prior to the start of CO2 injection and has been conducted continuously. In addition, seismic surveys are conducted to delineate the subsurface CO2 distribution.

PG301 Advance stripper configuration for energy-saving design using standard monoethanolamine absorbent for post-combustion carbon capture
Jialin LIU1, Ding-Sou CHEN2
1 Tunghai University, Taichung, Taiwan
2 China Steel Corporation, Kaohsiung, Taiwan

In a standard post-combustion carbon capture (PCC) process, the regeneration energy of the CO2 lean solvent dominates the overall energy consumption. The energy reduction in the CO2 stripper can be achieved by either formulating new solvents or optimizing the process configurations. The energy reduction achieved by stripper modifications, which include the rich-split process, the interheating process, and the integration of both configurations, have been reported in the literature. In the rich-split process, the cold rich stream is split to recover the energy contained in the overhead vapor, which was directly fed into the condenser in the traditional stripper configuration; therefore the regeneration energy can be reduced. The interheating process draws the liquid flow from the middle of the stripper and exchanges heat with the high-temperature lean solvent from the reboiler; thereby, the overall column temperature can be raised that favors CO2 desorption along the column. Therefore, the combined process, which is the rich-split process integrated with inter-heaters (IHs), takes both advantages of above modifications that can further reduce the energy requirement. However, the present work shows that energy-saving effect of the combined process is not as promising as the literature claimed. Once the design parameters of the rich-split process are selected properly, the rich-split process without IHs can achieve the same energy-saving effect as that achieved by the process of integration with IHs.

PG302 Thermodynamic model for predicting energy for amine absorbents
Takayuki KUSHIDA, Sakurako WADA, Yukio FURUKAWA
Waseda University, Tokyo, Japan

Aqueous solutions of alkanolamines are used for absorbents of the post-combustion capture of CO2. Energy requirements for the currently available systems are very high. Thus, it is important to lower the regeneration energy (ΔHreg, kJ/mol-CO2), which consists of three parts: the heat of chemical reactions for CO2 release (ΔHrxn, kJ/mol-CO2); sensible heat (ΔHsen, kJ/mol-CO2); heat of vaporization (ΔHvap, kJ/mol-CO2). In most previous works, it is assumed that the heat of CO2 release is equal to the absorption heat of CO2. However, it is a rough assumption. Thus, we present a thermodynamic model for predicting energy performance of amine absorbents (TMPEA) in order to evaluate the regeneration energy based on the enthalpies of chemical composition changes in a chemical equilibrium analysis. Firstly, we obtained the concentrations of chemical species at a low temperature Ta with a partial pressure of CO2, Pa(CO2), and at a high temperature Tr with Pr(CO2). Thus, we obtained the changes of the concentrations of chemical species from the low temperature state to the high temperature state. Secondly, the changes were expressed with reacted quantities of elementary chemical reactions. We calculated the ΔHrxn value from the enthalpies of the elementary reactions using the Hess's law. Finally, we calculated the ΔHsen and ΔHvap values according to the previous methods. We obtained the ΔHreg value as the sum of the ΔHrxn, ΔHsen, and ΔHvap values. We calculated the ΔHreg values for representative amines such as MEA, AMP, DEA, and IPAE. We found that calculated regeneration energies for MEA depends on working conditions. We demonstrated that TMPEA is useful for evaluating the regeneration energy of CO2.

PG303 CO2 solubilities and phase behaviors in phase separation solvents at high pressure
Andrzej-Alexander LITWINOWICZ1, Masaki WATANABE1, Takashi MAKINO1, Yuki KOHNO1, Hiroshi MACHIDA2, Koyo NORINAGA2, Mitsuhiro KANAKUBO1
1 Research Institute for Chemical Process Technology, National Institute of Advanced Industrial Science and Technology (AIST), 4-2-1 Nigatake, Miyagino-ku, Sendai, 983-8551, Japan
2 Graduated School of Engineering, Nagoya University, Furocho, Chikusaku, Nagoya, 464-8603, Japan

Carbon dioxide capture, utilization, and storage (CCUS) is a key technology to decrease the emission of greenhouse gas, CO2. The benchmark process using a 30% monoethanolamine aqueous solvent for CO2 capture requires a large amount of energy, in particular, for the regeneration of absorbent at high temperature up to 120 °C. In a recent decade, a variety of absorbents have been investigated to reduce such high energy consumption. Phase separation solvents, which separate into immiscible CO2-rich and CO2-lean phases after CO2 absorption, have been proposed to improve the process efficiency for CO2 capture at atmospheric pressure [1]. In the present study, we attempt to extend the phase separation solvents for high-pressure CO2 capture processes. The p-V-T-x behaviors are studied for the systems of CO2 and phase separation solvents, composed of some amines and ethers at different compositions, over a wider range of temperature and pressure. The could point, inducing the phase separation, can be controlled by the basicity and concentration of amine, which are the predominant factors in the formation of ionic species. The phase separation and p-V-T-x behaviors are discussed in detail for the development of efficient CO2 capture processes at high pressure.
[1] H. Machida, K. Oba, T. Tomikawa, T. Esaki, T. Yamaguchi, H. Horizoe, J. Chem. Thermodyn., 113 (2017) 64-70.

PG304 Energy saving CO2 capture process using circulating fluidized bed
Yasuki KANSHA, Masanori ISHIZUKA
The University of Tokyo, Tokyo, Japan

Carbone dioxide Capture, Utilization and Storage has attracted significant attention in the past two decades to reduce greenhouse gas (GHG) emissions and mitigate global warming. However, its capture cost should be further decreased to facilitate its commercial implementation. In fact, CO2 capture is considered as the most energy-intensive part.
In this research, an innovative process using chemical absorption by solid with a circulating fluidized bed has been proposed to reduce energy consumption of CO2 capture. In this process, reaction heat accompanying absorption is successfully supplied to thermal decomposition in regenerator through a heat pump, leading to circulation of whole process heat. To see the influence of the separation performance of the proposed process, some experiments have been conducted. An energy balance of the proposed process using experimental data is simulated and examined using a commercial process simulator (PRO/II, Ver. 9.1). The simulation results indicate that the proposed CO2 separation process has the large energy saving potential as compared with the conventional counterparts.

PG305 Simultaneous organic matter synthesis and absorbent regeneration by direct hydrothermal treatment of alkali bicarbonate as a CO2 absorbent
Ryo MIZUNO1, Iori SHIMADA2, Mitsumasa OSADA2, Hiroshi FUKUNAGA2, Nobuhide TAKAHASHI2
1 Graduate School of Science and Technology, Shinshu University, Ueda, Japan
2 Faculty of Textile Science and Technology, Shinshu University, Ueda, Japan

CCU (Carbon dioxide Capture and Utilization) technology, in which CO2 is captured from large-scale emission sources and the CO2 is converted into high-value added chemicals and fuels, is expected to improve the economical efficiency of CO2 separation and recovery and to enable its commercialization. Among the proposed CCU technologies, organic matter synthesis from water and CO2 under hydrothermal conditions has advantages such as no use of hydrogen and no use of precious metals as catalyst and reductant. Then, in CO2 chemical absorption method using potassium carbonate, we propose that the rich absorbent solution containing CO2 be directly subjected to hydrothermal treatment so as to convert CO2 into organic compounds simultaneously with the regeneration of the absorbent solution for the following absorption process. In this study, we aim to clarify the possibility of converting CO2 into organic compounds by hydrothermal treatment of KHCO3 as a CO2 source. Furthermore, another purpose of this study is to elucidate whether it is possible to regenerate CO2 absorbent solution during the hydrothermal treatment.
A stainless batch reactor was charged with specified amounts of KHCO3 or NaHCO3 as a CO2 source, Fe powders as a reductant, Ni powders as a catalyst and distilled water. The reactor was heated in a sand bath at 300 °C for 120 minutes. After cooling the reactor, the concentration of formic acid and inorganic carbon (IC) contained in the liquid sample were measured with HPLC and a TOC meter, respectively. The results confirmed the formation of formic acid from both KHCO3 and NaHCO3. The yield of formic acid was higher when KHCO3 was used. From the results of IC in the solution after the treatment, it was indicated that most of the introduced bicarbonate was converted to carbonate after the reaction and the absorbent solution could be regenerated.

PG306 CO2 absorption characteristics of aqueous blends of potassium serinate and piperazine
Sujeong SEO1,2, Hojun SONG1, Johong KANG1, Yongchul CHUNG2
1 Korea Institute of Industrial Technology Company, ULSAN City, South KOREA
2 Pusan National University, BUSAN City, South KOREA

A key factor for commercialization of CCUS (carbon dioxide capture, utilization, and sequestration) is to establish an efficient and effective CO2 capture process because the capture process possesses the 50 to 80 % of total CCUS operating expense. In this study, we suggests an energy efficient CO2 absorbent comprising the aqueous blend of potassium serinate (K-Ser) and piperazine (Pz). Especially, this CO2 absorbents have high surface tension which make them proper for use in polypropylene (PP) hollow fiber membrane contactor to reduce the membrane pore wetting. By fast solvent screening test, it is revealed that the cyclic capacity of the aqueous blend of K-Ser and Pz is 25 % higher than that of 30 wt% MEA (monoethanoleamine). Vapor-liquid equilibrium was measured to estimate the heat of reaction by calculation using Gibbs-Helmholtz equation. Heat capacity was measured to calculate the sensible heat. Finally, the solvent regeneration energy of the aqueous blend of K-Ser and Pz are estimated and compared with 30 wt% MEA by summation of heat of reaction, sensible heat and heat of vaporization. The long term CO2 removal experiment using Lab-scale membrane contactor will be our future work.

PG307 Degradation test on phase separation type absorbent using amine and ether for energy-saving CO2 capture
1 Kobe Steel, Ltd., Kobe, Japan
2 Nagoya University, Nagoya, Aichi, Japan

For the CO2 capture from high-volume and CO2-dilute gas such as combustion gas from power plants, chemical absorption with amine is expected to be one of the most feasible technologies. However, its application to the commercial plants for the explicit purpose of CO2 emission abatement still has been limited to a small number. Although there might be several reasons, one of the most critical reasons is its low profitability. Amine solvents require a lot of energy for regeneration, which results in high running cost for CO2 separation.
Our unique phase separation type amine/ether absorbent is expected to realize the CO2 separation process with low-energy consumption (target: less than 2.0 GJ/ton-CO2). This liquid shows a single uniform phase just by mixing the raw materials; amine, ether and water. And it is splitted into two phases consisting of an amine-rich phase and an ether-rich phase by absorbing CO2. Further, it returns to its original uniform phase after CO2 desorbing. During liquid regeneration the ether phase assists the CO2 desorption from the amine phase rich in CO2 by the extraction of CO2, which results in a reduction of energy input for liquid regeneration.
In this study, 500 hours degradation test on this absorbent under cyclic thermal load was conducted in order to clarify 1) the behavior of its performance declination for CO2 capture and 2) the behavior of amine loss. Its test condition was chosen based on two assumptions that a) high-oxidation atmosphere containing O2 and SOX which is destructive condition for the absorbent, and b) adopting practical operating temperature when absorbing or desorbing.

PG308 Lab. plant result of phase separation CO2 capture with H2 gas stripping
Hitoshi NISHIO1, Daiji MUROYA1, Takehiro ESAKI2, Hiroshi MACHIDA1, Koyo NORINAGA1
1 Nagoya University, Nagoya, Aichi, Japan
2 Fukuoka University, Fukuoka, Japan

As measures against global warming, CO2 capture and storage technology (CCS) and capture and utilization technology (CCU) has drawn attention of researchers all over the world. So far, our laboratory has developed a new phase separation type CO2 absorbent to improve energy problem in CO2 separation and recovery technology. The CO2·H2 mixed gas recovered from the top of the column can be supplied as it is to the conversion process to methane, methanol and the like. In this process, H2 a component of the source gas, was applied to the bottom of the regeneration tower and reacted with CO2 freed from regeneration process to create methane, methanol and others, which makes it a CCU process. Moreover, without purifying CO2 concentration, this process reduces the energy requirement as compared to the conventional method. In this study, experimental data on stripping regeneration characteristics of phase separated absorbents were acquired. From that, CO2 separation / recovery energy was calculated.

PG309 CO2 solubility measurement in phase separation solvent using in-situ FTIR
Miho SATO, Khuyen TRAN, Hiroshi MACHIDA, Koyo NORINAGA
Nagoya University, Nagoya, Aichi, Japan

Carbon capture and storage plays an important role in greenhouse gas reduction. Monoethanolamine(MEA) is now widely applied in industry. To overcome the energy penalty of this methods, phase separation solvent was suggested by Machida et al. Since the phase-separation solvent under developing composes of multiple components and separates into two liquid phases after CO2 absorption, it takes time to determine the composition.
Fourier transform infrared spectrometer (FTIR) can simultaneously collect spectra of chemicals within a short time. In order to establish an in-situ method to analyze the components of solution, process FTIR (reactIR) was applied during CO2 absorption. Calibration samples of amines, ethers and CO2 absorbed samples were used to build the model. TOC was used to verify the accuracy of method and model. From FTIR spectra, not only concentrations of components can be determined, phase separation was also observed. Therefore, this method has a prospective application in liquid composition monitoring in plant step.

PG310 Performance evaluation of phase separation process using high-concentration AMP promoted by MAPA for CO2 capture
Akihisa MATSUI1, Naoya OGIYAMA1, Takumi ENDO2, Jun ARAKAWA2, Takao NAKAGAKI1
1 Waseda University, Tokyo, Japan
2 IHI Corporation, Tokyo, Japan

As a countermeasure against the global warming, early introduction of CCS to large scale CO2 emission facilities, such as thermal power stations, is expected. In general, since CO2 capture process using amine-based solution requires a large quantity of heat for stripping CO2 and regeneration of rich loading solution, process improvement as well as exploring novel solutions is a key to reduction of energy penalty. High concentration 2-Amino-2-methyl-1-propanol (AMP) solution precipitates carbonate with absorption of CO2 and can be expected to reduce sensible heat of regeneration energy by sending the separated carbonate to the stripper. The solution of AMP50wt% promoted by adding Piperazine (PZ), has been tested and successfully operated with solid-liquid separation by a centrifuge. However, the CO2 recovery rate was up to 65% since PZ regeneration reaction did not occurred and PZ was circulated without regeneration. In this study, as a result of searching for new promoter, N-Methyl-1,3-diaminopropane (MAPA) was selected. MAPA primary-carbamate can form an eight-member ring which is easily regenerated, so it is expected to improve CO2 absorption rate in the low CO2 loading range without decrease in the CO2 loading capacity. The operating condition of the small-scale CO2 recovery test was updated by testing AMP/MAPA solution at various temperatures and CO2 loadings. No compounds derived from MAPA were detected in the precipitation solid by results of Raman spectroscopy and GC-MS. Precipitation characteristics of AMP carbonate was empirically obtained by batch tests to determine a stable condition of precipitation process, and cooling temperature was determined 53.4 °C. The injection of semi-lean liquid, which is separated from AMP carbonate by the centrifuge, to the middle inlet seems to be effective to keep the absorption rate even at the top of absorber where the CO2 concentration decreases. The rate-based 10 stages model of absorber using AMP/MAPA solution was built on Aspen Plus and CO2 recovery rate associated with precipitation rate was simulated to determine the position of middle inlet. Injecting the semi-lean liquid to the fifth stage showed the highest CO2 recovery rate. Aqueous solution of AMP 40 wt% + MAPA 5 wt% was evaluated by small-scale apparatus of CO2 capture and recovery with the middle injection process. As a result, the regeneration energy decreased, and CO2 recovery rate reached 90 %.

PG311 (canceled) <101466-1>
PG312 Reaction kinetics of carbon dioxide in aqueous blends of N-methyldiethanolamine and potassium salts of glycine using the stopped flow technique
Nafis Mahmud, Abdelbaki BENAMOR, Mustafa Nasser, Muftah El-Naas
1 School of Chemical Engineering, The University of New South Wales, Sydney 2052 NSW, Australia
2 Particle Catalysis Research Group, The University of New South Wales, Sydney 2052 NSW, Australia

Global warming and its harmful implications are a major concern for the government and scientific communities worldwide. CO2 being a greenhouse gas is considered to be a major contributor of the global warming. To reduce the anthropogenic emissions of CO2, capturing CO2 from the industrial processes is a must. The solvent based CO2 capture processes is considered to be the most mature and promising technology to capture CO2 from the exhaust streams. Alkanol amines are widely used as a solvent in these processes. However, they are energy intensive and there are still need for development of novel solvents that can make the CO2 capture technology more energy efficient. Potassium salts of amino acids have recently emerged as potential candidate to be used both as a single solvent or as a promoter in the CO2 capture technology. In this work, the potentials of Potassium Salts of Glycine (KGly) as promoter is explored via a kinetics study of reactions of CO2 with different blends of N-Methyldiethanolamine (MDEA) and KGly. Stopped-flow technique was used to carry out the investigations. The experiments were performed over a temperature range of 298 to 313 K and solution concentration of 0.2 and 0.8 mole/l in different MDEA/KGly proportions. Obtained kinetics data were interpreted using zwitterion and termolecular mechanisms for the potassium salts of glycine. The individual rate constants of the participating reactions were regressed and their corresponding activation energies were estimated

PG313 (canceled) <100011-1>

Session S8. Materials and systems engineering for electrical energy devices —fuel cell, battery, solar cell, and energy carriers—

M201 The effect of zeolite filling into the plasma membrane reactor on hydrogen separation performance
Yukio HAYAKAWA1, Shintaro WAKAZONO1, Tomonori MIURA2, Shinji KAMBARA1
1 Gifu University, Gifu, Japan
2 Sawafuji Electric Co., Ltd., Gunma, Japan

The bottleneck of realizing a hydrogen energy society is energy loss during hydrogen transport and storage. Ammonia is a promising raw material for hydrogen production because it may solve several problems related to hydrogen transport and storage. Ammonia has four advantages as an energy carrier: (1) Liquefaction is easy. (2) The transport and storage mechanisms have been established. (3) Carbon dioxide is not removed when ammonia is converted to hydrogen. (4) Ammonia has high weight-based and volume-based energy densities as fossil fuel. Hydrogen can be effectively produced from ammonia via catalytic thermal decomposition; however, the resulting residual ammonia negatively influences the fuel cells. Therefore, a high-purity hydrogen production system comprising a catalytic decomposition reactor and a plasma membrane reactor (PMR) has been developed. In this hydrogen production system, ammonia is quickly decomposed into hydrogen and nitrogen in a catalytic reactor, and hydrogen is separated from ammonia decomposition gas by PMR. However, the hydrogen yield of this hydrogen production system was low (16 %). The cause of the low yield was the low hydrogen separation capacity of the PMR with ununiformed plasma firing.
In this study, the state of plasma firing was improved by filling dielectric in the PMR. A columnar zeolite (Tosoh Corporation) was used as a dielectric. In the PMR filled with zeolite, plasma was uniformly fired. By packing the zeolite in the PMR, the hydrogen generation performance of the PMR was also improved. It was also found that the improvement of the production performance is affected by the properties of the zeolite to be filled. The hydrogen refining flow rate obtained 199 L-H2/h from 150L-NH3/h. The hydrogen yield of this hydrogen production system improved from 16 % to 88 %.

M202 Reversible dehydrogenation of formate on N-doped graphene-supported Pd nanoparticles for renewable hydrogen energy
Dong Yun SHIN1, Min-Su KIM1, Jeong An KWON1, Yeon-Jeong SHIN1, Chang Won YOON2,3, Dong-Hee LIM1
1 Chungbuk National University, Cheongju, Korea
2 Korea Institute of Science and Technology, Seoul, Korea
3 Kyung Hee University, Seoul, Korea

We investigated the reaction pathways for reversible formate (HCOO) dehydrogenation and bicarbonate (HCO3) hydrogenation on N-doped graphene-supported Pd nanoparticles such as Pd12NC-G, Pd12NC-N1G, Pd12NC-N2G, and Pd12NC-N3G using density functional theory (DFT) calculations, and proposed key factors for the enhancement of the reversible reaction efficiency. In order to achieve this, an anion environment caused by HCOO and HCO3 was simulated by designing two-sided Pd12NC-G systems with extra electrons. The difficulty of conventional DFT calculations related to simulating the anion environment were overcome by using the two-sided systems. Using the systems, we analyzed reaction pathways for the HCOO dehydrogenation and HCO3hydrogenation, and demonstrated that the desorption strength of hydrogen was the potential limiting step for the HCOO dehydrogenation with the energy barriers as 1.24 (1.49), 1.12 (1.27), 0.76 (0.96), and 1.35 (1.90) eV on Pd12NC-G, -N1G, -N2G, and -N3G, respectively (values for the HCO3 hydrogenation were indicated in parentheses). These results indicate that the adsorption energy of hydrogen can be utilized as a descriptor for the reversible reactions on other surface systems. In addition, we confirmed that the Pd12NC-N2G with the proper amount of N dopants showed optimal hydrogen adsorption strength depending on the smallest d-band center and spin density values, resulting in the lowest energy barriers for HCOO dehydrogenation (0.76 eV) and HCO3 hydrogenation (0.96 eV). This showed that the appropriate number of nitrogen dopants can provide the optimal balance for the reversible reactions.

M203 Plasma flow reactor with a flow channel for hydrogen production from ammonia
Ryoma SAKAI1, Yukio HAYAKAWA1, Shinji KAMBARA1, Tomonori MIURA2
1 Gifu University, Gifu, Japan
2 Sawafuji Electric Co., Ltd., Gunma, Japan

Ammonia is a hydrogen storage material that may solve several problems related to hydrogen transportation and storage in the hydrogen society. Catalytic thermal decomposition is a promising technique for producing hydrogen from ammonia. However, Catalytic thermal decomposition of ammonia needs long start-up time for heating reaction field. So, it is not suitable for power generation on site. Cylindrical plasma membrane reactors have been developed to produce pure hydrogen from ammonia. However, the gas flow is not uniform; therefore, the plasma state is unstable, resulting in a low ammonia decomposition rate in the cylindrical plasma reactor. A plasma membrane reactor with a flow channel was considered in order to address this issue, assuming that this configuration would simulate a fuel cell separator to create a uniform gas flow. A 1-mm-wide and 1-mm-deep flow channel was fabricated on the metal plate. 0.1% ammonia gas was supplied to the flow channel plasma reactor at a 0.1-L/min flow rate in an object to test the configuration. Stable plasma was observed; the ammonia decomposition rate reached 20.3 %, which represents a higher conversion efficiency than that measured in a cylindrical plasma membrane reactor with the same gas residence time. Because the plate plasma reactor can be laminated, it can be easily scaled up for large-scale hydrogen production. The effects of the applied voltage, gas flow rates, and ammonia concentration on the ammonia decomposition rate were investigated. The results showed that an increase in the applied voltage leads to a higher ammonia decomposition rate because the high plasma density causes greater dissociation of molecular ammonia by electron impacts. Further, increases in the ammonia gas flow rate or the ammonia concentration reduces the ammonia decomposition rate.

M204 Hydrogen production by packed bed plasma reactor with hydrogen separator
Akitsugu SAKAI1, Yukio HAYAKAWA1, Shinji KAMBARA1, Tomonori MIURA2
1 Gifu University, Gifu, Japan
2 Sawafuji Electric Co., Ltd., Ota, Gumma, Japan

An efficient method for using pulsed plasma to produce hydrogen from ammonia was developed.
To keep the plasma steady under pressurized conditions, internals such as zeolite particles was available. Actually, hydrogen production rate from ammonia was increased by the packed bed plasma membrane reactor. This report discusses the cause of the increase of hydrogen. The V-Q lissajous and fundamental characterization of the particles was investigated for some kinds of zeolite particles. It seems that the dominant factor is H radical generation by the zeolite.

M205 Electrochemical device with reaction, separation, compression processes for pressurized hydrogen from 2-propanol
Gunma University, Kiryu, Japan

The technical issue of hydrogen, which is used for fuel cell electronic vehicle, is the storage and the transportation. Some chemicals, i.e., 2-propanol and methyl-cyclohexane, have potential as a carrier of hydrogen due to their advantages such as liquid phase at room temperature, lower toxicity, etc. The conventional hydrogen production process from these “hydrogen carrier” was complex and energy-wasting because the process consists of (1) dehydrogenation reactor (endothermic step), (2) condenser of an organic compound (exothermic step), and (3) mechanical compressor.
We propose a new electrochemical device which able to produce a proton, separate hydrogen, and compress hydrogen in one step. The setup of the device is similar to the polymer electrolyte fuel cell (PEFC). The proton forms at anode, hydrogen gas at the cathode is separated from the organic compounds by the polymer electrolyte membrane, and hydrogen is compressed by the conversion from electronic potential to chemical potential (Nernst equation).
In this work, we developed the electrochemical device to obtain pressurized hydrogen from 2-propanol. The one-pass conversion and obtained pressure were measured during constant voltage operation.
We prepared a PEFC-like device with Pt/C catalyst (for anode and cathode) and Nafion 117 membrane. A hydrogen carrier, 2 M 2-propanol, was supplied to the anode. The –1 V of voltage was applied to the device, the one-pass conversion was evaluated from the composition of anode effluent, and cathode gas pressure was measured by a pressure transducer.
The obtained one-pass conversion was ca. 8% at –1 V, and cathode gas pressure increased 0.9 bar during 1 h. The major component in cathode gas was hydrogen, in the meanwhile, some impurities, i.e., 2-propanol, acetone, and methane, were found. Methane is considered to be formed from acetone and hydrogen with Pt catalyst.

M206 Development of plate-type plasma membrane reactor
Hiroki SATO1, Yukio HAYAKAWA1, Shinji KAMBARA1, Tomonori MIURA2
1 Gifu University, Gifu, Japan
2 Sawafuji Electric Co., Ltd, Ota, Gumma, Japan

Plasma membrane reactor has been developed to produce hydrogen from ammonia. A cylindrical type reactor is available for hydrogen production; however, a plate-type reactor is desired for a mobility use. A plate type plasma membrane reactor has made by a flow channel plate and original electrode, which shows stable plasma firing by dielectric barrier discharge. Effect of membrane thickness on hydrogen permeation characteristics was examined, and its characteristics were compared with the cylindrical plasma membrane reactor.

M213 First-principles investigation of phase stability of magnesium alanate (Mg(AlH4)2) for hydrogen storage
Dong-Hee LIM1, Tim MUELLER2, Yeon-Jeong SHIN1, Dong Yun SHIN1, Jennifer WILCOX3
1 Chungbuk National University, Cheongju, Republic of Korea.
2 Johns Hopkins University, Baltimore, MD, USA.
3 Colorado School of Mines, Golden, CO, USA

The equilibrium diagrams for the decomposition of magnesium alanate (Mg(AlH4)2) nanoparticles were constructed as a function of particle size and temperature to better understand nanostructuring of the complex hydrides for hydrogen storage. Relatively smaller nanoparticles of Mg(AlH4)2, MgH2, and Al ranging from 1 to 2 nm were directly calculated by using density functional theory (DFT) calculations, and cluster expansion and Monte Carlo simulation methods were developed to predict the free energy contours of 1 ~ 50 nm nanoparticles. Our prediction demonstrates that bulk Mg(AlH4)2 can release hydrogen but its uptake reaction is unfavorable, and bulk Mg(AlH4)2 is metastable with respect to bulk MgH2. However, in the cases of nanoparticle systems, hydrogen release and its recharging may be possible by controlling the particle size and temperature, which may facilitate experimental studies to determine the thermodynamically favored reaction pathways for the dehydrogenation and hydrogenation processes of Mg(AlH4)2 nanoparticles. We also provide the equilibrium diagrams for Mg(AlH4)2 nanoparticle decomposition depending on a hydrogen partial pressure.

M214 Highly durable membrane electrode assembly using carbon-free connected platinum–iron catalyst for direct formate solid alkaline fuel cells
Hidenori KUROKI1,2,3, Shoji MIYANISHI2,3, Takanori TAMAKI1,2,3, Sankar SASIDHARAN2,3, Gopinathan M. ANILKUMAR3,4, Takeo YAMAGUCHI1,2,3
1 Kanagawa Institute of Industrial Science and Technology, Kanagawa, Japan
2 Tokyo Institute of Technology, Kanagawa, Japan
3 JST-CREST, Tokyo, Japan
4 R&D Center, Noritake Co., Ltd., Aichi, Japan

Solid alkaline fuel cells (SAFCs) have attracted much attention as next-generation energy conversion electrochemical devices. However, practical applications of these devices are limited because of the drastic decrease in the cell performance during the high temperature operation, under alkaline condition. This low performance of the device is mainly attributed to the severe degradation of membrane–electrode-assembly (MEA). Therefore, the development of a durable and stable MEA is critical to improve the cell performances and stabilities in this system.
Here we report the development of a highly durable MEA, as shown in Fig. 1A, using a carbon-free cathode catalyst [1,2] and an aromatic polyelectrolyte without ether linkage [3]. The carbon-free catalyst consists of a nanosized beaded network formed by the connection of Pt–Fe nanoparticles. The beaded metal network is electrically conductive, enabling the removal of carbon support from catalyst layers. Hence, carbon corrosion problems can be avoided, leading to high durability against the cyclic start-stop operation of the system.
The fabricated MEA, operating at a high temperature of 80 °C, exhibited high power density of 220 mW cm–2 and high open-circuit voltage of about 1.0 V (Fig. 1B), wherein, a mixture of aqueous solutions of 4 M HCOOK and 2 M KOH was used as the fuel. Further, more importantly, the high performance of the MEA was retained even after the operation at 80 °C and 0.2 A cm–2 for 150 h. Thus, for the first time, we demonstrated a highly durable and stable MEA in alkaline medium for the direct formate SAFCs.
[1] T. Tamaki, H. Kuroki, T. Yamaguchi et al., Energy Environ. Sci., 8, 3545–3549 (2015).
[2] H. Kuroki, T. Tamaki, T. Yamaguchi et al., ACS Appl. Energy Mater., 1(2), 324–330 (2018).
[3] S. Miyanishi and T. Yamaguchi, J. Mater. Chem. A, 7, 2219–2224 (2019).

M215 CO2 Hydrogenation to methanol over highly loaded Cu nanoparticles on ZrO2 prepared by flame spray pyrolysis
Shohei TADA1, Kakeru FUJIWARA2, Taihei YAMAMURA1, Masahiko NISHIJIMA3, Sayaka UCHIDA4, Ryuji KIKUCHI1
1 Department of Chemical System Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo, Tokyo 113-8656, Japan
2 Department of Chemistry and Chemical Engineering, Yamagata University, 4-3-16 Jonan, Yonezawa, Yamagata 992-8510, Japan
3 The Electron Microscopy Center, Tohoku University, 2-1-1 Katahira, Aoba-ku, Miyagi 980-8577, Japan
4 Department of Basic Sciences, The University of Tokyo, 3-8-1 Komaba, Meguro, Tokyo 153-8902, Japan

Methanol synthesis from CO2 hydrogenation has been recently an object of study because CO2 is a potential feedstock based on the concept of a methanol-based economy. However, the commercial catalyst Cu/ZnO/Al2O3 does not show enough activity and selectivity of the CO2 hydrogenation. Hence, it is important to develop suitable catalysts for the CO2 hydrogenation. So far, we reported that Cu/ZrO2 catalysts hydrogenate CO2 selectively to methanol. In this study, we focused on flame spray pyrolysis (FSP) which are widely used for producing nanosized metals/metal oxides on an industrial scale. One of the advantages of FSP is the formation of small metal nanoparticles at extremely high metal loading on metal oxide particles. This time, we tried to prepare highly loaded Cu nanoparticles on ZrO2 (20-80 wt%_Cu) by the FSP technique and investigated the effect of Cu loading on activity and selectivity of CO2-to-methanol hydrogenation. When Cu loading was 60 wt%, the catalysts showed higher methanol yield and methanol selectivity than did a commercial catalyst Cu/ZnO/Al2O3. Its catalytic performance was derived from the unique structure: Cu nanoparticles (10-20 nm) were deposited on ZrO2 nanoparticles (5-10 nm). In addition, the Cu nanoparticles were strongly interacted with the ZrO2 nanoparticles, leading to electron transfer from Cu to ZrO2. The interaction might create specific active sites for the CO2 hydrogenation.

M216 Enhancing noble metal alkaline formate oxidation (FOR) kinetics: Engineering transition metal and post-transition metal based nanoalloys
Sankar Sasidharan1, Gopinathan M. Anilkumar2, Takanori TAMAKI1, Takeo YAMAGUCHI1
1 Laboratory for Chemistry and Life Science, Tokyo Institute of Technology, R1-17, 4259 Nagatsuta, Midori- ku, Yokohama 226-8503, Japan
2 Noritake Co., Ltd., 300 Higashiyama, Miyochi-cho, Miyoshi, Japan 470-0293

Direct Formate Fuel Cells (DFFCs) hold a key stake in the energy systems looked into for answers to the increasing futuristic energy demand, largely due to the offered potential practical energy generation capability along with the safety, low cost and environment friendliness compared to the counterpart alcohol fuels (DEFCs & DMFCs). Palladium has shown the most promising results in recent years for enhanced liquid-fuel oxidation kinetics that could effectively replace platinum in terms of performance and extensive application span, particularly in alkaline medium. In our study, we engineer alloys based on Pd and transition metal (Pd-Ni) /post-transition metal (Pd-Sn) over carbon support using an exclusive wet chemical technique. The formed alloy compositions showed overall enhanced formate oxidation half-cell performance and longer stability compared to Pd/C in alkaline medium. The performance analysis based on the structural and surface characteristics of these nanoalloys obtained over carbon support is elucidated and presented. The successfully developed catalyst compositions and technique employed paves way for a scalable strategy for realizing highly efficient anode catalysts for DFFCs.

M217 [Keynote] Structured Cu-based/γ-Al2O3/Al catalysts for steam reforming of dimethyl ether and applied in a microreactor
Qi ZHANG, Taotao YANG, Xiaoqian DENG, Li ZHANG
Department of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China

The depletion of fossil fuels and increasing energy demand has driven the research and exploration of new energy alternatives. Hydrogen is considered to be a clean source of energy and steam reforming of dimethyl ether (DME) is regarded as a promising hydrogen production process for fuel cell applications. A plate-type anodic alumina supported Cu composition catalyst was developed to investigate its catalytic performance in steam reforming of DME. It is found that the fresh Cu/γ-Al2O3/Al catalyst without H2 pre-reduction treatment exhibited the similar catalytic activity as the pre-reduced one. The XPS results show that Cu+ species exist in the surface of the fresh catalyst, which results in the self-activation reaction. However, the Cu/γ-Al2O3/Al catalyst showed a quick deactivation at 350 °C due to the sintering of copper. As an approach, a second component Ni was doped to the Cu-based catalyst. Furthermore, the effect of nickel loading and chemical state on the activity of catalyst was extensively investigated. The proper amount of nickel doping is helpful in improving the dispersion of copper species, and thus enhancing the catalytic activity. Finally, a 180 h stability evaluation was carried out and the results show that the optimized Cu/Ni/γ-Al2O3/Al catalyst has an excellent stability under critical conditions with 400 °C, and gives a 100% DME conversion. However, a high CO concentration (ca. 26%) was detected. As such, a multifunctional catalyst combined DME SR and high temperature water gas shift reaction (HT-WGSR) was developed. The CO reduction mechanism was proposed over the Fe-doped Cu-based multifunctional catalyst. Furthermore, the effects of iron loading on the physicochemical properties and performance of catalysts were extensively investigated. The results show that the proper amount of iron doping was helpful in improving the dispersion of Cu, and thus enhancing the catalytic performance and decreasing CO concentration. Finally, it is found that the optimized Cu/Ni/Fe/γ-Al2O3/Al multifunctional catalyst has excellent stability during a 200 h test, and gives a 100% DME conversion at 400 °C in both the microreactor and fixed-bed reactor. Furthermore, crossflow channels and parallel-flow channels were built respectively by mesh-type catalyst and plate-type catalyst in the microreactor. The gas/solid mass transfer limitations in both flow channels were investigated by Damköhler number (Da). The results showed that the Da values of cross flow were always < 0.01, while the values of parallel flow were > 0.01. It indicated that the diffusion over mesh-type catalyst was less influenced by temperature and reactor height, making it a more appropriate choice for the microreactor.

M221 Ion-beam irradiation to the CECNF support of the anode catalyst for DMFC
Nobuyoshi NAKAGAWA1, Hirokazu ISHITOBI1, Soma ABE1, Masaki KAKIMUMA1,2, Hiroshi KOSHIKAWA2, Shunya YAMAMOTO2, Testuya YAMAKI2
1 Gunma University, Kiryu, Japan
2 National Institutes for Quantum and Radiological Science and Technology, Takasaki, Japan

One of the issues for commercialization of direct methanol fuel cell (DMFC) is the slow kinetics of the anode reaction, and an alternative catalyst with high activity has been desired. PtRu nanoparticles supported on CeO2 nanoparticles embedded carbon nanofibers (CECNF), PtRu/CECNF, showed two to three times higher methanol oxidation reaction (MOR) activities due to the support effect of CECNF which efficiently develops the positive interaction between Pt and CeO2 by the CeO2 embedding fiber structure. The interaction can be explained by the reaction mechanism with an oxygen vacancy of the CeO2. In this study, the ion-beam irradiation was employed to introduce oxygen vacancies to the support material in order to increase the MOR activity of the catalyst.
A sheet of CECNF was prepared by using the electrospinning technique. To the CECNF sheet, irradiation of high-energy ion-beam, Ar9+ 127 MeV, was conducted at the different fluence (ion-beam density based on subjected area). After that, PtRu nanoparticles were deposited on the CECNF by a microwave polyol method. The catalytic activity for methanol oxidation reaction was evaluated by using a three -electrode cell with a glassy carbon electrode as a working electrode.
It was found that the MOR mass activity of the PtRu/CECNF increased, up to about 25%, with the increase of the fluence up to a certain value, then decreased with further increase of the fluence as shown in Table 1. The crystalline size of CeO2 in PtRu/CECNF, obtained from XRD profile using Scherrer's equation, decreased with the increase of fluence. EDX results elucidated a decrease of oxygen content in the catalyst due to the irradiation. These results suggested that the ion-beam irradiation destroyed a part of the crystal structure of CeO2, and it enhanced the MOR activity at the proper fluence.

M222 Design strategy of palladium-based catalysts for formate oxidation reaction in alkaline conditions based on mechanistic studies
Takanori TAMAKI1,2, Naoto WATANABE1, Sasidharan SANKAR1,2, Gopinathan ANILKUMAR3,2, Masashi MATSUMOTO4,2, Naoki TAKAO4,2, Qiuyi YUAN 4,2, Hideto IMAI 4,2, Takeo YAMAGUCHI 1,2
1 Tokyo Institute of Technology, Yokohama, Japan
2 Core Research for Evolutionary Science and Technology, Japan Science and Technology Agency (JST-CREST), Japan
3 Noritake Co., Ltd., Miyoshi, Japan
4 Nissan ARC Ltd., Yokosuka, Japan

Recent rapid decline in the price of renewable energy increases the importance of energy carriers. Formate solution is one of the envisaged candidate for liquid energy carriers, since formate can be electrochemically regenerated in high energy efficiency from carbon dioxide. For the use of formate solution as an energy carrier, formate needs to be converted to electricity with high energy efficiency.
Our aim in this study is to clarify design strategy of electrocatalysts for formate oxidation reaction (FOR) in alkaline conditions. Palladium (Pd) is known to show better activity for FOR in alkaline solution than platinum. The reaction mechanism of FOR on Pd in alkaline condition remains controversial; although many groups suggested a reaction mechanism without any poisoning species (strongly bound species) such as carbon monoxide (CO), a few studies showed the presence of bound CO. If CO exists, the FOR activity of Pd can be improved by reducing CO adsorption on its surface, which is possible by incorporating oxophilic materials such as ceria (CeO2) and ruthenium (Ru).
Herein, we sequentially deposited CeO2 and Pd over carbon support (Pd/CeO2-C). This Pd/CeO2-C showed better activity for FOR in alkaline medium than Pd/C. The result of an in-situ x-ray absorption spectroscopy (XAS) measurement at Pd K-edge showed the formation of CO on Pd in the presence of formate. Also, the comparison of the spectra between Pd/CeO2-C and Pd/C showed a decrease in CO adsorption with the concomitant increase in OH adsorption on Pd/CeO2-C. We then synthesized Pd-Ru alloy to more effectively incorporate oxophilic materials with Pd. PdRu/C showed better activity than Pd-CeO2/C and Pd/C. These results suggest that the incorporation of oxophilic materials improves the FOR activity on Pd-based catalysts in alkaline medium by reducing the CO adsorption.

M223 Distribution of water permeation in polymer electrolyte fuel cell system with hydrogen recycling
Yulei MA, Kazuhiro YAMAGUCHI, Miho KAGEYAMA, Motoaki KAWASE
Department of Chemical Engineering, Kyoto University, Kyotodaigaku-Katsura, Nishikyo-Ku, Kyoto 615-8510 Japan

At present, polymer electrolyte fuel cell (PEFC) technology is supposed to be commercialized in a wide range. However, water management is an essential problem to achieve maximum performance. The relative humidity (RH) of gases should be controlled to prevent membrane dehydration and liquid water flooding to maintain a high performance level. Hydrogen recycling is one of methods to humidify the cell with water produced in redox reaction, while the overall hydrogen utilization can be 100%. In this study, water transport in a PEFC system with hydrogen recycling was analyzed by combining plug flow reactor model and dimensionless modulus model in the through-plane direction in steady state, when the dry hydrogen and humidified air are fed to an 80 °C isothermal cell. The gas channel was regarded as a straight line in the model. Although the water flux through proton exchange membrane (PEM) has different distribution at different current density, total water permeation rate is 0, as far as the outlet gas of anode recycles to the inlet entirely (Fig. 1). In the case of co-current which the gas flows have the same direction on the anode and cathode sides, current density as well as electroosmosis increases from inlet to outlet of gas channel in low current region, because of humidification by produced water, which enhances the proton conduction in PEM and cathode layer. Besides, the difference in RH of gas flow on two sides of PEM creates water diffusion. When the gas flowrate increases, decreasing proportion of produced water makes PEM dehydrated, and the performance deteriorated (Fig. 2). The RH in the cell increases with decrease in flowrate. At 1 A/cm2 and H2/O2=2, RH becomes 68% at the exit of the cathode in case of 300 mL/min oxygen and RH reaches 100% at 21 mL/min.

M224 Stability, strain, and electronic structure of Pt3M (M = Co, Ni, and Cu) nanoparticles
David RIVERA1, Yusuke NANBA1, Michihisa KOYAMA1,2
1 National Institute for Materials Science, Tsukuba, Japan
2 Shinshu University, Nagano, Japan

The use of bimetallic nanoparticles (NPs) reduces the noble metal usage without sacrificing the electrocatalytic activity. To theoretically investigate the influence of the NPs' properties, such as strain, stability, or electronic structures on the catalytic activity requires the use of a “close to real size” cluster models. In this study, the phase stability, its origin and electronic structure of Pt3M (M = Co, Ni, and Cu) are investigated using density functional theory (DFT) method. Bimetallic Pt3M-NPs containing 201 (Pt150M51), 405 (Pt303M102), and 711 (Pt533M178) atoms in total were modeled considering three different configurations; 1-skin layer (S1), 2-skin layers (S2), and solid solution (SS). The stability of the Pt3M-NPs was approximated by the excess energy, which contains the mixing enthalpy and configurational entropy. In all cases, the bimetallic NPs were more stable than the monometallic Pt-NPs. For the S1 systems, the mixing enthalpy is the dominant term, and the configurational entropy value is the smallest compared to SS, and S2 systems, as shown in Figure 1. Electronic equilibration in line with the work function difference between Pt and M led to charge transfer from the M to Pt, reducing the surface Pt atoms in the S1 configuration. Additionally, the presence of M of smaller atomic radius than Pt in the core of the nanoparticle made the surface atoms more relaxed compared to the monometallic system, thus decreasing the stress in the structure and helping to accommodate the extra electrons from the M in the subsurface. These changes in the electronic structure and geometrical features were used as descriptors of the Pt3M stability. For Pt3Co and Pt3Ni the stability is largely determined by the surface charge, while for Pt3Cu the dominant factor is the surface strain.

M225 Experimental investigation on impact of thicknesses of PEM and GDL on temperature distribution in single PEFC generated at high temperature
Akira NISHIMURA, Satoru KAMIYA, Tatsuya OKADO, Kouhei YAMAMOTO, Masafumi HIROTA
Mie University, Tsu, Mie 514-8507, Japan

Polymer Electrolyte Fuel Cell (PEFC) is desired to be operated at high temperature such as 90 °C for stationary applications during the period from 2020 to 2025 in Japan. It can be expected thinner polymer electrolyte membrane (PEM) and gas diffusion layer (GDL) would promote the power generation performance of PEFC at this temperature. However, the current PEFC has Nafion membrane and is usually operated within the temperature range between 60 °C and 80 °C. The aim of this study is to clarify the impact of thicknesses of PEM and GDL on temperature distribution in single PEFC generated at high temperature such as 90 °C and to propose the optimum components combination.
As a result, from the investigation of impact of thickness of GDL on the power generation characteristics using the thickest PEM, Nafion 115, the impact of relative humidity of supply gas on the power generation characteristics was small for thin GDL. In addition, in-plane temperature distribution from the inlet to the outlet was flat by promotion of water transfer when using thin GDL. On the other hand, from the investigation of impact of thickness of PEM on the power generation characteristics using thin GDL, i.e., TGP-H-030, the impact of relative humidity of supply gas on the power generation characteristics was not acknowledged. However, the power generation performances using Nafion 212 and Nafion 211 were higher than that using Nafion 115. As to in-plane temperature distribution, it was flat when using Nafion 115 and Nafion 211, while it was increased from the inlet to the outlet using Nafion 212.
It was revealed that the thinnest combination of Nafion 211 and TGP-H-030 was the optimum for high temperature operation such as 90 °C from the viewpoint of the power generation performance as well as controlling in-plane temperature distribution.

M301 Development of novel preparation method of core-shell catalyst layer for PEFC using Ru nanosheet as core material
Shinshu University

Polymer electrolyte fuel cell (PEFC) has been attracting attention as a highly efficient power generation system. Since Pt used in a catalyst is scarce and expensive, it is important to develop a low-Pt catalyst. A core-shell catalyst, which consists of thin Pt shell on non-Pt metal core, has been developed to reduce the amount of Pt. Typically, Cu-UPD (underpotential deposition) followed by surface limited redox replacement (SLRR) is used to fabricate the core-shell catalysts. We have been developing a novel method suitable for mass production of membrane-electrode assembly (MEA) by initially fabricating a catalyst layer (CL) from the core material, and then perform Cu-UPD and SLRR on the CL to obtain a new CL of core-shell catalyst. Moreover, we focused on nanosheet (ns) catalysts. A general Pt-supported carbon catalyst has a problem in durability, since small Pt particles are easily aggregated and dissolved due to its large surface energy. It was reported that Ru@Pt-ns/C catalyst using Ru-ns as the core and Pt as the shell, exhibits high specific activity and high durability due to the low surface energy. In this study, a novel method to produce an electrode with low-Pt core-shell nanosheet catalyst was developed by using Cu-UPD/SLRR in the CL.
The effect of the ionomer ratio on the formation of core shell was investigated. Metallic luster was observed on the surface of the CL for I/C = 0.5 and I/C = 1, indicating abnormal deposition of Pt. However, it was not observed for I/C = 0.25, suggesting uniform core-shell formation. The influence of the number of times of Cu-UPD/SLRR was investigated. The Pt mass activity was low when 2 cycles of Cu-UPD/SLRR were applied but it improved when 4 cycles were applied. The Pt mass activity of Ru@Pt-ns/C prepared by the novel method was higher than Pt/C.

M302 Visualization of liquid water in micro porous layer formed by water vaper diffusion into gas diffusion layer for PEFC using X-ray computed tomography
Satoru KATO, Satoshi YAMAGUCHI, Akihiko KATO, Yoriko MATSUOKA, Wataru YOSHIMUNE, Yasutaka NAGAI, Takahisa SUZUKI
TOYOTA Central R&D Labs., Inc.

It is well known that laminating a microporous layer (MPL) to substrate such as carbon paper prevents from flooding in catalyst layer (CL) for polymer electrolyte fuel cell (PEFC). It is therefore important to visualize 3D water distribution in both the MPL and substrate to design the material. Visualization of 3D water distribution in the substrate was conventionally achieved by operando X-ray Computed Tomography (CT). However, 3D water distribution in the MPL has not been visualized due to the strong X-ray adsorption of the Pt in the CL. Here we present new method for visualizing 3D water distribution for the MPL. In the experiment, water vaper was diffused in the MPL, and its condensation process was measured by X-ray CT. This method does not need the CL. Conventional problem strong X-ray adsorption of the CL for Operando-CT can be avoided. Obtained sliced image of MPL is shown in Figure 1. Water in the MPL is observed as polka-dot patterns. This suggests that pore to water drain and pore to gas diffusion is separately exists in the MPL. In addition, water movement from wet domain from the MPL to substrate was visualized. These results show potential of the method to understand water condense and drain phenomena in the MPLs.

M303 Determination of Mass Transfer Resistances in PEFC by a Dimensionless Analysis
Department of Chemical Engineering, Kyoto University, Kyotodaigaku-Katsura, Nishikyo-Ku, Kyoto 615-8510 Japan

Optimization of the PEFC design is a crucial subject for its deployment and production expenses. However, a comprehensive understanding of its behaviour is needed, including its own structure, electrochemical reaction, reactants and products mass transfer limitations concerning proton and oxygen in principal. The mass transfer takes place through electrostatic drag for proton, and convection and diffusion of oxygen in the cathode catalyst layer (CCL). The authors introduced four dimensionless moduli which govern behavior of CCL.
Effectiveness factor is one under the reaction rate controlled regime, yet, is inversely proportional to Thiele modulus, as far as the convective flow effects are negligible and under oxygen transport control conditions. Under proton transport control conditions, the effectiveness factor is inversely proportional to the modulus that represents the ratio of the reaction rate constant to the effective proton conductivity.
To determine the effectiveness factor and dimensionless moduli, experiments were done on NR-212 (50 μm) with Pt/C weight ratio of 0.3, 0.4, and 0.5. For each Pt/C weight ratio, cathode catalyst layer thickness was 10, 30, 50 μm, using electrochemical measurement system. The impedance spectra were measured in a range of frequency from 10 mHz to 100 kHz.
Figure 1 shows the relation between IR-corrected cell voltage and current density for 10 μm cathode catalyst layer having a Pt/C ratio of 0.3, 0.4 and 0.5. The overall mass transfer limitation between Pt/C = 0.3 and 0.4 was comparable. Oxygen and proton transfer resistances were estimated.

M304 Conceptual Design for Significant Improvement in Efficiency of Long-Term Energy Storage with Reversible Solid Oxide Cells(R-SOCs)
Hiroki IINUMA1,2, Yoshio MATSUZAKI1,2, Koki SATO1,2, Yoshitaka BABA1,2, Yuya TACHIKAWA2, Hironori NAKAJIMA2, Shunsuke TANIGUCHI2, Junichiro OTOMO3
1 Tokyo Gas Co., Ltd., Yokohama, Kanagawa, Japan
2 Kyushu University, Fukuoka City, Fukuoka, Japan
3 University of Tokyo, Kashiwa, Chiba, Japan

Solid Oxide Fuel Cells and Solid Oxide Electrolysis Cells (SOFCs / SOECs) have much attention because SOFCs have the advantage of being able to convert fossil fuels to electricity with the highest efficiency and SOECs have the advantage of requiring less power for electrolysis compared to PEMs due to high temperature operation. From these backgrounds, both have been considered for practical use.
In recent years, studies on reversible Solid Oxide Cells (R-SOCs) which means a combination of SOFCs and SOECs are in progress. R-SOCs can be regarded as an energy storage system similar to a battery, but have the drawback of a smaller conversion efficiency than that of a battery. In this work, we performed theoretical efficiency calculations of R-SOCs system using an oxide-ion conductor and a proton conductor to show the merit in comparison with a battery.

M305 Development of low Ni-containing SOFC anodes based on percolation theory
Naoya FUJIWARA, Tatsushi MINAMI, Shohei TADA, Ryuji KIKUCHI
The University of Tokyo, Tokyo, Japan

Ni-based cermets are typically used for anodes of solid oxide fuel cells. However, the Ni phase in such anodes can cause durability problems. One possible approach for mitigating the problems is to reduce the Ni content in the anode, although decreased Ni amount in turn reduces conductivity and electrochemical activity of the anode. In this study, Ni-SDC (samarium-doped ceria) cermet anodes were prepared with different SDC particle sizes and Ni contents, and it was investigated how particle size ratio of the SDC and Ni affected the performance at low Ni contents. Ni-SDC|YSZ|LSM cells were fabricated, then current-voltage characteristics and AC impedance spectra were measured. Impedance analyses with equivalent circuits revealed that ohmic resistance was the primary factor affecting the anode performance in the tested system, and it was found that large SDC particles were effective in reducing the ohmic resistance even at low Ni contents. To further investigate the effects of the particle size ratio, conductances of the Ni-SDC anodes with different SDC particle sizes were calculated from the measured ohmic resistances. The conductances decreased sharply at certain volume fractions of Ni, and the threshold volume fractions shifted toward lower Ni contents when large SDC particles were used. Independently, threshold Ni volume fractions were calculated according to percolation theory, using particle sizes of Ni and SDC estimated from SEM observations. The thresholds thus calculated were in good agreement with those obtained from the ohmic resistance, indicating that the electrical conductivity of the Ni-SDC anodes was governed by the formation of segregated and conductive Ni clusters.

M306 Kinetics model to describe reversible operation of solid oxide fuel cell / electrolysis with competitive adsorption reaction on anode triple phase boundary
Kei HASEGAWA, Hyojae LEE, Keisuke KAMEDA, Yuta IIDA, Manabu IHARA
Tokyo Institute of Technology, Tokyo, Japan

Due to the expanding installation of renewable energy, to solve the gap between the unsteady power supply and the demand becomes a key issue, and the reversible solid oxide fuel cell/ electrolyzer (rSOFC/EC) are increased their attention as a large-scale energy storage. To control their unsteady operations, the quantitative understanding of the reversible reaction kinetics is required. A number of reaction kinetics models of SOFC on Ni/ yttria stabilized zirconia (YSZ) have been proposed [1-3]. The rate determining was described as a surface chemistry on triple phase boundary (TPB) under the local equilibrium between oxygen, O2- and electron [1, 2], or the charge transfer reaction of neutral absorbent, surface ion and electron between Ni and YSZ [3]. In both case, the reaction of SOFC/EC have not been successfully described as a unified kinetics.
We applied the existing reaction model of SOFC anode, which we previously developed [2], to the reversible SOFC/EC with the series of H2/H2O gas components to discuss the SOEC anode reaction. The model is described the kinetics by competitive adsorption reaction at TPB with oxygen activity (aO) calculated from anode potential. As a result, the current density of SOEC was much larger than the extrapolated value by SOFC data at any H2/H2O gas condition. By reinvestigating the local equilibrium of adsorbents, oxide ion and electron on Ni, we proposed a modified kinetics model by defining the electron activity ratio as another independent variable. The kinetics is discussed with the shift of local oxygen equilibrium by changing the charge balance.
Acknowledgement: a part of this work is supported by the New Energy and Industrial Technology Development Organization (NEDO)
[1] Mizusaki et al., Solid State Ionics, 70/71. 52 (1994).
[2] Ihara et al., J. Electrochem. Soc., 148(3), A209 (2001).
[3] Bieberle et al., J. Electrochem. Soc., 148(6), A646 (2001).

M313 Triple phase boundary reactions in solid oxide fuel cell anode: combined atomic-resolution microscopy and reaction dynamics simulation
Michihisa KOYAMA1,2,3, Shusheng LIU3, Leton SAHA3,4
1 Center for Green Research on Energy and Environmental Materials, National Institute for Materials Science
2 Research Initiative for Supra-Materials, Shinshu University
3 INAMORI Frontier Research Center, Kyushu University
4 Institute of Fluid Science, Tohoku University

The triple phase boundary (TPB) of metal, oxide, and gas phases in the anode of solid oxide
fuel cells plays an important role in determining their performance. In this study, we explored the TPB structures and reaction at TPB combining two approaches: atomic-resolution microscopy observation based on HAADF-STEM (High-angle annular dark field scanning transmission electron microscopy) and reaction dynamics simulation based on reactive force field. From HAADF-STEM observations, two distinct structures are found with different contact angles of metal/oxide interfaces, metal surfaces, and pore opening sizes, which have never been adopted in theoretical simulations in literature. Chemical reaction dynamics simulations for the hydrogen oxidation reaction (HOR) at the TPB are performed using realistic models reconstructed from HAADF-STEM observations. In addition, extensive development of accurate reactive force field parameters was conducted to accurately trace the reaction pathways at TPB. As a result, the activity of different structures towards HOR is clarified, and a higher activity is obtained on the TPB with smaller pore opening size. Three HOR pathways are identified: two types of hydrogen diffusion processes, and one type of oxygen migration process which is a new pathway.

M314 Microfabrication of anode functional layer in SOFC by using 3D printer
Waseda Univerisity, Tokyo, Japan

After the Great East Japan Earthquake, there is demand for transformation to a bidirectional system introducing distributed power sources, and a fuel cell cogeneration system with advanced energy utilization has been attracting attention. Even among them, solid oxide fuel cell (SOFC) are high efficiency power generation systems and expected as a promising power source. It is necessary to reduce the raw material cost by improving the power density for further penetration of SOFC. Electrochemical reactions occur only on an effective triple phase boundary (TPB) where each network path of the electron, the oxide ion and the fuel gas connects uninterruptedly. The power generation performance was affected by the effectiveness of TPB. This work aims to realize a microstructure expanded effective TPB between the anode and electrolyte by using a commercial ink-jet 3D printer. Anode and electrolyte inks suitable for material jetting were prepared by changing the viscosity and the particle size. The anode ink formed a porous structure by adding acrylic particles, which ensured the path of the fuel gas. The electrolyte ink formed a dense structure to avoid cross leakage. The microstructure was formed by laminating linear structures in which the porous anode and the dense electrolyte lines were alternately arranged in parallel and orthogonally stacked. The microstructure was inserted between the anode and electrolyte as the anode functional layer of which width and thickness of linear structure were approximately 100 and 1 microns, respectively. The single cell with the microstructure was tested at 600 °C being fueled by dry methane and showed a high performance.

M315 Effect of thin bilayer electrolytes on performance of anode-supported proton-conducting solid oxide fuel cells
Hiroki MATSUO, Junichiro OTOMO
The University of Tokyo, Kashiwa, Chiba, Japan

Fuel cells are one of the electrochemical energy conversion devices which can directly convert the chemical energy into electric energy with a high efficiency. Conventional solid oxide fuel cells (SOFC) using oxide ion conducting electrolyte have various difficulties arising from high operating temperatures (700–1000 oC) such as degradation of materials and slow start up and cooldown. Development of electrolytes which can operate at intermediate temperature (500–700 oC) has been desired to overcome these problems.
In this situation, researchers have investigated proton conducting solid oxide fuel cells (PCFC) with thin-film proton-conducting electrolyte to realize intermediate temperature operation. Rare earth-doped BaZrO3 and BaCeO3 have been intensively studied as thin-film electrolytes for PCFC because of their high proton conductivity at intermediate temperatures. However, current leakage through the electrolyte layer occurs as the electrolyte thickness becomes thinner owning to a high hole conductivity in oxidative atmosphere at air side of the cell. Therefore, development of an approach to reduce the current leakage of proton-conducting electrolytes at oxidative atmosphere is required to realize intermediate temperature operation with a high power density.
In the SOFC with ceria-based oxide-ion-conducting electrolyte, formation of bilayer electrolyte consisting of a rare earth-doped ceria layer and a thin Y-doped zirconate layer at fuel side was reported to be effective in suppression of current leakage arising from reduction of ceria. In this research, we extended the concept of the bilayer electrolyte to PCFC in which oxidation of electrolytes at air side is an origin of the current leakage. Anode-supported PCFCs with bilayer electrolyte consisting of Y-doped SrZrO3 layer and Y-doped BaZrO3 layer were prepared by a pulsed-laser deposition (PLD) method and current-voltage measurements and electrochemical impedance spectroscopy measurements were carried out. We will discuss the effect of the bilayer electrolyte on the cell performance of anode-supported PCFC.

M316 Proposal of carbon-air secondary battery system and evaluation of its potential as a large-capacity energy storage
Keisuke KAMEDA, Yuta IIDA, Mankichi HOSODA, Tatsuya MATSUHIRA, Kei HASEGAWA, Manabu IHARA
1 Tokyo Gas Co., Ltd., Yokohama, Kanagawa, Japan
2 Kyushu University, Fukuoka City, Fukuoka, Japan
3 University of Tokyo, Kashiwa, Chiba, Japan

To introduce renewable energy or electric vehicles, hydrogen power to gas to power (PtoGtoP) or lithium air battery have been developed for increasing energy density of batteries. However, there remains issues that hydrogen needs to be compressed to several tens of MPa or to be below -250 °C for increasing the energy density, and reduction of Li2O2 needs large overvoltage. Therefore, we made an idea to apply the redox reaction of CO2 and carbon to secondary battery because of easy storage of CO2 and high energy density of carbon. Here we proposed carbon-air secondary battery (CASB) system.
The CASB system can be composed of solid oxide fuel cell (SOFC), stored liquid CO2 and solid carbon. The CASB system works as secondary battery by electrolysis of CO2 and power generation using carbon directly. Storage of CO2 can be easier and safer than storage of hydrogen because CO2 liquefies under 6 MPa. In addition, the theoretical conversion efficiency of the redox reaction C+O2⇄CO2 equals to 1, so that the CASB system is expected to work efficiently.
In this research, we demonstrated the redox reaction and evaluated potential of the CASB system as large-capacity energy storage by comparing the theoretical volumetric power density and energy density with existing and developing secondary batteries and hydrogen PtoGtoP.
We prepared a coin type SOFC supported by the electrolyte, and repeated electrolysis of CO2 and power generation using generated fuel at 800 °C, 100 mA/cm2. During charge operation, analysis of Nernst potential revealed that carbon deposited by Boudouard reaction 2CO→C+CO2 with increasing partial pressure of CO due to electrochemical reaction CO2+2e-→CO+O2-. During discharge operation, carbon or CO was used for power generation. A discussion about potential of the CASB system showed that it can have larger gravimetric and volumetric energy density than secondary batteries and hydrogen PtoGtoP.

M317 [Keynote] Electrical energy storage in functionalized renewable materials
Rajan JOSE
Universiti Malaysia Pahang

Sustainability has emerged as a keyword in all aspects of life whether it is resources or technologies and products or processes. Besides, nearly a billion new consumers join the society in 13-15 years; and the growing demand for higher standards of living make the worldwide materials consumption continuously growing. Strategic solutions are therefore required not only for addressing the gaps but also for eliminating the undesirable environmental effects of supply chain to ensure quality and sustainable living. Energy storage is currently a multibillion dollar industry and is expected to be continuously growing because (i) electrification of products and services has been emerged as an efficient strategy to mitigate carbon footprints from major emitting sectors such as automobiles and (ii) internet of things, advanced communication devices and other modern electrical appliances such as drones and robots demand efficient electrical energy storage devices. Source of primary materials supply for this large industrial sector is therefore crucial; extensive use of earthborn materials as energy storage medium would not only lead to disasters but also would result in expensive devices. Functionalization of renewable materials such as biomass carbon, cellulose, oils etc. as components of energy storage devices would ensure a sustainable living. This lecture will focus on the current state of renewable materials as an energy storage medium, both in the lecturer's laboratory and elsewhere, and foreseeable initiatives required to build efficient energy storage devices using renewable materials.

M321 Selective Electrochemical Carbon Dioxide Conversion to Hydrocarbons on Ni/Cu Binary Electrodes
Naoki YOSHIHARA, Hiroki SAITO, Masaru NODA
Department of Chemical Engineering, Fukuoka University, 8-19-1 Nanakuma, Jonan-ku, Fukuoka 814-0180, Japan

Due to population and economic growth, further increases in energy demand are predicted globally. Therefore, the construction of a sustainable carbon cycle system is essential to address fossil fuel depletion. The conversion of carbon dioxide (CO2) to hydrocarbons is currently a major challenge.
Among available technologies, the electrochemical conversion of CO2 on copper (Cu) electrodes has gained popularity as a novel technique to realize a sustainable carbon cycle because of improvements in power generation using renewable energy sources, such as solar and wind energy. However, the electrochemical conversion of CO2 on Cu electrodes not only produces valuable hydrocarbon products but also emits byproducts such as carbon monoxide (CO) and hydrogen (H2) because the product selectivity of this conversion is sensitive to the Cu electrode's surface properties, such as atomic arrangement and morphology. Therefore, electrodes for a more selective electrochemical conversion of CO2, which promote hydrocarbon formation and suppress byproduct formation, are required for practical technology.
In this work, we report the selective electrochemical conversion of CO2 on nickel (Ni) / Cu binary electrodes. The formation of hydrocarbons on these electrodes was strongly dependent on both the crystal structure of the supporting Cu electrode and the amount of Ni deposition. This suggested that the adsorption of a carbonate intermediate on the surface of Ni/Cu binary electrodes, formed by the electrochemical conversion of CO2, improves to the selective electrochemical CO2 conversion for hydrocarbon formation compared with pristine Cu electrodes. Based on these results, we discuss the mechanism of the selective electrochemical CO2 conversion and the inhibition of H2 byproduct formation on Ni/Cu binary electrodes.

M322 Effect of Pd doping on Sn surface for the electrochemical reduction of CO2/HCO3 to HCO2
Sreekanth Narayanaru1, Anilkumar Gopinathan1,2, Tamaki TAKANORI1, Takeo YAMAGUCHI1
1 Tokyo Institute of Technology, Tokyo, Japan
2 Noritake Co. Ltd, Nagoya, Aichi, Japan

Formic acid or formate is considered as a perfect fuel for clean energy generation through fuel cells. Formate can be electrochemically generated from CO2/HCO3. According to techno economic analysis, formic acid/formte is one of the most profitable products of electrochemical CO2 reduction reaction. Sn based electrocatalysts are known for the selective production of formate from CO2 with a faradaic efficiency >80%. But main drawback of these catalysts is high overpotential for the reaction. Various methods have been tried to reduce the overpotential and to improve the catalytic activity of Sn. In this work, we investigated the effect of Pd doping on the surface of Sn for the electrochemical generation formate from CO2 and HCO3.
We prepared Sn and Pd nanoparticles decorated N doped carbon fibers (SnPd-NCF) from SnCl2, PdCl2 and polyacrylonitrile using electrospinning method. SEM and TEM analysis confirm the uniform distribution of Sn and Pd nanoparticles over N doped carbon fibers. XPS spectra confirmed nitrogen-doping on carbon fibers. We found that an addition nearly 1.5 wt % of Pd on Sn surface greatly enhance the faradaic efficiency of formate formation and reduce the overpotential nearly by 0.3 V compared to that of Sn nanoparticles decorated N doped carbon fibers (Sn-NCF).
Figure. (a) Voltammetric response of CO2 reduction on Sn-NCF and SnPd-NCF in 0.5 M KHCO3 solution saturated with CO2. (b) Faradic efficiency of formate produced on Sn-NCF and SnPd-NCF during CO2 reduction reaction at -0.85 V vs RHE.

M323 First-principles study of catalytic activity modifications with electric field
Katsuhiro WAKAMATSU, Teppei OGURA
Kwansei Gakuin University, 2-1 Gakuen Sanda, Hyogo, Japan

Non-Faradaic electrochemical modification of catalytic activity (NEMCA) by impression of electric field (EF) is one of the methods to improve catalyst performance. It has been discussed that oxygen anions forced electrochemically to adsorb on catalyst surface alter the catalyst electric property. However, given EF also changes the catalyst electric property directly. Because it is difficult to divide down these effects with an experimental approach, we have tried to theoretically investigate the mechanism of NEMCA in CO2 methanation (CO2 + 4H2 → CH4 + 2H2O (1)) in solid oxide electrolysis cell (SOEC) using the density functional theory (DFT). In concreate, we have focused on the rate-determining steps (RDSs) of CO2 methanation proposed by our detailed reaction mechanism analysis. We have calculated the adsorption energies of hydrocarbon species related to RDSs on Ni(111) (CO2 → CO + O (2), CHO → CH + O (3), CH4 → CH3 + H (4)) with EF or co-adsorbed oxygen atoms. In our calculative setup, used is the model sandwiched between thin film condenser boards connected to the outlet electrode for direct EF impression calculations, While used is the Ni(111) surface with different number of oxygen atoms for co-adsorption calculations. Due to space limitation, just an example of our calculations is shown in this abstract. With external EF, the equilibriums in reactions (2), (3) and (4) are all leaned to products side in the EF from the gas phase to the Ni surface (negative values in Table 1), which means CO2 methanation is promoted in this EF direction. This tendency is caused by the destabilization of reactants (CH3 in reaction (3)) or the stabilization of products (O, CO in reactions (1), (2)) with an EF as shown in Table 1 (right side). Other results and detailed discussion will be reported at our presentation in this conference.

M324 Structural analysis of furfural resin -based active carbon to control electric double layer capacitor
Takeyasu SAITO1, Kanade HOKARI1, Shinichiro SUZUKI1, Naoki OKAMOTO1, Isamu IDE2, Masanobu NISHIKAWA2, Yoshikazu ONISHI2
1 Dept. of Chemical Engineering, Osaka Prefecture University, Sakai, Japan
2 Lignyte. Co., Ltd., Sakai, Japan

Electric double layer capacitor (EDLC) can store energy by an electric double layer at the interface between the electrode and the electrolyte, which is one of the emerging energy storing devices. High capacity, high durability and rapid charge-discharge capability are attractive, however, low energy density poses drawback to practical use. Specific surface area, surface functional group, and pore size distribution are important controlling factors to improve energy density. In this study, the relationship between the surface functional group and the pore size distribution, and the EDLC capacity was investigated while the specific surface area was nearly equal value as 1200±100 m2/g. In addition, the effect of particle was investigated.
We prepared activated carburized furfural resin particles (1 μm in diameter) with KOH activation for 0 to 0.5 h at 700 to 800 °C in N2 flow, then investigated the electrostatic characteristics of the capacitors in 6M KOH by using a two coin-shaped electrodes. Activated carbon (1 μm in diameter) treated by 750 °C-0 h or 800 °C-0 h had 2.5 times larger mesopore volume and 1.9 times larger mesopore ratio than the one by 700 °C-0.5 h. The fractional order of lactone increased from 700 °C-0.5 h (9.7%), 800 °C-0 h (10.6%) to 750 °C-0 h (24.5%). The fractional order of carboxyl groups increased from 750 °C-0 h (18.1%), 800 °C-0 h (23.0%) to 700 °C-0.5 h (31.4%). Activated carbon treated by 750 °C-0 h (227 F/g) and 800 °C-0 h (225 F/g) were higher than 700 °C-0.5 h (198 F/g). From these relationship, there would be no clear trend for specific capacity per weight under the situation having the nearly equal SBET. We assumed that mesopore ratio should be a main factor to obtain high specific capacity per weight at this moment.

M325 Efficient production of TiO2 / porous carbon nanocomposites through the vacuum liquid pulse chemical vapor deposition technique
Shinichiroh IWAMURA, Shota MOTOHASHI, Shin R. MUKAI
Hokkaido University, Sapporo, Japan

TiO2 is a promising material for the development of lithium-ion capacitors, because side reactions hardly occur at the charge/discharge potential of TiO2, compared to graphite. When using TiO2 as an electrode material, it is necessary to combine it with carbon at the nanometer level to improve its low electrical conductivity and low rate of reaction with Li+. However, preparation methods of reported TiO2/carbon nanocomposites are generally not cost effective, and their productivities are low. In this study, the vacuum liquid pulse chemical vapor deposition (VLP-CVD) technique was developed to easily prepare nanocomposites of TiO2 nanoparticles and commercially-available porous carbons. Using this technique, TiO2 nanoparticles with a diameter of ~4 nm could be homogeneously deposited inside pores of meso- or macroporous carbon. Because the deposited TiO2 nanoparticles connect to electrical conductive paths of the porous-carbon substrates, they showed a high discharge capacity of ~200 mAh/g-TiO2 (based on the TiO2 weight). In particular, the composite prepared from macroporous carbon showed extremely high rate performance, where 50% of the discharge capacity was retained at a current density of 15000 mA/g when compared to that measured at 50 mA/g. In addition, the composite also showed very high cyclability, where 80% of the discharge capacity was retained at the 10000th cycle. Because the VLP-CVD technique can be performed using simple apparatus and commercially available starting materials, it can be expected to apply this technique to industrial production of TiO2/porous-carbon nanocomposites for lithium-ion capacitors.

M326 Study of Si/TiO2/Perovskite interfaces for perovskite/Si tandem solar cell
Gekko BUDIUTAMA1, Kazuma SUZUKI1, Methawee NUKUNUDOMPANICH1, Kei HASEGAWA1, Xiaomei ZHANG1, Erwann FOURMOND2, Alain FAVE2, Manabu IHARA1
1 Tokyo Institute of Technology, Tokyo, Japan
2 Institut National des Sciences Appliquées de Lyon, Lyon, Japan

The utilization of crystalline silicon solar cell and organometal halide perovskite solar cell in tandem application has attracted a lot of attention for its high theoretical energy conversion efficiency (>35%). However, the approach of superposing these two solar cells raised issues that have to be clarified and rectified in order for this technology to reach its potential.
In a 2-terminal perovskite/Si solar cell configuration, the bottom silicon solar cell is superposed by perovskite based top cell using highly doped silicon layers as a tunnel junction. This approach comes with three main issues: 1. interface between silicon and TiO2, 2. quality of the perovskite thin layer, 3. transparency and conductivity of front electrode.
The main challenge in the Si/TiO2 interface is to reduce carrier recombination. In addition, constraints on fabrication techniques such as high temperature treatment in TiO2 deposition requires careful consideration to make sure a good surface passivating layer is fabricated properly. Secondly, as topological structure of substrate affects the structure of the thin film, the quality of perovskite layer when fabricated on silicon substrate and ITO covered glass has to be compared and analyzed. Thirdly, as light has to pass through the front electrode in order to reach perovskite absorbing layer, the transparency and conductivity of front electrode has to be optimized in order to achieve the maximum performance of the tandem solar cell.
In this study, we designed an experimental approach to understand these challenges by fabricating perovskite solar cell using highly doped n-type silicon wafer as substrate (Figure). We found that when typical TiO2 is used to passivate silicon wafer, the carrier lifetime decreased dramatically. To mitigate this phenomenon, we are currently modifying the structure of TiO2 with various annealing methods and analyzing the relationship between TiO2 structure and its properties as passivating layer.

M401 Atomically dispersed Ni–N x Species anchored porous carbon with embedded Ni nanoparticles for efficient alkaline hydrogen evolution
Yang Hou
Key Laboratory of Biological Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, China.

Exploring earth-abundant, active and stable electrocatalysts to replace noble metal materials for hydrogen evolution reaction through alkaline water electrolysis system is key to the development of sustainable energy conversion technologies. Here, we report a novel hybrid electrocatalyst comprised of atomically dispersed Ni-Nx species anchored porous carbon matrix with embedded Ni nanoparticles. Benefiting from the high surface area and strong coupling interaction of the Ni NP and Ni-N-C, the achieved Ni NP Ni-N-C EG hybrid electrode displays excellent electrocatalytic activity for HER in basic condition with a low overpotential of 147 mV to reach current density of 10 mA cm-2. The overpotential for the Ni NP Ni-N-C EG is well comparable to the best reported value in literature for all existing heteroatom doped nanocarbon catalysts and even lower than those reported for other transition metal based compounds in basic media. Furthermore, the Ni NP Ni-N-C EG hybrid electrode exhibits outstanding catalytic activity for overall water splitting under alkaline condition, as reflected by delivering a current density of 10 mA cm 2 at 1.58 V, which surpasses that of the benchmark combination catalyst for sufficiently high overpotentials. Electrochemical results, coupled with the thiocyanate poisoning experiments, HAADF-STEM analyses, XPS analysis, as well as the EXAFS and XANES results, reveal that the hybridization of atomically dispersed Ni-Nx active centers with that of embedding Ni NP modulates the electronic structure and facilitates electron transfer at the constructed interface, which synergistically boost the HER performance of Ni NP Ni-N-C. Theoretical calculations manifest that the incorporation of Ni NP into atomically dispersed Ni-N-C frameworks can effectively promote initial water dissociation process and simultaneously optimize the OH adsorption free energy on the Ni NP Ni-N-C, resulting in the improved kinetics of the HER in alkaline solutions.

M402 Anion exchange membrane with thermally convertible polymer system for alkaline water electrolysis application
Hafis Pratama Rendra GRAHA1, Shoji MIYANISHI2, Shinji ANDO3, Takeo YAMAGUCHI1,2,3
1 Tokyo Institute of Technology, Japan
2 JST-CREST, Japan
3 KISTEC, Japan

Hydrogen is a promising energy carrier to utilize renewable energy sources. It can be generated by using water electrolysis technology. Alkaline water electrolysis using anion exchange membranes (AEMs) draws a lot of attention. Besides being able to use non-noble metal catalysts, its performance is better than conventional alkaline water electrolysis thanks to lower internal cell resistance. However, the development of this technology is hindered by the lack of high performance and durable AEMs. Ether-free aromatic AEMs can be promising candidates to overcome the performance and durability issues. In this research, we proposed a unique AEMs molecular design using thermally convertible polymer system (Fig.1). Highly soluble precursor polymer is used to prepare a thin membrane. This precursor membrane then heated to obtain ether free backbone membrane.
We prepared the precursor polymer by Suzuki-Miyaura coupling of the monomers followed by bromination then quaternized to afford TPP-V2. Number average molecular weight (Mn), polydispersity (PDI) and ion exchange capacity (IEC) of TPP-V2 are Mn= 24,600 g/mol,, PDI=2.9 and IEC= 2.90 meq/g, respectively. Ultra-thin flexible membrane as thin as 8 μm can be cast from TPP-V2 solution in dimethylsulfoxide. TP-V2 membrane was obtained by heating TPP-V2 membrane at 180 oC for 1 h under vacuum. After conversion to TP-V2, IEC value increases to 3.78 meq/g. Despite higher IEC, water uptake of the TP-V2 is lower than it's precursor as π-π stacking appears. TP-V2 shows high alkaline and oxidative durability after exposed to 8M NaOH for 120 h at 80 oC (alkaline stability test) and 3% H2O2 & 3 ppm FeSO4 60 oC for 8 h (oxidative stability test). The ionic conductivity was almost the same even after exposure to such very harsh conditions. These results suggest our approach is promising for making high-performance AEM for alkaline water electrolysis application.
Acknowledgement: Part of this paper is based on results obtained from a project commissioned by the New Energy and Industrial Technology Development Organization (NEDO).

M403 Carbon-free connected Ir nanoparticle catalysts for oxygen evolution reaction in polymer electrolyte water electrolysis
Yoshiyuki SUGITA1, Takanori TAMAKI1,2, Hidenori KUROKI2,1, Takeo YAMAGUCHI1,2
1 Tokyo Institute of Technology, Yokohama, Kanagawa, Japan
2 Kanagawa Institute of Industrial Science and Technology, Yokohama, Kanagawa, Japan

Oxygen evolution reaction (OER) catalysts for polymer electrolyte water electrolysis (PEWE) suffered from their low surface area because carbon support cannot be used for OER operating at high potential. Connecting metal nanoparticles enable catalysts to conduct electrons through nanoparticle networks without any support materials while keeping their high surface area. Thus, connected nanoparticle catalysts (Fig. 1 (A)) are promising for OER. Previously, we have developed connected Pt-Fe nanoparticle catalysts with hollow capsule structure for oxygen reduction reaction (ORR) in polymer electrolyte fuel cells (PEFCs).[1]
In this study, we proposed Ir nanoparticle catalysts for OER in water electrolysis because Ir has high OER activity. Ir nanoparticle catalysts were synthesized as follows. First, Ir nanoparticles were synthesized on silica template via polyol method using tetraethylene glycol as reducing agent and Ir(III) acetylacetonate as the metallic precursors (Ir/PDDA/SiO2). Then, these nanoparticles were coated with SiO2 using tetraethoxysilane in a mixed solvent of ethanol and NH3 solution. After coating, they treated in supercritical ethanol at 330 °C for 90 min. Dissolution of SiO2 in 3 M NaOH solution at 85 °C for 3 h made porous hollow structure (Ir capsule). OER performance were evaluated by cyclic voltammetry in 0.1 M HClO4 solution. A membrane electrode assembly (MEA) was fabricated by Ir/PDDA/SiO2 as an anode catalyst, and its water electrolysis performance was measured.
Fig. 1 (B) shows TEM image of Ir capsule. Capsule and networks structure of the catalyst were observed by TEM images. Fig. 1 (C) and (D) show OER curves and mass activities of Ir catalysts. Mass activity of Ir/PDDA/SiO2 was 2–3 times higher than Ir capsule and commercial Ir black. MEA using Ir/PDDA/SiO2 showed good performance.
[1] T. Tamaki, H. Kuroki, T. Yamaguchi et al., Energy Environ. Sci., 8, 3545-3549 (2015).
Acknowledgement: This paper is based on results obtained from a project commissioned by the New Energy and Industrial Technology Development Organization (NEDO).

M404 Cu nanowire@MnNiP Electrocatalysts for Water Splitting in Neutral Solution
Suchada SIRISOMBOONCHAI1,2, Akihiro YOSHIDA1,2, Abuliti Abudula2, Guoqing GUAN1,2
1 Energy Conversion Engineering Laboratory, Institute of Regional Innovation (IRI), Hirosaki University, 2-1-3, Matsubara, Aomori 030-0813, Japan
2 Graduate School of Science and Technology, Hirosaki University, 1-Bunkyocho, Hirosaki 036-8560, Japan

Water electrolysis by using renewable energy such as wind and solar energy for hydrogen production is considered a promising way to storage the unstable electricity and realize low-carbon society. However, for large-scale application of water electrolysis, the key is to design low-cost electrocatalysts with high performance for the replacing of the noble metal based catalysts. Meanwhile, in the water electrolysis, the electrolyte includes acidic, alkaline, industrial waste water, and seawater with different pH values. It is expected to have the electrocatalysts which can work in a wide pH range, especially in the neutral solution so that it can be applied anywhere. Moreover, the solutions with the neutral pH value is harmless and environmentally friendly. In this study, nanostructured manganese-nickel mixed oxide with nanosheet array was fabricated on the Cu nanowires growning on the copper form <CF> by electrodeposition method, and then further phosphorized to MnNiP. The obtained Cu nanowire @ MnNiP/CF electrode was used for the hydrogen evolution reaction in water electrolysis. As a result, a low overpotential of 104 mV@10mAcm-2 with a small Tafel slope of 55.1 mV dec-1 in the neutral solution was achieved due to the enhanced charge transfer ability, improved surface active area and fast reaction kinetics.

M405 Effect of cell temperature on relative humidity in a polymer electrolyte fuel cell
Beste BALCI, MA Yulei, Bixiao ZHANG, Kazuhiro YAMAGUCHI, Miho KAGEYAMA, Motoaki KAWASE
Department of Chemical Engineering, Kyoto University, Kyotodaigaku-Katsura, Nishikyo-Ku, Kyoto 615-8510, Japan

Recent studies on polymer electrolyte fuel cell (PEFC) based energy generation have focused more on elevated temperature (above 100 °C), since high temperature PEFC (HT-PEFC) enhances tolerance to CO and prevents flooding as well as makes waste heat emission and its utilization easy. However, relative humidity (RH) management appears more difficult at elevated temperature. RH profile inside the cell should be well analyzed to ensure proton exchange membrane (PEM) is sufficiently hydrated to keep moisture content. In the current study, 1D model in the direction along the gas channel has been built for the straight co-current flow channels for analyzing water behavior at varied cell temperature and total pressure. Water permeation flux, moisture content, and proton conductivity of PEM were calculated. Employing straight channels, RH profile in the cell can be measured as change in RH at the cell outlet with varying the gas flow rate in experiments. Measured and calculated RH profiles through the gas channel were investigated at varied cell temperature. Total water flow rate at the outlet increases as the current increases. Partition of generated water to two sides is determined by the inlet RH and flow rate conditions. As the cell temperature is higher, the saturated vapor pressure is the higher. The more water generation is required to attain a certain RH through the cell at the higher cell temperature. This is the most important reason that water management is more difficult at elevated temperature.

M406 (canceled) <100859-1>
M413 Possible energy system with H2 storage contributing to grid power stability under large-scale implementation of solar cells
Fumitaka HIRAHARA, Tatsuya OKUBO, Kei HASEGAWA, Manabu IHARA
Department of Chemical Science and Engineering, Tokyo Institute of Technology, Tokyo, Japan

The power grid supplies electric power while maintaining 1. voltage, 2. frequency, and 3. transient stability, three conditions for stable power supply from the electric grid. However, recent large-scale implementation of solar cells has caused difficulties in meeting these conditions because of the power supply-demand gap. To solve this problem “leveling power”, the ability to keep the balance of supply and demand of power, is required. Although power has been leveled by power grid, the leveling by distributed energy system is also required. Energy storage technology is one of the methods to introduce power leveling in the distributed energy system. Combination of energy storage technologies, such as battery or Power to Gas (P2G), which converts power to hydrogen, is expected to contribute to the stability of power supply. Actual data with the range of minute to second is required to investigate the feasibility of each technology as power leveling.
In this research, firstly we analyzed the current status of power leveling required for power-grid by using actual generation and power demand data published by power companies across Japan and the actual data at Ookayama campus in Tokyo Institute of Technology. Smart energy system “Ene-swallow” installed at Ookayama campus accumulates power demand data in a second and solar generation data in a minute. Secondly, we calculated total supply-demand gap in the assumption of large-scale implementation of solar cells by using actual annual data in a minute from “Ene-swallow” and then we designed required amount of P2G system and battery for the leveling. The analysis showed that the total system cost could be reduced by using the combined system of P2G and battery.
[Acknowledgements] A part of this study is supported by the New Energy and Industrial Technology Development Organization (NEDO) and MIRAI program of Japan Science and Technology Agency (MIRAI JST).

M414 Possible cost reduction with high volume 2D manufacturing concept for fuel cells
Nissan Motor Corporation
M415 Techno-economic analysis of a distributed hydrogen energy storage system considering horizontal and vertical installation of solar cells
Tatsuya OKUBO1, Teruyuki SHIMIZU1,2, Kei HASEGAWA1, Manabu IHARA1
1 Department of Chemical Science and Engineering, Tokyo Institute of Technology, Tokyo, Japan
2 Presidential Endowed Chair for “Platinum Society”, The University of Tokyo, Tokyo, Japan

Recently, the implementation of renewable energy, especially photovoltaics (PVs), has been rapidly expanded due to its significant cost decline with technology and market development. However, the supply fluctuation of renewable power sources makes keeping the balance of electricity demand and supply difficult. In order to make the best use of renewable power sources, the electricity demand-supply gap has to be balanced using energy storage technologies. Power-to-Gas (P2G), which converts electricity to hydrogen, is a promising candidate for a large-scale, long-term energy storage technology.
In this research, we analyzed the economic efficiency of distributed P2G system considering not only horizontal but also vertical installation of PVs. This analysis was carried out based on actual data accumulated in smart energy system “Ene-Swallow”. We used electricity demand data from the Ookayama campus in Tokyo Institute of Technology, and power generation data of PVs installed at the Environmental Energy Innovation (EEI) building, where PVs are installed on the rooftop, the south and west walls as shown in figure 1. We modeled the P2G system to simulate power generation and consumption at every hour of a single year, and to evaluate the total cost including the fixed and variable cost.
This analysis shows that if the price of each device decreases due to technology and/or market development in the future, appropriate implementation of a distributed P2G system will lower the total cost compared to the case where all of the required power was purchased from the power grid. This study also shows that in Tokyo area, appropriate combination of horizontal and vertical PV installation can lower the total cost compared to the case where only horizontal PV is installed. In addition, to discuss the feasibility of this analysis results, we investigated the possible installation amount of PVs at the Ookayama campus.

M416 Customized water electrolysis cell towards the efficient production of hydrogen
Xunyu LU, Emma LOVELL, Jian PAN, Rose Amal
Particles and Catalysis Research Group, School of Chemical Engineering, The University of New South Wales, Sydney, NSW 2052, Australia

Photovoltaic (PV) cells powered water electrolysis cells (WECs) are capable of converting and storing the solar energy in the form of hydrogen (H2), thereby facilitating the continuous usage as well as distributing of this intermittent and diffusive energy resource (1). However, precious metal based catalysts are required to catalyse the two half reactions in WEC, e.g. Pt and its alloys for hydrogen evolution reaction (HER), and oxides of Ru and Ir for oxygen evolution reaction (OER), which has constrained the widespread applications of PV-WEC systems. Thus, advanced electrode materials for WECs that are active and cost-effective are highly sought after.
Herein, I will present some of our recent research progress regarding the development of advanced electrodes for WECs. These electrodes are mainly comprised of earth abundant elements, such as first row transition metals (Ni, Co, Mn, Fe) and/or carbon. For instance, by depositing mesoporous NiFe nanosheets onto the skeleton of macroporous nickel foam (NiF), a highly efficient, freestanding oxygen evolution electrode is prepared, showing hierarchical micro- to nanoscale porosities, and is among the most active in bases (2). Besides that, a Mn doped NiO/Ni heterostructured electrode (Mn-NiO-Ni/NiF) is also successfully synthesized. The prepared material is highly active for HER in both neutral electrolytes and natural seawater, exhibiting a Pt-like catalytic activity (3). A customised WEC was assembled based on the NiFe/Ni-F anode and the Mn–NiO–Ni/Ni-F cathode, which is highly active in splitting water, reaching a high current of 0.2 A at 1.8 V. Moreover, the WEC can be directly powered by PV cells tol enable the production of renewable hydrogen (Figure 1).
(1) X. Lu, et. al, J. Am. Chem. Soc. 2015, 137, 2901-2907
(2) X. Lu, et. al, Nat. Commun. 2015, 6, 6616
(3) X. Lu, et. al, Energy Environ. Sci. 2018, 11, 1898-1910

M417 [Keynote] Review of new energy vehicle development in China and construction of Shanghai AI NEV Innovative Platform with battery materials analysis function
Jiping YE
Tongji University; Shanghai AI NEV Innovative Platform Co., Ltd., 36, Yu Tian (South) Rd., An Ting Town, JiaDing, Shanghai, China

Automobile sales in China decreased by 2.76% to 28 million vehicles in 2018, that is the first decrease in the past 28 years. Market developments in New Energy Vehicle (NEV) including hybrid and pure electrical vehicles (BEV), as well as fuel cell vehicles (FCV) are inevitable and the number of NEV will break through up to 1.5 million vehicles in 2019. However, LIB with high energy density used in BEV is facing many safety risks with various faults and life issues due to less development accumulation in material process and manufacture. Meanwhile FCV is difficult to form into a mature commercial market, where many relative core materials and components are lower in quality and less reliable as compared with overseas products and most of them are depended on imports.
Shanghai AI NEV Innovative Platform upholds a critical function position for supporting industrial chain innovation, supporting R&D transformation to key products and servicing entrepreneurship in automotive field, by focusing on promoting the opening and coordination of innovative resources to reduce the cost of starting a new business. One of the major functions is battery material analytical service to give key solutions to safety, energy density and life of on-board LIB and to support developing high-performance FC stacks with low lost materials.
In this presentation, China's NEV policy, regulation, EV evaluation, material analysis situation will be explained and the function position of Shanghai AI NEV Innovative Platform will be introduced. Some LIB estimation methods and corresponding material analytical results relative to battery capacity (energy density), degradation (life), failure (warning) and exothermic (safety) items are given.

M421 (canceled) <101243-1>
M422 Evaluation of porous structure on dynamic behavior in Lithium-ion batteries by numerical simulation
Gen INOUE, Hiroki MASHIOKA, Yoshifumi TSUGE
Kyushu University, Fukuoka, Japan

Lithium ion batteries (LiBs) are used in electric vehicles (EVs), hybrid electric vehicles (HEVs), compact devices and so on. However, both more power density and energy density is required, so active materials, binders, electrolytes, and separators are enthusiastically developed. Moreover, the ability of LiB determines not only materials but also the electrode structure. In the case of high output density cell, in other words, in the case of rapid charge or discharge condition, ionic conduction in porous electrode layer is dominant resistance, and it strongly depends on the heterogeneous porous structure. Recently, some researchers have been trying to understand the relationship between this porous structure and the effective ionic conductivity. In our previous research, the relative ionic conductivity was simulated in different porous electrode structure which consists of active material and binder, and the effect of morphology was discussed with electrochemical experiment, direct observation and numerical simulation. However, most of these research focused on only single component which is anode, cathode and separator. In order to increase the cell performance that is capacity, power density and durability, the effect of combination of these porous component have to be considered. In this study, various porous structure is modeled with direct observation results obtained by FIB-SEM and X-ray CT, and the charge and discharge simulation is carried out with some combination of these porous component. From this result, the morphology and the anisotropy of porous structure are evaluated to check the not only the internal resistance but also the ion flux distribution which cause to generate the Li dendrite. In addition, the effect of micro protective layer on ion flux distribution and conductive resistance is considered.

M423 Conducting and flexible polymer coating on silicon nanoparticles as anode for lithium-ion batteries
Jingwei WANG1,2, Shenhua SONG2, CHEN Guohua1
1 Department of Mechanical Engineering, The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong SAR, China
2 Shenzhen Key Laboratory of Advanced Materials, School of Materials Science and Engineering, Harbin Institute of Technology, Shenzhen, Guangdong 518055, China

Silicon anode material has been considered as one of the most promising candidates for next-generation Li-ion batteries due to its high specific capacity. Its low conductivity and large volume change during charge-discharge process still hinder its practical applications. In this work, a conducting and flexible polymer is employed as a protective coating layer on the surface of commercially available silicon nanoparticles. The polymer can be prepared through hydrosilylation between hydride terminated poly(dimethylsiloxane)s (h2PDMS) and 3,4-Ethylenedioxythiophene (EDOT). The PDMS-b-EDOT was found successfully coated on the Si nanoparticles. The coated Si was found to show a much improved performance when it is used in making the anode for lithium ion battery. The cell assembled with a conventional PVDF binder shows reversible capacity of 1400 mAh g-1 after 50 cycles at the rate of 0.1C.
Acknowledgments: This work was supported by the Area of Excellence Grant from HKPolyU (1-ZE30), and the Science and Technology Foundation of Shenzhen (Grant No. JCYJ20170307150808594).

M424 Effect of electrolyte additive on the performance of Lithium metal batteries
Zhengkun XIE1, Zhijun WU1,2, Xiyan YUE1, Akihiro YOSHIDA1,2, Abuliti Abudula1, Guoqing GUAN1,2
1 Graduate School of Science and Technology, Hirosaki University, 1-Bunkyocho, Hirosaki 036-8560, Japan
2 Energy Conversion Engineering Laboratory, Institute of Regional Innovation (IRI), Hirosaki University, 2-1-3, Matsubara, Aomori 030-0813, Japan

Lithium metal batteries <LMBs> are considered promising energy storage systems because of their high energy density and low redox potential. However, safety issue associated with the dendrite growth hinders their practical applications. One of the effective ways to suppress the dendrite growth and extend the cycle life is addition of the additive in the electrolyte. In this study, a novel low-cost electrolyte additive named as THP-Li salt was synthesized with a handy method for the first time, and introduced into both the solid-state electrolyte and the liquid electrolyte. For the solid-state electrolyte, the impedance value of solid polymer electrolyte <SPE> membrane was decreased apparently, and meanwhile, the all-solid-state LMBs with it delivered the excellent discharge capacity at high current density with good cycling performance <the capacity retention 78.7 % after 200 cycles> and higher coulombic efficiency. For the liquid ester-based and ether-based electrolytes, the addition of it greatly enhanced the overall cell performance of LMBs and particularly resulted in a higher discharge capacity, and remarkable improvement of the capacity retention <the capacity retention 68.4 % after 1000 cycles>. It is found that this novel additive can participate in the formation of stable solid electrolyte interphase <SEI> layer, preventing the side reaction between the electrolyte and electrode, suppressing the Li dendrites growth, which finally improved the safety and stability of LMBs.

Michihisa KOYAMA, National Institute for Materials Science/Shinshu University
M425 [Keynote] Synthesis and characterization of bifunctional air electrodes for rechargeable zinc-air batteries
Chi-Chang HU, Po-Chieh LI, Yu-Ju CHIEN
National Tsing Hua University, Hcin-Chu 30013 Taiwan

A novel configuration by pressing two electrodes containing electrocatalysts for the oxygen reduction and evolution reactions (ORR and OER) into a bi-functional air electrode is designed for rechargeable Zn-air batteries. MOC/25BC carbon paper (MOC consisting of a-MnO2 and XC-72 carbon black) and Fe0.1Ni0.9CO2O4/Ti mesh on this air electrode mainly serve as the cathode of the ORR and the anode of the OER, respectively. Electrochemical studies include linear sweep voltammetry (LSV), rotating ring-disk electrode (RRDE) voltammetry, and the full-cell charge-discharge-cycling test. The discharge peak power density of a Zn-air battery with this unique air electrode reaches 88.8 mW cm-2 at 133.6 mA cm-2 and 0.66 V in the alkaline electrolyte under the ambient condition. After 100 discharge-charge cycles at 10 mA cm-2, an increase in 0.3 V between charge and discharge cell voltages is found. The long-time discharge-charge-cycling curve (10 h in each step) shows that the cell voltages of discharge (1.3 V) and charge (1.97 V) keep constant during the entire process. The performances of this rechargeable Zn-air battery are superior to most reports in recent literature.
Carbons in various forms are also chosen as substrates for uniform dispersion of a-MnO2 to form air electrode catalysts to evaluate the influences of carbon types on the catalytic activities of the ORR and OER (oxygen evolution reaction). The morphology and physicochemical properties of various a-MnO2/carbon composites are characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray diffraction (XRD). Electrochemical studies include rotating ring-disk electrode (RRDE) voltammetry of catalysts, linear sweep voltammetry (LSV) of air electrodes, and the charge-discharge-cycling test of full cells. The discharge peak power density of Zn-air batteries varies from 66.3 (a-MnO2/carbon nanotubes with diameter ca. 10 nm, denoted as a-MnO2/CNT10) to 40.5 mW cm-2 (a-MnO2/super fine mesophase graphite powder) in 6 M KOH under ambient condition. The rechargeable Zn-air battery with the air electrode containing a-MnO2/CNT10 is stably operated for 100 cycles at 10 mA cm-2, which shows that an increase in 0.09 V between charge (decayed ca. 0.05 V) and discharge (decayed ca. 0.04 V) cell voltages.

PM201 Carbon gels heated at various temperatures for Li-air battery cathodes
Shintaroh NAGAISHI, Kazuki FUJITA, Kazuki SAKAI, Shinichiroh IWAMURA, Shin R. MUKAI
Hokkaido University, Sapporo, Japan

For the practical use of Lithium-air batteries (LABs), their cycle performance must be improved. In this system, oxygen supplied from the atmosphere reacts with Li+ and Li2O2 is deposited in the cathode during discharging. To obtain a large capacity and a high rate performance, the cathodes need to have a high surface area and a high electrical conductivity. Therefore, porous carbons are generally used for the cathodes.
To improve cycle performance, side reactions, which involve the decomposition of the electrolyte and result in irreversible capacity, need to be suppressed. It has been reported that oxygen functional groups existing on carbon materials, promote such side reactions. On the other hand, it has been also reported that amorphous Li2O2 tend to be formed on carbon materials having oxygen functional groups more than pristine carbon materials. Such amorphous Li2O2 easily decomposes during subsequent charging, and the charge over potential is relatively low. These facts indicate that there is a suitable amount of oxygen functional groups to increase cycle performance, which has not been clarified.
In this study, the quantitative effect of oxygen functional groups on cycle performance was investigated using carbon gels (CGs) as a model carbon material. CGs have a large mesopore volume which can contribute to the capacity of LABs, and their surface properties can also be tuned. While CGs originally have many oxygen functional groups, they were reduced by heat treatment at various temperatures. Then, the oxygen functional groups were quantitatively evaluated by temperature programed desorption analysis (TPD) performed under vacuum. The results obtained using CGs heated at 2200 °C showed that most of the functional groups were removed at this temperature and the resulting carbon can maintain a discharge capacity of 500 mAh g-1 for 21 cycles, while CGs heated at 1000 °C could maintain this capacity only for 8 cycles.

PM202 (canceled) <101483-1>
PM203 Development of a high-capacity cathode for Li-air batteries from carbon nanofibers
Keita USHIJIMA, Ryo SUMIDA, Shinichiroh IWAMURA, Isao OGINO, Shin R. MUKAI
Hokkaido University, Sapporo, Japan

Lithium-air batteries are expected to become a secondary battery of the next generation owing to their high theoretical energy density. Carbon paper combined with a porous carbon are generally used as the cathode in this system because the surface area of a typical carbon paper is too low to be used independently. In contrast, carbon nanofibers (CNFs) with a fiber diameter of several tens of nanometers have a sufficient surface area for this purpose. In this study, sheet electrodes were developed using CNFs produced through the liquid pulse injection (LPI) technique. The CNFs can be efficiently synthesized and easily casted into a sheet electrode only by vacuum filtration. Cathode performance of the sheet electrodes for lithium-air batteries was evaluated and optimal conditions to obtain higher capacities were explored.
LPI-CNFs with a diameter around 20 nm were dispersed into ethylene glycol. The resulting dispersion was filtered under vacuum to form a sheet. Coin cells of 2032-type were assembled using the sheet and a solution of CF3SO4Li in tetraglyme (1:4, molar ratio) as the cathode and electrolyte, respectively, and the cells were galvanostatically discharged and charged in an oxygen atmosphere.
The LPI-CNF sheets had a mechanical strength similar to that of a commercial carbon paper and much higher surface area than that of them, suggesting that the LPI-CNF sheets can be used independently as cathodes.
From results of discharge/charge measurements, the LPI-CNF sheets showed about a 3 times larger discharge capacity than that of an electrode prepared from a carbon paper and porous carbon.
It has been reported that usable depth of electrodes is limited because of the influence of oxygen diffusion. Thus, the structure of the LPI-CNF cathodes such as porosity and thickness were optimized to increase discharge capacity.

PM204 Silicon nanoparticle composited with N-dope carbon as anode in Li-ion storage
Yen-Ju WU1, Po-Yuan CHENG1, Yu-An CHEN2
1 Department of Chemical Engineering, National Tsing Hua University, Hsinchu City 30013, Taiwan
2 Department of Engineering and System Science, National Tsing Hua University, Hsinchu City 30013, Taiwan

Lithium ion storage devices are indispensable for modern society because of their high energy densities, low self-discharge, no memory effects, and applications in many high-tech industries such as electronic devices, military, and battery powered vehicles. However, most commercial lithium ion storage devices use carbon electrodes, which have low theoretical capacity (≈ 372 mAh g-1) and are not expected to meet the future needs of the energy storage industry. Consequently, silicon, possessing high theoretical capacity (≈ 4200 mAh g-1), being abundant in nature, and exhibiting low discharge potentials, has become a promising anode material. Despite these advantages, the use of Si anode is hindered by its low electrical conductivity and large volume changes during the lithiation/de-lithiation cycles leading to subsequent pulverization. Herein we designed a porous composite nanostructure of silicon with N-doped carbon (NDC) from mesoporous silica sphere and dopamine, which can offer space to accommodate the volume changes and improve the electrical conductivity of the electrode for performance enhancements. Indeed, the as-synthesized Si/NDC composite delivered a high capacity of 2,518 mAh g-1 at a current density of 200 mA g-1 and maintained a high capacity of 980 mAh g-1 at a high current density of 5,000 mA g-1.

PM205 Suitable Carbon Black Conductor in High-Voltage cathode for Lithium ion Secondary Batteries
1 Asahi Carbon Co., Ltd., Niigata, Japan
2 Yamagata University, Yamagata, Japan

Side reactions on high-voltage cathode for lithium ion batteries would be influenced by physicochemical properties of carbon black (CB) conductor used in it. We have prepared various CB conductors with different surface characteristics and crystallinity, and have applied them to a 5V cathode, LiNi0.5Mn1.5O4 (LNMO) as conductors. By electrochemical evaluation some samples were found to be suitable for the 5V cathode. The reaction mechanism would be reported.

PM206 Preparation of NCM523/PI composite cathode materials
WenChen CHIEN1,2, WeiKai CHEN1
1 Department of Chemical Engineering, Ming Chi University of Technology No.84 Gongzhuan Rd., Taishan Dist., New Taipei City 24301, Taiwan
2 Battery Research Center of Green Energy, Ming Chi University of Technology No.84 Gongzhuan Rd., Taishan Dist., New Taipei City 24301, Taiwan

At the present time, ternary cathode materials, NCM, have attracted many researchers to study due to their excellent electrochemical properties, such as high specific capacity and high charge-discharge voltage. By tuning the portions of nickel, cobalt and manganese, NCM can obtain different electrode characteristic. However, their poor stability when worked at high operating voltage have limited their applications in industry. In this study, polyimide (PI) was covered on the surface of NCM523 cathode material by a simple liquid phase modification. At first, 2,2-Bis(3-amino-4- hydroxyphenyl)hexafluoropropane (BisAPAF) and 2,3,3,4-oxydiphthalic anhydride (ODPA) were mixed in the solvent, N-Methyl-2-Pyrrolidone (NMP), at room temperature to synthesize the polyamic acid (PAA). Then, a desired amount of NCM523 powder were added and dispersed in PAA solution by stirring for 4h to obtain NCM523/PAA material. Finally, the NCM523/PAA material was converted into NCM523/PI by multistep heating process. XRD analysis showed that the addition of PI did not affect the original layered structure of NCM523 cathode material. The energy dispersive spectroscopy (EDS) analysis showed that polyimide could be evenly distributed on the surface of NCM523 particles. TGA analysis also confirmed a slight weight percentage of PI was added to the NCM523 material. The effect of PI addition on the electrochemical properties of NCM523 cathode material is still under investigation, and it is hoped that the present polyimide (PI) coating can effectively prevent the undesired interfacial reaction between the electrode material and the liquid electrolyte.

PM207 Simulation for all-solid state batteries with multi-element network model
Ryusei HIRATE, Hiroki MASHIOKA, Shinichiro YANO, Gen INOUE, Yoshifumi TSUGE
Kyushu University, Fukuoka, Japan

All-solid state batteries (ASSBs) are expected as next-generation battery for electric vehicles (EVs), hybrid electric vehicles (HEVs) because it is safer than usual liquid-type Lithium-ion battery. Recently, the innovative solid electrolyte have been developed, and it is comparable to organic liquid electrolyte in ionic conductivity. However, it is desired to attain more power density and more energy density. In order to improve the performance of ASSBs, it is required to optimize an electrode structure as well as material characteristics such as active materials and electrolytes. Therefore, monitoring the state in electrode layer during charge and discharge using the numerical computation is a critical measure to understand the phenomena in a cell. In the relatively micro-scale system such as the electrode layer, even a slight difference in structure remarkably affects the battery performance. However, usual simulations employ the empirical overall characteristics such as the reactive interface area and the tortuosity factor, so the phenomena resulting from minute structure of electrode layer which notably affect the cell performance might be overlooked. Hence, in this study, the numerical computation technique that can reflect the micro-characteristics of electrode structure directly by building a multi-element network model based on porous structures was developed. And the effect of heterogeneous electrode structure on cell performance was considered.

PM208 (canceled) <101444-1>
PM209 Preparation of hydroxide for NCM ternary cathode material precursor by precipitation
Wen-Chen CHIEN1, Wei-Ting CHEN2
1 Department of Chemical Engineering, Ming Chi University of Technology, 84 Gunzhjuan Rd., Taishan Dist., New Taipei City 24301, Taiwan
2 Battery Research Center of Green Energy, Ming Chi University of Technology, 84 Gunzhjuan Rd., Taishan Dist., New Taipei City 24301, Taiwan

In this study, 0.5 M nickel hydroxide, cobalt nitrate, and manganese nitrate were used as the metal sources with molar ratio of Ni:Co:Mn=1:1:1 and sodium hydroxide as the precipitant to prepare the NCM(OH)2 precursor by co-precipitation for application in the synthesis of NCM ternary cathode materials. The volume flow ratio of metal nitrate and NaOH was 1:2 and the pH value of the precipitation reaction was controlled at 10-12. After the reactants were mixed, the mixture was stirred at 50 °C for 12 h under nitrogen atmosphere. It was found that the color of the precipitate gradually changed from grey to brown in the experiment. It was speculated that the color change was resulted from the formation of manganese oxide-hydroxide. It was known that the manganese hydroxide could be reacted easily with trace oxygen even in a nitrogen atmosphere. SEM images showed that the precursor powder obtained by the preparation was irregular granular and had the obvious aggregation phenomenon. Besides, the XRD analysis showed that the precursor powder of the ternary positive electrode material was successfully prepared in this study and the precursor was composed of nickel cobalt manganese-hydroxide NCM(OH)2 and nickel cobalt manganese-oxygen-hydroxide NCMO(OH)2.

PM210 Activation of carbon electrode for vanadium redox flow battery by electron beam-irradiation
Honoka DOKI1, Hirokazu ISHITOBI1, Shunya YAMAMOTO2, Kosuke OBA1, Nobuyoshi NAKAGAWA1
1 Gunma University, Kiryu, Japan
2 National Institutes for Quantum and Radiological Science and Technology, Takasaki, Japan

Vanadium redox flow batteries (VRFB), which use vanadium species as the active materials, have advantages such as the flexible design between power and capacity. Thus, VRFB is expected to store renewable energy. However, the current density of a single cell is small due to the higher internal resistance such as reaction resistances. Therefore, researches have been conducted to reduce the reaction resistance by addition of surface oxygen functional groups by heat treatment in air or liquid phase oxidation to the carbon electrode material. However, the conventional treatment methods have issues such as longer treatment time and necessity of waste liquid treatment. In consequence, in this research, we focused on electron beam irradiation as the effective oxidation method. It is considered that the surface oxygen groups can be added by the reaction between surface carbon and radicals and/or ozone from the water or the oxygen formed by the irradiation. This processing method can be performed in a short time of 60 minutes or less at room temperature.
In this study, Electron beam irradiation was performed on the carbon cloth, then, characterization and electrochemical measurement were performed. Two-sheet of Carbon cloth (CC) was used as the electrode material. The electron beam with acceleration voltage of 2.0 MV was irradiated to the CC under air atmosphere at Takasaki Advanced Radiation Research Institute. To evaluate the cell performance, current-voltage curves were obtained using a single cell with interdigitated flow channel. The current density of the irradiated electrode under air was improved compared with the non-irradiated electrode. X-ray photoelectron spectroscopy (XPS) measurements were performed to analyze surface oxygen groups. As a result, the surface oxygen, i.e., C-O, COO, etc., of electrode material increased by electron beam irradiation within 60 minutes.

PM211 Mn-Fe based Bimetallic Metal-Organic Framework as Electrode Materials for Supercapacitors
Jia-Yu TAN, Po-Yuan CHENG, Shih-Yuan LU*
Department of Chemical Engineering, National Tsing Hua University, Hsinchu 30013, Taiwan

Supercapacitors are one of the most promising energy storage devices because of their long cycle life, high power densities, and high discharge efficiencies. The power and energy densities of supercapacitors depend critically on the electrode materials. In recent years, metal-organic frameworks (MOF) have attracted much research attention as electrode materials for supercapacitors, because of their unique properties such as high porosities, large surface areas, and tunable morphologies, which are beneficial to the capacitive performances of supercapacitors. In this work, we synthesized Mn-based and Mn-Fe based MOFs via a simple solvothermal method, using 1,4-benzenedicarboxylate as the organic linker. The incorporation of Fe into the Mn-based MOF significantly enhanced the capacitive performances. The specific capacitances of Mn-based MOF and Mn-Fe based MOF were 21 and 75 F/g, respectively in 2M KOH at a scan rate of 5 mV/s. The enhancement is attributable to the synergistic effect between Mn and Fe.

PM212 Synthesis of reduced graphene oxide composites using microwave treatment as high-performance electrodes for supercapacitor devices
Jiao JIAO, Koji MIYAKE, Chang Yi KONG
Shizuoka University

Recently, Microwave is an efficient, green and selective heating method, it has been employed to reduce graphene oxide (GO) in solvent or under dry condition. Firstly, we used modifification of Hummers method to fabricate graphene oxide (GO), then graphene oxide (GO)/Titanium oxide (TiO2) nanocomposites were synthesized with different wt/wt % of GO/TiO2 (1:1; 1:2; 1:3; 1:4 and 1:5), finally the nanocomposites were reduced by microwave method. To assess the properties of materials for use in supercapacitors, cyclic voltammetry and galvanostatic charging–discharging measurements were performed. And the results show that the microwave method synthesis of reduced graphene oxide (GO)/Titanium oxide composites with wt/wt % of GO/TiO2 (1:4) has the highest specific capacitance of 454 F/g at a scan rate of 10 mV/s. What's more, as shown in Figure 1, it has a high energy density of E = 24.2 Wh/kg and high power density of P = 500.1 kW/kg. As a result, graphene-based material obtained by MW-assisted reduction has a porous and loose structure and relatively high special surface area, making it perfectly suitable for supercapacitor devices.

PM213 Electrosynthesis of ammonia with tungsten-Iron catalyst using proton-conducting solid oxide fuel cell
Chien-I LI, Hiroki MATSUO, Junichiro OTOMO
Department of Environment Systems, Graduate School of Frontier Sciences, The University of Tokyo

For widespread use of renewable energy, effective utilization of excess energy from the renewable energy is a key issue. Electrolysis of hydrogen carrier, especially ammonia, is a possible solution because ammonia possesses some advantages including stable chemical property, high hydrogen density, easier storage and non-explosion. Unfortunately, during electrochemical reaction of ammonia synthesis with metal catalysts, hydrogen evolution reaction also occurs, and thus the faraday efficiency of ammonia electrosynthesis becomes low. In this study, the effect of addition of tungsten into iron on improving electrochemical reaction of ammonia synthesis and suppressing hydrogen evolution reaction were investigated using 90%N2-10%H2, W-Fe-BaCe0.9Y0.1O3 (BCY)|BCY|Pt, 3%H2O-77%Ar-20%H2. W-Fe-BCY catalyst cathode was fabricated by the incipient wetness co-impregnation method. After addition of W into Fe catalyst, the current density decreased because of larger energy of tungsten hydride formation which suppresses hydrogen evolution reaction. Impedance spectroscopic analysis also suggested the same result of suppression of hydrogen evolution reaction. Furthermore, the ammonia formation rate became higher at lower operating temperatures than those of pure Fe catalyst. This was probably caused by lower coverage of hydrogen adatoms on W-Fe catalyst surface and retaining active sites for N2 dissociation. In addition, with an increase in ammonia formation rate and a decrease in current density, the faraday efficiency also increased by around two times with the addition of W into Fe catalyst.

PM214 Performance investigation of SOFC single cell for renewable energy interconnection
Satoshi NIINUMA, Shin'ya OBARA
Kitami Institute of Technology, Kitami, Japan

Recently, Global warming has become a serious problem. Therefore, Japan is aiming at a hydrogen society and conducting demonstration experiments of hydrogen supply chains in various places. Fuel cells are the most popular source of hydrogen energy. However, the load followability of fuel cells has not been studied. In this study, we will construct a power generator using the SOFC single cell which is the highest temperature operation and the highest efficiency among fuel cells, and investigate the load following ability. Currently, it is desirable to make SOFC operable at low temperatures. Therefore, in this experiment, the operating temperature is 700 degrees, and the flow rate of each gas is 200 mL/min. First, the I-V characteristic of a single cell is measured in order to investigate whether it is a suitable experimental device. From the experiment, the power per unit area at peak was 0.1 W/cm2. Since this power value is equal to the nominal value, it can be said that an appropriate experimental device has been produced. Next, based on this value, a variable load is created using the programmable load function of the DC electronic load. The loading rate is repeated at 20% and 100% every 10 seconds from 40 seconds to 80 seconds. The single cell output when the created variable load is input to the single cell is shown in the figure. From the figure, it can be seen that in any case, tracking follows less than 0.6 seconds. From the experimental results described above, it is found that the SOFC single cell has high load followability. In the future, CO2 is expected to be reduced by replacing the thermal power generator with a SOFC generator for the peak load power supply.

PM215 Carbon supported metal phosphide anodes for intermediate temperature fuel cells
Ryuji KIKUCHI, Seiya TAJIMA, Shohei TADA, Yasukazu KOBAYASHI, S. Ted OYAMA
Department of Chemical System Engineering, Graduate School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan

Anode materials based on transition metal phosphides were investigated for intermediate temperature fuel cells (ITFCs). Metal phosphides are world-widely investigated as highly-active and selective catalysts for hydrodesulfurization, hydrodenitrogenation, and hydrodeoxygenation. These reactions require catalytic ability for dissociation of H-H bond as well as C-S, C-N, or C-O bond. In addition to the catalytic activity, metal phosphides are known to be thermally and chemically stable and to possess electric conductivity comparable to metals and hardness similar to ceramics. Because of these features, metal phosphides are expected to function as electrodes in electrochemical cells. We have reported that molybdenum phosphide and tungsten phosphide as the anode of ITFCs demonstrated high power generation characteristics per electrochemical surface area. Accordingly, this study aimed to increase electrochemical surface area by supporting metal phosphides on carbon materials. Also, to increase the porosity of the anodes for ITFCs, carbon black (CB) and carbon nanofiber (CNF) were mixed with commercial platinum carbon (Pt/C) catalysts. Power generation and cyclic voltammetry were conducted to evaluate the catalysts' electrochemical activities. From the results of power generation and CV, molybdenum phosphide loaded on CB shows higher power generation characteristics per electrochemical surface area than Pt/C. It is suggested that phosphides loaded on carbon were well dispersed and many active sites were produced. Power generation measurements revealed that Pt/C and CB with the weight ratio 1: 1 and Pt/C and CNF with the weight ratio 1: 1 exhibited good cell performances. It indicates that increased porosity in the electrode gave rise to large triple-phase boundary.

PM216 Dual sulfonated poly(arylene ether ketone) membrane grafted with 15-crown-5-ether for enhanced proton conductivity and anti-oxidation stability
Dinh Cong Tinh VO, Minh Dat Thinh NGUYEN, Dukjoon KIM
Sungkyunkwan University, Suwon City, Gyeonggydo, South Korea

In the proton exchange membrane fuel cell, the durability is recently the critical issue in its operation. As the Ce+3 cerium ion (Ce) is a potential scavenger for ·OH and ·OOH radicals, the main causes of the chemical degradation of the membrane, aminomethyl-15-crown-5-ether (CRE) and dual sulfonated 3,3-diphenylpropylamine (DSDPA) were grafted onto the poly(arylene ether ketone) (PAEK) to maintain high proton conductivity and chemical stability by alleviating the migration of Ce from the membrane. The chemical and physical structures of the synthesized CRE grafted dual sulfonated PAEK membrane (DSPAEK-CRE) along with the coordination complex of CRE and Ce ions were investigated using FT-IR, 1H-NMR and SAXs, and XPS spectroscopy. The Fenton's test showed huge improvement of anti-oxidation stability by the presence of CRE. While the CRE/Ce coordinated membrane showed higher proton conductivity and better chemical stability than the Ce+3 dispersed one, other properties such as water uptake, swelling ratio, and mechanical strength were not significantly affected by CRE.

PM217 Mass balance model for Solid-state Alkaline Fuel Cells considering water transport in polymer electrolyte membrane.
Haruka YAMAZAKI1, Yuhei OSHIBA1,2, Takeo YAMAGUCHI1,2
1 Tokyo Institute of Technology, Yokohama, Japan
2 Core Research for Evolutionary Science and Technology, Japan Science and Technology Agency (JST-CREST), Japan

Recently, solid-state alkaline fuel cells (SAFCs) with anion-exchange membranes (AEMs) have attracted considerable attention as next generation fuel cells, because they can use non-noble catalysts and various fuels. The SAFCs show complex water behaviors; water is generated at the anode and is reacted at the cathode. Hence, SAFCs using gas as the fuel show low cell performance due to anode flooding and membrane drying. Although control of water behavior is crucial to improve cell performance, there are many parameters to be considered such as AEM properties and operating conditions. In such situation, modeling approach is effective because of less time-consuming, inexpensive, and more versatile than experimental approaches.
In this study, we make a mass balance model for SAFCs considering water transport in AEM and clarify guidelines to suppress anode flooding and membrane drying. Pore-filling anion conducting membrane[1] is used as AEM, and parameters needed for the calculation such as ion conductivity and water content of AEM were experimentally obtained. To make the AEM model, two mass balances of whole cell and AEM are considered. Then, outlet RHs and membrane IR loss were calculated by solving the two mass balances simultaneously under specific operating conditions and AEM thickness.
Fig. 1(a) and 1(b) show current density dependence of calculated outlet anode RHs and membrane IR losses with different AEM thickness, respectively. With thinner AEM, an increase in current density was obtained at 100% RH, which indicate the flooding is suppressed. Further, the suppression of membrane drying in the thinner AEM was confirmed by the low membrane IR loss. These results show that thinner AEM is effective for suppressing both anode flooding and membrane drying.
[1]Y. Oshiba et al., Journal of Power Sources , 345, 221-226 (2017)

PM218 Effect of RGO particle size on the catalytic activity of PtRu/RGO used for direct methanol fuel cell
Kenta DEJIMA, Hirokazu ISHITOBI, Nobuyoshi NAKAGAWA
Gunma University, Kiryu, Japan

Direct methanol fuel cell (DMFC) has attracted attention as an alternative power source because of high energy density of liquid methanol. One of the main issues for DMFC is the sluggish kinetics of methanol oxidation reaction (MOR) at the anode. Therefore, we focused on developing a highly active anode catalyst by using reduced graphene oxide (RGO) having a high specific surface-area and a high electric conductivity as a catalyst support. Although many studies using RGO have been conducted so far, the effect of the particle size of RGO on the catalytic activity has not been sufficiently investigated. In this study, the catalyst was prepared using RGO with different average particle size, i.e., 5 μm (RGOL) and 0.5 μm (RGOS) and the effect of particle size of RGO on the catalytic activity was investigated.
PtRu catalyst supported on RGOL or RGOS was prepared from a GO slurry by using a high-power ultrasonic crusher followed by adding polydopamine (PDA) as a dispersant and PtRu deposition by a chemical reduction method using NaBH4.
For the prepared catalysts, PtRu/RGOL and PtRu/RGOS, characterization was carried out using TEM, FE-SEM, XRD and EDX. Catalytic activity of the catalyst was evaluated by cyclic voltammetry in an aqueous solution with 0.5 M CH3OH and 0.5 M H2SO4. Electrochemical surface area (ECSA) for the catalyst was also evaluated by CO stripping method.
PtRu/RGOS showed about 1.6 times higher ECSA and about 2.1 times higher MOR mass activity compared to that of PtRu/RGOL. The higher performance of PtRu/RGOS was attributed to the superior structure of the catalyst layer for facilitated mass transfer and ease of fuel access. This result suggested that RGO with the small particle size is proper for the support of PtRu nanoparticles to increase the MOR activity of PtRu/RGO in DMFC.

PM219 Single atom cobalt-doped graphene and its ORR activity
Yasuhiro SHU1, Koji MIYAKE2, Yuichiro HIROTA1, Yosiaki UCHIDA1, Chang Yi KONG2, Norikazu NISHIYAMA1
1 Osaka University, Toyonaka, Japan
2 Shizuoka University, Hamamatsu, Japan

The efficient conversion of energy is one of the urgent problems because of the sharp increase in current energy consumption. To meet the electricity demand, the development of fuel cells (FCs) have attracted great interest by their sustainable, renewable, efficient and eco-friendly electrochemical conversion of energy. For widespread commercialization of FCs, the main challenge is to reduce the cost of catalysts although expensive platinum-based catalysts have been applied. However, it is still challenging to develop an inexpensive and effective alternative catalyst, due to its sluggish reaction towards the oxygen reduction reaction (ORR).
As the alternative catalysts, transition metal and heteroatoms co-doped carbon material have been attracted by their low-cost and high performance. In particular, the carbon materials containing the bonding of cobalt and nitrogen (CoNx) acted as high-performance catalysts for ORR. However, the fine design of CoNx is difficult, due to the aggregation of metal. Herein, we present a new synthesis method of graphene (G) with highly-dispersed CoNx species as an excellent electrocatalysts, by using sequential treatments of mixing with sulfuric acid, Co2+ ion-exchanging and 2-methylimidazole coordination. And we also report its excellent electrocatalytic performance.
The highly dispersed cobalt species was observed on the graphene by TEM images and STEM images. The results of ORR measurements were shown in Table 1. The samples after the treatment of Co2+ ion-exchanging and 2-methylimidazole coordination were carbonized under N2 atmosphere and denoted as Co/GS and Co-N/GS, respectively. Obviously, G and Co/GS performed sluggish ORR, while Co-N/GS showed both excellent onset potential and limiting current density. In particular, the limiting current density is comparable to commercial platinum catalysts (Pt/C). Moreover, Co-N/GS exhibits a high current density, and the number of electrons (n) in the ORR are also higher than other samples.

PM220 Effect of electrode microstructure using metal-free carbon catalyst as cathode catalyst for polymer electrolyte fuel cell
Takahiro KAWAKAMI, Naofumi ANTO, Iori SHIMADA, Mitsumasa OSADA, Nobuhide TAKAHASHI, Hiroshi FUKUNAGA
Shinshu University, Ueda, Nagano, Japan

Polymer electrolyte fuel cell (PEFC) is beginning to be put into practical use as residential and transportation power generation system. However, the cost of PEFC is still high, since expensive platinum (Pt) is used as the catalyst. Therefore, development of non-Pt catalyst is required. We have been studying silk-derived activated carbon (SAC) as non-Pt catalyst, which is inexpensive but fairly active compared to the conventional Pt catalyst. The structure of the electrodes fabricated from such catalyst should be designed with a different concept. In this study, we investigated the effect of catalyst layer thickness on the performance of PEFC using non-Pt catalyst.
Membrane electrode assembly (MEA) was prepared using SAC as cathode catalyst. Catalyst layers with different thicknesses were fabricated on a carbon paper and was hot pressed to a Nafion membrane. Terminal voltage vs. current density and electrochemical impedance spectra of each MEA were measured at 80 °C.
The iR-free polarization curves of each MEA were deconvoluted by fitting the activation overpotential. As the amount of catalyst was increased, the activation overpotential decreased and the remaining overpotential increased. It was assumed that this residual overpotential was not concentration overpotential, since the shape of the curve was not convex downward. The applied voltage dependence of the impedance spectrum was observed. As the applied voltage was increased, the interfacial resistance initially decreased and then became constant. Interfacial resistance independent of the applied voltage was assumed to be related to the proton conduction in the catalyst layer. The interfacial resistance related to the proton conduction in the catalyst layer increased as the amount of catalyst increased. Therefore, it is considered that the increase of the residual overpotential was due to the increase of the proton conduction resistance in the catalyst layer.

PM221 Preparation of a graphene oxide membrane for a fuel cell application
Gunma University, Kiryu, Japan

Graphene oxide (GO) membrane is expected to be an alternative electrolyte membrane having high proton-conductivity and less fuel-crossover for a fuel cell application. However, the proton-conductivity of GO membrane is still not enough. In this study, effect of an additional oxidation of GO and an addition of sulfonic acid group to GO on the proton conductivity were investigated.
A commercial GO slurry with 1.0 wt% GO was subsequently treated with NaNO3, KMNO4 and H2O2 to obtain the additionally oxidized GO (GOh). By adding vinyl sulfonic acid (VS) to the GO and GOh slurries, VS treated GO (GOVS) and VS treated GOh (GOhVS) membranes were prepared after filtering and drying. Membrane electrode assembly (MEA) was fabricated by sandwiching the membrane by carbon papers with Pt/C catalyst on both sides. Current-voltage performance of the MEA as a H2-O2 fuel cell was evaluated, and the proton conductivity of the membrane was calculated from the ohmic resistance assuming that the cell resistance was governed by that of the membrane.
The proton conductivity of the membrane was higher in the order of GOhVS > GOVS > GOh > GO and found that each of the additional oxidation of GO and the VS treatment increased the proton conductivity as shown in Table 1. GOhVS membrane of which GO was additionally oxidized and also treated with VS showed the highest conductivity with 118 mW cm-2 fuel cell power-density. It was more than one order of magnitude higher than that of GO. It was found that the additional oxidation tof GO and the VS treatment are effective in improving the conductivity of GO membrane.

PM222 Pore-filling Membrane with Hydrocarbon Ionomer for Polymer Electrolyte Water Electrolysis
Tokyo Institute of Technology, Yokohama, Kanagawa, Japan

Polymer electrolyte water electrolysis (PEWE) is a key technology for the production of hydrogen in the power-to-gas process. As polymer electrolyte membranes for PEWE, perfluorosulfonic acid (PFSA) polymer membranes such as Nafion® are commonly used. In PEWE, although the produced hydrogen needs to be stored in pressurized gas tanks for transportation, the cell performance drops by high hydrogen crossover under the pressured condition. On the other hand, hydrocarbon-based polymer membranes including poly (arylene ether sulfone) (SPES) are expected to have a lower gas permeation property than the PFSA polymer membranes. However, the swelling of these hydrocarbon membranes is higher than the PFSA polymer membranes, which is a severe problem in fully humidified operating conditions of PEWE. The membrane with reduced swelling could be fabricated by a pore-filling technique, where the polymer electrolyte is filled inside pores of the porous substrate [1].
In our study, we prepared a pore-filling polymer electrolyte membrane using SPES for PEWE (Fig. 1A). This pore-filling membrane was prepared by drop casting 3 wt% SPES (IEC: 2.1 meq/g) solution over a 24 μm polyethylene porous substrate at 80 °C. The properties of the SPES pore-filling membrane was compared with that of SPES cast membrane and commercial Nafion 211.
The hydrogen permeability coefficient of the SPES cast membrane was found lower than Nafion 211, and that of the SPES pore-filling membrane is comparable with that of the SPES cast membrane (Fig. 1B). Moreover, the pore-filling membrane showed a lower swelling ratio between dry and wet conditions compared to the cast membrane (Fig. 1C). The results indicate that the SPES pore-filling membrane has both reduced hydrogen permeation and lowered swelling properties, which is suitable for PEWE applications.
[1] Nishimura, H. and T. Yamaguchi, Electrochemical and solid-state letters, 2004. 7(11): p. A385-A388.

PM223 Electrochemical fabrication of alloy catalysts for fuel cell and water electrolyzer
Hoyoung KIM, Hyanjoo PARK, SeonHwa OH, Hyeon Jeong PARK, Soo-Kil KIM
School of Integrative Engineering, Chung-Ang University, 84 Heukseok-ro, Dongjak-gu, Seoul 06974, Republic of Korea

Fuel cells combined with carbon-free hydrogen productions, such as water electrolysis, are the most promising energy strategy to mitigate the global warming and climate changes. Since the reactions for fuel cells (oxygen reduction reaction, ORR and hydrogen oxidation reaction, HOR) and water electrolysis (oxygen evolution reaction, OER and hydrogen evolution reaction, HER) are heterogeneous electrochemical reactions, they require catalysts to reduce the activation barriers during the electrochemical reactions. In addition, since the ordinary catalysts used in the systems are noble metal such as Pt, Ru, Ir, etc., development of cheap catalysts is another key issue in the fields. In this presentation, alloys of both noble and transition metals are fabricated by electrodeposition method. The composition and shape of the catalysts were controlled through the modification of the electrolyte composition and the deposition potential. For the ORR of fuel cells, PtM alloys were electrodeposited and their ORR characteristics through the modification of the electronic structures were studied. In the case of hydrogen-involving reactions such as HOR and HER, the relatively fast kinetics enables the possible use of cheap Ni-based alloys as the catalysts materials. Addition of small amounts of noble metals to Ni or control of the electrochemical surface area as well as the crystalline structures enhance the reaction kinetics close to those by Pt-based materials. A variety of combinations of Ni-based alloys was fabricated by electrodeposition and their characteristics on HOR and HER were investigated.

PM224 Ni-Fe Based Bi-metallic Metal-Organic Framework in-situ Grown on Nickel Foam as High Efficiency Overall Water Splitting Catalysts
Chih-Chieh CHENG1, Yu-An CHEN2, Shih-Yuan LU1
1 Department of Chemical Engineering, National Tsing Hua University, Hsinchu, Taiwan
2 Department of Engineering and System Science, National Tsing Hua University, Hsinchu, Taiwan

Energy issue has become a considerable topic because of the rapid population growth and industrialization of the world. To reduce carbon emission and environmental pollution from burning fossil fuels, the development of alternative energies is urgent and essential nowadays. Hydrogen has been regarded as one of the most promising energy carriers because of its high gravimetric energy density and clean byproduct, water, when in use as an energy source. Electrolytic water splitting driven by renewable energies such solar and wind energies is considered a most promising environmentally friendly hydrogen production technology, which splits water into hydrogen and oxygen without hazardous byproducts. The development of high-efficiency and noble-metal-free electrocatalysts is the most crucial and challenging part of electrolytic water splitting. In this study, we successfully grown Ni-Fe based bi-metallic metal-organic frameworks (MOF) on nickel foam, denoted as (Ni, Fe)(BDC-NH2)(DMF,F)/NF, for both oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) involved in alkaline electrolytic water splitting. The as prepared MOF loaded nickel foam exhibited outstanding electrolytic activities, achieving overpotentials of 286 and 348 mV for the OER and 250 and 353 mV for the HER at current densities of 50 and 500 mA cm-2, respectively in 1.0 M KOH, showing substantial activity enhancements as compared to pristine nickel foam. The OER efficiency enhancement may be attributed to the synergistic effects between Ni and Fe and the presence of fluoride, which is a strong electron withdrawing ion. As for the HER, the presence of the electron donating group, –NH2, in the organic linker is beneficial to the reduction power of the catalyst.

PM225 Design of Stable Composite Catalyst Composed of Perovskite-Type Oxide and Metal Oxide Support for the Oxygen Evolution Reaction in Alkaline Solutions
1 Chemical Resources Laboratory, Tokyo Institute of Technology, 4259 Nagatsudacho, Midori-ku, Yokohama, Kanagawa, 226-8503, Japan
2 Laboratory for Materials & Structures, Tokyo Institute of Technology, 4259 Nagatsudacho, Midori-ku, Yokohama, Kanagawa, 226-8503, Japan

Efficient use of renewable energy resources is crucial to meet our future energy demand. Alkaline water splitting can produce hydrogen using electricity generated from intermittent natural energies, such as solar and wind. The oxygen evolution reaction (OER) is often considered as the bottleneck in water splitting because the OER still has large overpotential. RuO2 and IrO2 have high activities for OER, but these catalysts based on precious metals are very costly. In addition, high operating potential in OER region triggers corrosion of carbon supports of catalysts, leading their low durability.
Perovskite oxides with nonprecious metals have been recently attracting much interest because they are inexpensive and show high electrocatalytic activity. For electrochemical reaction, conductive supports need to be combined since most perovskite oxides have insufficient electrical conductivity. However, carbon supports are not suitable due to carbon corrosion.
Herein, we develop a composite electrocatalyst composed of perovskite oxide as catalyst and conductive metal oxide as support as shown in Fig. 1(a), and we have chosen LaCoO3 and SnO2, respectively. LaCoO3 is a model perovskite compound, which is well-known as OER catalyst. SnO2 is electrical conductive oxide and possesses high thermal stability and alkaline stability, suggesting that SnO2 can be stable during the synthesis of LaCoO3 and measurements in alkaline solution. Fig. 1(b) shows OER activities of LaCoO3, LaCoO3/SnO2 and physically-mixed LaCoO3+SnO2 and demonstrates that LaCoO3/SnO2 exhibited higher current than others. It implies a good interfacial contact in LaCoO3/SnO2. Moreover, Fig. 1(c) proves higher durability of LaCoO3/SnO2 than that of LaCoO3/CNT which employed carbon as support. These findings indicated that the composite electrocatalyst based on perovskite and conductive metal oxide support is a promising platform for development of highly durable OER catalysts.

PM226 Ni-Fe-Mo based Nanorod Arrays as Bifunctional Electrocatalyst for Overall Water Splitting
Liang-Guo HE, Cheng-Ting HSIEH, Chun-Lung HUANG
Department of Chemical Engineering, National Tsing Hua University, Hsinchu 30013, Taiwan

The development of green energy are getting increasing research attention. Hydrogen is an excellent energy carrier and is also considered an energy source suitable to serve as an intermediate energy carrier for solar and wind energies. The development of highly efficient, stable, and low-cost electrocatalysts to reduce the reaction potential of electrolytic water splitting can facilitate conversion of green energies into hydrogen energy. In this study, we successfully grew Ni-Fe-Mo based nanorod arrays on nickel foam, denoted as (Ni, Fe)MoO4@NF, as bifunctional electrocatalysts for overall water splitting. The product catalysts exhibited excellent electrocatalytic activities toward the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in 1.0 M KOH, achieving overpotentials of 128, 226, and 305 mV at 10, 50, and 500 mA cm-2, respectively for the HER and overpotentials of 227 and 333 mV at 50 and 500 mA cm-2, respectively for the OER. The enhancement in OER efficiencies can be mainly attributed to the synergistic effects between Ni and Fe. And the enhancement in HER efficiencies can be mainly attributed to the synergistic effects between Ni and Mo. Furthermore, the nanorod array structure on nickel foam enlarges the reaction surface areas and thus the active site number for the water splitting reaction.

PM227 Ab-initio studies on reversible dehydrogenation of biphenyl and diphenylmethane depending on functional groups
Yeon-Jeong SHIN, Yu-Gyeong LEE, Dong-Hee LIM
Chungbuk National University, Cheongju, Korea

Hydrogen energy, an eco-friendly energy source for replacing fossil fuels, is widely regarded as a next-generation energy source with highly versatile application. However, there are technical limitations on hydrogen storage and production that should be satisfied for aspects of economy and efficiency. Among many technologies for solving the problems, liquid organic hydrogen carriers (LOHC) technology has been receiving much attention since it can be stored for a long time and safely transported to a destination using existing gasoline infrastructure. Recently, it has been experimentally reported that when biphenyl was mixed with diphenylmethane, it showed a reversible hydrogen storage and production capacity of 6.9 wt% H2 and 60 gH2/L, existing in a liquid state at room temperature. To understand this mechanism in detail, density functional theory (DFT) calculations were conducted using Gaussian 16 software package. We analyzed the reversible dehydrogenation reaction mechanisms based on the dehydrogenation enthalpy and free energy calculations. Furthermore, the same calculations were conducted with a various functional groups to propose higher efficient LOHC materials, which would make a great contribution to the development of optimal LOHC materials for the reversible hydrogen storage and production system.

PM228 Investigation of anode catalyst on liquid ammonia electrolysis for hydrogen production
Natsuho AKAGI, Keisuke HORI, Hisashi SUGIME, Suguru NODA, Nobuko HANADA
Waseda University, Tokyo, Japan

Hydrogen is a secondary energy source and can generate electricity by fuel cells without CO2 emission. Ammonia is considered for one of the promising hydrogen storage media. Ammonia has high gravimetric and volumetric hydrogen capacities (17.8 mass% and 107.3 kgH2/m3). And ammonia is easily liquefied at 1.0 MPa at room temperature. Hydrogen can be obtained by electrolysis of liquid ammonia. The theoretical standard voltage is 0.077 V, however the actual operation voltage is much higher due to the large overpotential for the anode reaction. In the anode reaction of N2 formation from NH2-, it is considered that either NH2- adsorption or N2 desorption can be the limiting step. Therefore, the catalyst effect on anode reaction was investigated by focusing on the metal nitride formation enthalpy ΔHfMNx which corresponds to the strength of metal-nitrogen bond. The electrolysis of liquid ammonia was performed using a three-electrode system with a counter electrode of a Pt plate, a reference electrode of a Pt wire (-2.59 V vs. SHE) and a working electrode of a catalyst plate (Ti, Ta, Fe, Co, Ni, Ru, Ir, Pt, Au, or Ag). The cyclic voltammetry (CV) of mono-component catalysts showed different activities for different metals (Fig. 1a). By plotting the current density at 0.3 V against the ΔHfMNx, the volcano plot was obtained (Fig. 1b). Next, to increase the catalytic performance, binary metal catalyst of Fe and Pt (Fe-Pt) having different bond strengths with nitrogen was prepared. Fe-Pt showed higher current density than the mono-Fe and mono-Pt catalysts at a low potential of 0.3 V.

PM229 Experimental Manner for Ammonia Electrochemical Synthesis at Intermediate Temperatures
Shohei TADA, Shuya SUZU, Hironori NAGASE, Ryuji KIKUCHI
The University of Tokyo, 7-3-1 Hongo, Bunkyo-Ku, 113-8656 Tokyo, Japan

NH3 is one of the key chemicals in the world. For example, NH3-based chemicals occupy the vital position of a fertilizer, which directly affects the world's food supply. Besides, NH3 is considered a promising H2 carrier because of its high energy density, easy liquefaction, and no CO2 emission during H2 evolution reaction. Today, NH3 is synthesized from syngas and N2 at high pressure (15-30 MPa) and at high temperature (500 °C), which is known as a Haber-Bosch process. If this synthesis is achieved without using fossil fuel, we will obtain carbon-free NH3. We focused on electrochemical synthesis of NH3 which can be operated at atmospheric pressure by electricity from renewable energy resources. We chose a solid phosphate electrolyte (a CsH2PO4/SiP2O7 composite) which conducts protons at around 200 °C, based on the studies of intermediate-temperature fuel cells. Both electrodes consisted of Pt on carbon with 1 mg_Pt cm-2. Ideally, the electrochemical synthesis proceeds as follows. At an anode side, H2 is separated to protons and electrons (H2 → 2H+ + 2e-). At a cathode side, N2 reacts with protons and electrons (N2 + 6H+ + 6e- → 2NH3). Using the electrolyte and electrodes, however, NH3 was detected not only from cathode but also from anode probably because of the NH3 leakage from the cathode to the anode and desorption/decomposition of NH3-like contaminations. Thus, we struggled with changes in experimental conditions and improvement in the apparatus and experimental procedure. Ag-Pd membrane was found to be effective for preventing the gas leak, and by inserting Ag-Pd membrane between anode and electrolyte, NH3 detection in the anode side was limited, and electrochemical NH3 synthesis was confirmed in the cathode side.

PM230 Electrolysis of ammonia in aqueous solution by platinum nanoparticle supported carbon nanotube film electrode
Yusuke KOHASE, Suguru NODA, Nobuko HANADA
Waseda University, Tokyo, Japan

Ammonia has been paid attention as a hydrogen medium for hydrogen energy. The aqueous ammonia solution has a high hydrogen mass density (6.1 mass%) and a vapor pressure (0.08 Pa) lower than atmospheric pressure at 20 °C. Electrolysis is one of the methods of generating hydrogen from aqueous ammonia solution. Hydrogen and nitrogen are generated at the anode and cathode, respectively, and the theoretical decomposition voltage is 0.06 V. Platinum is often used for the electrode catalyst but has a problem of the large overvoltage of the anode.
In this study, an electrode with platinum nanoparticles supported on carbon nanotube (Pt-CNT) was fabricated. CNT is a carbon material possessing a high specific surface area, that forms a sponge-like film by a dispersion-filtration process. The Pt-CNT electrode was adapted to electrolysis of ammonia aqueous solution to reduce the anode overpotential by increasing the Pt surface area.
Pt nanoparticles were deposited on CNT by polyol method at various temperatures of 100-180 °C. The electrochemical surface area of Pt was calculated from the amount of hydrogen adsorption and desorption in 0.5 M H2SO4 aq. The largest platinum surface area, 268 cm2 per 1 cm2 of electrode, was obtained for the Pt-CNT with Pt deposited at 160 °C. The ammonia electrolysis results at the anode with 1 M NH3 + 1 M KOH aqueous solution are shown in Fig. 1. The Pt-CNT electrode prepared at 160 °C and having the largest platinum surface area showed the highest peak current density and the lowest potential at 10 mA cm-2.

PM231 Investigation of bis-BN cyclohexane-based LOHC systems for improving renewable hydrogen energy storage using density functional theory
Yuri MIN, Yu-Gyeong LEE, Dong-Hee LIM
Chungbuk National University, Cheong ju, Korea

Among many eco-friendly energy sources, hydrogen energy has been attracting attention due to a higher versatility, but there is a difficulty in the practical use due to technical limitations in storing and transporting hydrogen. Liquid organic hydrogen carriers (LOHC) technology is one of the most promising alternative methods, storing hydrogen in a liquid state compound, thereby enabling stable and high-density hydrogen storage. Previou studies have reported various LOHCs such as metylcyclohexane, dibenzyl toluene, N ethylcarbazole, ammonia borane and bis-BN cyclohexane. Among them, it has been reported that bis-BN cyclohexane, a derivative of AB, can overcome the disadvantage of ammonia borane (i.e., AB is rapidly decomposed below 150 °C), because it is thermodynamically stable at 150 °C and has a hydrogen storage capacity of 4.7 wt%. In the current study, we conducted an ab-initio study to develop hydrogen storage materials with higher efficiency and reversibility using Gaussian 16 software package. The dehydrogenation mechanism of bis-BN cyclohexane was investigated by calculating the reaction enthalpies and free energies, and then highly efficient materials were screened by conducting the same calculation depending on various functional groups such as F, Cl, and CH3. When F was replaced in one of the H atom of bis-BN cyclohexane, the enthalpy and free energy for the dehydrogenation were 26 kcal/mol and 0.1 kcal/mol, respectively, which proved to be enhanced reversibility of bis-BN cyclohexane-based LOHC.

PM232 Development of electrochemical pump for hydrogen transport and storage from methylcyclohexane
Masaki KAKINUMA1, Hirokazu ISHITOBI1, Hiroshi KOSHIKAWA2, Shunya YAMAMOTO2, Testuya YAMAKI2, Nobuyoshi NAKAGAWA1
1 Gunma University, Kiryu, Gunma
2 National Institutes for Quantum and Radiological Science and Technology, Takasaki, Gunma

Electronic power generation in Japan contributed by thermal power generation in terms of economics, environmental compatibility, and stable supply. However, there is a problem that the environmental negative influence is high, such as the formation of greenhouse gases emitted when burning fossil fuels. Therefore, hydrogen has recently been attracted attention as a power source. Hydrogen has an advantage compared to the other energy medias, i.e., hydrogen can use be produced from various primary energies including renewable energies, and electricity is obtained by using a fuel cell. However, there is also an issue that the cost is high for transportation and storage due to the use of a high pressure tank because of the low volumetric energy density. Therefore, we propose an electrochemical device for production of hydrogen from methylcyclohexane, which is an energy carrier. The reaction, separation, and compression processes are performed by one device, the cell structure is similar to a PEFC, and the reaction principle is the electrolysis of methylcyclohexane by an external voltage.The formation of proton from methylcyclohexane carries out at an anode catalyst (reaction process), separation between hydrogen and organic compound by the Nafion membrane (separation process), and electrochemical compression based on the Nernst equation (compression process). In this study, hydrogen was obtained from reaction, separation, and compression from pure methylcyclohexane, and the concentrations of hydrogen and impurities were evaluated by gas chromatography. As a result, a current density was more than 50 mA cm–2 at a cell voltage of –2.0 V.

PM233 First principles study on the reversible dehydrogenation mechanisms of BN-biphenyl and BN-diphenylmethane for renewable hydrogen energy
Yu-Gyeong LEE, Yeon-Jeong SHIN, Yuri MIN, Dong-Hee LIM*
Chungbuk National University, Cheong-Ju, Korea

As an eco-friendly energy source to replace fossil fuels, hydrogen energy is seen as a next-generation energy source with its high general purpose applicable. However, there are technical limitations to stable hydrogen storage and release for economic feasibility and efficiency. Liquid organic hydrogen carriers (LOHCs) can be one of the ways to overcome this. In previous studies, it was demonstrated experimentally that biphenyl exists in a liquid state at room temperature when mixed with diphenylmethane, and has a hydrogen storage capacity of 6.9 %wtH2 and 60 g/L. Our preliminary study demonstrated that the dehydrogenation efficiency of biphenyl has increased when carbons were replaced with boron (B) and nitrogen (N) in the molecule. Based on the findings, the current study investigated the reversible dehydrogenation and hydrogenation mechanisms of BN-biphenyl and BN-diphenylmethane by predicting reaction enthalpies ($Delta;H) and free energies ($Delta;G) based on density function theory (DFT) calculations. In addition, alternative materials with higher efficiency are to be screened by adding functional groups (F, Cl, NH2, etc.) in the molecules. This will contribute to the development of an optimal hydrogen storage and release of highly efficient LOHCs.

PM234 Kinetic study of H2 production and CO2 activation by methane in chemical looping methane cracking system with Iron-doped Barium Zirconate
Shu HIKIMA, Martin KELLER, Hiroki MATSUO, Junichiro OTOMO
The University of Tokyo, Kashiwa, Japan

Hydrogen, which is clean and storable fuel, is an attractive energy carrier for energy and environmental issues. In addition, hydrogen plays a vital role in chemical industry as a reactant. Nowadays, hydrogen is mainly produced from fossil fuels by steam reforming with CO2 emissions, so new hydrogen production process which is eco-friendly has been desired. Thermocatalytic decomposition of hydrocarbon is attracting attention because there is no emission of greenhouse gases such as CO2 during hydrogen production. Several researchers have investigated various catalysts for this reaction, but there is a problem of carbon deposition on the surface which blocks active sites of the catalyst. Based on the situation, “chemical looping methane cracking system” has been proposed. This system is composed of two reactors. In a first reactor, methane is cracked into H2 and carbon, and in a second reactor, deposited carbon is oxidized by CO2 into CO. The system has advantages in terms of separated syngas production and CO2 utilization. As an oxygen carrier, Fe/BaZr0.9Y0.1O3 composite was reported in our previous study, which exhibited high reaction kinetics for methane cracking because of high proton conductivity of BaZr0.9Y0.1O3
In this study, we synthesized Fe-doped BaZr0.9Y0.1O3 and investigated the reaction activity of these catalysts by thermal gravimetric analysis and gas analysis. Fe-supporting method, i.e., Fe doping, and the amount of Fe influenced the states of deposited carbon in methane cracking. For example, direction of growth and diameter of carbon fiber, and reaction kinetics also changed by the oxygen carriers. On the other hand, the carbon oxidation reaction with CO2 completed in a relatively short time for each catalyst. Besides, cyclic stability was investigated. Through the kinetic measurements, we discussed the effect of the feature of prepared catalysts on reaction kinetics and the efficiency of the system.

PM235 Fabrication of highly dispersed Co/N catalyst in zeolite templated carbon using Co/2-methylimidazole anchored to Y zeolite and its application in oxygen reaction reduction
Yexin ZHU1, Koji MIYAKE2, Yasuhiro SHU1, Yuichiro HIROTA1, Yoshiaki UCHIDA1, Chang Yi KONG2, Norikazu NISHIYAMA1
1 Osaka University, Toyonaka, Osaka, Japan
2 Shizuoka University, Hamamatsu, Shizuoka, Japan

Zeolite templated carbons (ZTCs) composed of curved and single-layer graphene frameworks have uniform micropores (ca. 1.2 nm) and high surface areas (~4000 m2 g-1). Due to their outstanding properties originating from the porous structures, ZTCs have been utilized in many applications, e.g. hydrogen storage, CO2 capture, catalysts and electrochemical capacitors. To expand the utilization of ZTCs, metal atoms or heteroatoms have been doped to ZTCs. However, it is still challenging to fabricate single atomic transition metals coordinated with heteroatoms in ZTCs. In this work, we synthesized Co/N doped ZTC (Co/N-ZTC) by complexing Co ion with 2-methylimidazole in Y zeolite to expand the further utilization of ZTCs as shown in Figure 1. The first step is to anchor Co/2-methylimizole complex into HY zeolite as a precursor of Co/N-ZTC by complexing Co ion with 2-methylimidazole in HY zeolite. The next step is chemical vapor deposition (CVD) using methanol as a carbon source, followed by carbonization process. The last step is base and acid treatments to remove HY zeolite and aggregated Co particles. The obtained Co/N-ZTC has a high surface area (ca. 2000 m2 g-1) and single atomic Co species in CoNx moieties, which actually contributes to its excellent catalytic performance on oxygen reduction reaction. This synthetic concept is beneficial to fabricate single atomic transition metals coordinated with heteroatoms in ZTCs.

PM236 Hydrogen storage properties of MgH2-carbon nanotube composite
Kosuke KAJIWARA, Hisashi SUGIME, Suguru NODA, Nobuko HANADA
Waseda University, Tokyo, Japan

Hydrogen is paid attention as clean energy because it does not emit CO2 when converted to electricity. MgH2 is one of the promising hydrogen storage materials because of its high volumetric and gravimetric hydrogen densities and abundance. However, Mg expands and shrinks during hydrogen absorption and desorption, respectively. MgH2 powder pulverizes during hydrogen absorption and desorption cycles. In the tank filled with MgH2, pulverized powder drops and the density of packed bed at the bottom increases. This causes a problem of tank deformation during cycles. In this research, in order to absorb volume change of MgH2 and fix pulverized powder during cycles, MgH2 particles were retained in carbon nanotubes film. MgH2 and carbon nanotubes were co-dispersed in N-methyl-2-pyrrolidone. The MgH2-CNT composite was synthesized by vacuum filtration of the dispersion. The structure of MgH2-CNT composite (MgH2-CNT w/o press) was maintained after hydrogen ab/desorption (Fig.1 a), however, the hydrogen desorption rate was lower than that of MgH2 powder (Fig.1 b). In order to improve desorption rate, the MgH2-CNT composite was pressed to decrease its porosity. As the result, the desorption rate of pressed MgH2-CNT composite (MgH2-CNT w/ press) was improved compared to MgH2-CNT w/o press, but the film structure was broken into pieces. The MgH2-CNT composite was wrapped in stainless mesh and pressed (MgH2-CNT w/ mesh, press) to support the film structure. The composite achieved improved desorption rate and maintained film structure during hydrogen ab/desorption cycles.

Session S9. Diversity in chemical engineering (Invited talks only)

F301 [Keynote] Preparing for tomorrow's workforce
Kimberly OGDEN
AlChE and Chemical Engineering, University of Arizona

The world population is growing rapidly, which requires unique solutions to assure safe water, food and energy for all. Concurrently, the numbers of women and ethnic minorities entering Science, Technology, Engineering and Math (STEM) fields in the US is stagnant. An inclusive and diverse workforce is required in order to find sustainable ways to address these challenges by thinking globally but working regionally. This presentation will review where we are in terms of workforce development and provide examples of how we are teaming together to provide safer water, healthier food, and off the grid energy in rural areas of the Southwestern United States.

F303 [Invited] Typical green chemical processes in China
Xiangping ZHANG
Insitutue of Process Engineering, Chinese Academy of Sciences

In recent years, China's chemical industry has made great development, which greatly promotes the national economic power and living standard but also faces a series of new challenges, such as environmental problems. In order to resolve these problems fundamentally, Chinese scientists have been undertaking research in the area of green chemical engineering for many years and achieved great progresses. In this presentation, several typical green chemical processes related to the Chinese resources characteristics and environmental requirements were presented, i.e. the C2/C4 processes for green methyl methacrylate production, CO2 green utilization by convert to dimethyl carbonate and ethylene glycol, green processes for gas (CO2, SO2, H2S, NH3) separation and recovery based on ionic liquids, green solvent-mediated extraction technologies, as well as utilization technologies of cellulous. Afterwards, the perspectives and development tendencies of green chemical engineering in China were proposed, and the solvent and process innovation for developing sustainable industrial technologies in China will remain a key point in the visible future.

F304 [Invited] From social network to research network
Joung Sook HONG
Seoul National University, Institute of Chemical Processes

The Korean Society of Rheology is a small academic society mostly focusing on fluid mechanics of non-Newtonian fluid. The number of member is about 1000 but a real acting member is about 200. In the society, a diversity committee was organized recently in 2018 during annual spring meeting of the society, 15 female rheologists and 3 student members were involved in the committee. The aims and main role of the committee is a build-up of network of female rheologists and rheologist candidates and share the information.
The challenge to organize the committee is a lack of self-motivation of each female rheologist to join the committee. Most of them believed that being a part of the committee is nothing to do with progress in academic activity or already gave up to make a progress in research even though they do not develop how to keep up a professional career as scientist in their own way. Right! the aims and role of the committee of “build-up of network” is not directly related to the academic activity. However, as long as the society plays a role to providing a playground for academic activity, the committee is a good way for female rheologist to gather or to share research and life along with the society of itself. Especially, female scientists working on a similar research area shares several hindrances from custom, life, and research is useful to find identity as well as to achieve successful career.

F305 [Invited] Current status and future outlook of woman engineer in Taiwan
Department of Chemical and Materials Engineering, National Central University

The situation of women in fields related to natural sciences, technology, engineering and mathematics (STEM) is one of the significant research topics of the 2000s. The main argument behind this agenda is that some professions traditionally considered to be suitable for women and some for men, due to gender stereotypes. It is also argued that provided the necessary social and economic conditions, women can accomplish as well as men do in mentioned fields. Engineering is one of these professions which is traditionally attributed to men. Same as other countries in the world, more than a quarter students are female in STEM in university. All of them can find a job in industry. However, 20 years after graduation, two out of ten women are leaving STEM careers despite STEM jobs being some of the fastest growing and highest paying around the world. One of the biggest factors that sees women leaving their STEM careers is a realistic work-life balance. More than 20% of women quit their jobs when they have children, as they cannot afford daycare or a full-time nanny. It is why flexible working conditions have become a non-negotiable point for women engineer. In this presentation, the current situation and future outlook of woman engineering in Taiwan will be reported.

F306 [Invited] Challenges for diversity promotion in the Society of Chemical Engineers, Japan
Functional Fluids Ltd.

The Society of Chemical Engineers, Japan (SCEJ) was founded in 1936. In 2002, we joined the Japan Inter-society Liaison Association Committee for Promoting Equal Participation of Men and Women in Science and Engineering (EPMEWSE) as one of the twelve initial members. EPMEWSE grew into the association of about 100 academic societies in STEM field, whose main roles are large-scale surveys on gender equality, proposals and requests to government, and symposiums. In 2003, the committee for gender equality was established in SCEJ. Since then, we have carried out various activities, such as “female engineer forum” in annual academic meeting, networking women engineers, dissemination of information on diversity by our journal and website. The number of female members of SCEJ has increased slowly but steadily and its ratio has doubled during the last 15 years. Recent technological breakthroughs symbolized by AI, IoT and robotics are significantly changing the human society beyond technology. At such times, it is increasingly important to maximize the capabilities of diverse members as an essential element for active innovation. In SCEJ, we share this vision and encouragement of constructive female participation is one of the main pillars of our strategy toward sustainable future. In this paper, an overview of the present situation of gender equality in Japan and the challenges for diversity promotion in SCEJ is presented.

Session S10. Industry 4.0 and the future of chemical engineering (Invited talks only)

A401 [Special keynote] Challenges on artificial intelligence for Japan and chemical industry
Mitsubishi Chemical Holdings, Tokyo Japan / The Japanese Society for Artificial Intelligence, Tokyo Japan

The spread of artificial intelligence (AI) technology and its application is going to make major changes in business and society. While AI technology has come to be used in more complex and important situations in industries, technical or social issues have also been visible. In this talk, I will outline the history and latest technology trends in AI. I also introduce examples of activities in chemical industry, including anomaly detection, predictive analysis, and knowledge management powered by AI technology. Real application of AI raises both technical and social issues. I will also discuss on the challenges to resolve these issues and directions for the future. which will be discussed in my talk. Finally, I will introduce the activities of The Japanese Society for Artificial Intelligence, which is the largest academic society in Japan.

A404 [Keynote] Model-free and model-based deep reinforcement learning for control and optimization of process systems
Jong Woo KIM, Tae Hoon OH, Yeonsoo KIM, Jae Jung URM, Jong Min LEE
Seoul National University, Seoul 08826 Korea

Dynamic programming (DP) provides the optimal closed-loop solution in the presence of uncertainty, and the solution is free from online computation time. Reinforcement learning (RL) method aims to acquire the approximate solution of DP by resolving the intractability in the curse-of-dimensionality, while maintaining the advantages of DP. Recent advances of RL are rooted in two agnostic characteristics: first, the development of deep neural networks (DNNs) enables the approximation of high-dimensional nonlinear functions by automatically extracting the feature of the domain, and second, the algorithm does not require the structures of system and cost.
Herein, this presentation introduces both model-free and model-based applications of RL to the control and optimization of process systems engineering problems. The model-free formulation is advantageous to the system which cannot be expressed as a continuous state space model such as hybrid model and commercial simulation software. To the system where the massive trial-and-error data acquisition is impossible, the model knowledge should be taken into account to enhance the data efficiency. Based on the Hamilton-Jacobi-Bellman (HJB) formalism which states the optimality, differential dynamic programming (DDP) method is utilized as a numerical method for solving the HJB equation. The feedback control law is obtained with the local second-order approximation of the cost function and system dynamics. The resulting model-based RL formulations for a tracking problem and a constrained dynamic optimization problem are presented.

A406 [Keynote] Small Data Integration for Process Modeling by Using Deep Neural Network-based Word Embedding
Yuan YAO
National Tsing Hua University, Hsinchu, Taiwan

In the big data era, small data problems still exist in many industrial sectors. Taking the high-value process industries as an example, a large number of materials and process methods are often tested at the design stage. However, only a small amount of data can be collected for each material-process combination (referred to as a “task”), which poses a serious challenge to data-driven process modeling. There is a great necessity to integrate the small data measured in different tasks and build the process model by sharing the information. In this work, a deep neural network-based word embedding technique is adopted to extract the qualitative task information for process modeling. Specifically, an autoencoder is used to learn embeddings which are combined with the quantitative process conditions as the inputs of a feed-forward neural network to produce the final predictions. The feasibility of the developed method is illustrated with an extrusion process. In the studied case, the proposed network shows both good interpretability and prediction accuracy.

A408 [Keynote] Revolution in chemical industry triggered by modular flow technology
Ken-Ichiro SOTOWA
Kyoto University, Kyotodaigaku-Katsura, Nishikyo-Ku, Kyoto 615-8510 Japan

Many pharmaceutical companies and academic researchers are working together to develop continuous processing or flow manufacturing technology for small scale processes. Migration from batch to continuous is expected to bring about various benefits including reduction in production cost and waste, and improvement in product quality. Another advantage is the flexibility. The production volume can be easily adjusted by changing the operation time or the number of production lines. Flexibility can be further improved by modular approach, in which modules for unit operations are prepared, and processes are constructed on-demand by just connecting them each other. To achieve these goals, we need to acquire several new technologies. First, small scale continuous separation units must be developed. A new design strategy for modular flow system should be established. The modules must be designed by taking account of flexibility and optimality of production processes to be built with them. Process design will be to find the best configuration of modules, rather than calculating the flow rates and sizes. To start the operation right after connecting the modules, we must be able to build the instrumentation and control systems. The information system for the each module should be designed carefully so that the operation system, as well as the flow process itself, can be reconfigured easily. It is expected that this can be achieved through employment of IoT sensors and actuators. A database for managing the operation records, and data processing technology, including AI, are also necessary to handle and analyze a large amount of data collected from the IoT devices. The advancement in small scale modular flow technology, together with the information systems, promotes the creation of new systems concept in chemistry, including fully automated chemistry labs.

Session 1. Physical properties and physical chemistry

O313 Phase-equilibrium measurement of Carbon dioxide/Toluene/Poly(styrene) ternary system using laser turbidmetry
Masaya OTSUKA, Hiroaki MATSUKAWA, Masakazu NAYA, Atsushi SHONO, Katsuto OTAKE
Tokyo University of Science, Tokyo, Japan

Recently, the application of supercritical fluid, particularly supercritical carbon dioxide (scCO2), and polymer has been expected because it is safe and harmless for environment in increasing social interest in global environmental deterioration and rising costs of fossil fuels. For example, a polymer foam is one in which cells are dispersed inside a polymer, and the amount of material used can be reduced by the presence of the cells. Other examples include atomization and fiberization. Unfortunately, it is difficult to obtain sufficient products with only supercritical carbon dioxide and polymers. Therefore, attempts have been made to add a solvent as the third component. As a result, it is beginning to be reported that the performance can be changed more broadly than when no additive is added. The cause of this change is expected to be due to the change in physical properties by the addition of solvent, but the physical property data of the CO2/solvent/polymer ternary system are limited. Particularly, a phase behavior is important for the process design. In this study, the phase behavior of a CO2/toluene/polystyrene (PS) ternary system was measured.
The phase behavior was observed by an apparatus based on a synthetic method. In this system, two types of the phase boundary were observed; bubble point (BP) and cloud point (CP). The BP pressures were defined as the pressure at which small bubbles appear in the cell. The CP pressures were determined by measuring the turbidity of the system by the variation of reflected light intensity. In addition, the effects of composition, temperature, and polymer molecular weight for the phase behavior were examined.

O314 PVT Relationships of Hexyltrimethoxysilane
Aki FUJII1, Hiroaki MATSUKAWA1, Masakazu NAYA1, Atsushi SHONO1, Takaaki HOSHINA2, Tomoya TSUJI3, Katsuto OTAKE1
1 Tokyo University, Tokyo, Japan
2 Nihon University, Chiba, Japan
3 University of Technology Malaysia, Kuala Lumpur, Malaysia

Physical properties such as density, viscosity, and vapor-liquid equilibrium are indispensable information for the chemical process design. The demand for these physical properties is increasing in these days. In particular, the PVT relationship is one of the most basic and fundamental physical properties however, as the measurement needs specialized equipments and a long measurement period, the experimental data are always insufficient.
Silicon alkoxides are used extensively as raw materials of silica materials such as thin film, monolith, and silica aerogel which has high thermal insulation performance though, there are few reports on the thermodynamic properties of these substances. In this work, PVT relationships of hexyltrimethoxysilane(HTMS) was measured by an experimental apparatus based on a general variable volume method. Experiments were performed at temperatures from 303 to 363 K and pressures up to 160 MPa, and measurements were repeated at least three times.
Furthermore, from the above-mentioned subject in the measurement of physical properties, complementation of data by calculation as well as measurement is required. On this purpose, the equation of state (EoS) is a powerful tool. In this study, Sanchez-Lacombe Equation of state (SL EoS), whose parameters could be determined from only the PVT relationship. The measured PVT relationships of silicon alkoxides were correlated by SL EoS and the SL parameters were determined. In addition, estimation of the SL parameters of HTMS from the SL parameters of methyltrimethoxysilane (MTMS) reported previously was conducted with considering the molecular structure.

O315 Occupancy ratio of methane hydrates analyzed with Raman spectroscopy
Shinichiro YAMAMOTO1, Takuya SASAGAWA1, Yuya HIRAGA2, Masaki OTA2, Takao TSUKADA2, Hiroyuki KOMATSU3, Richard L. SMITH, Jr.1,4
1 Graduate School of Environmental Studies, Tohoku University, Sendai 980-8579 Japan
2 Graduate School of Engineering, Tohoku University, Sendai 980-8579 Japan
3 Graduate School of Science and Technology, Niigata University, Niigata 950-2181 Japan
4 Research Center of Supercritical Fluid Technology, Tohoku University, Sendai 980-8579 Japan

Methane hydrates (MH) in the Nankai Trough of Japan are considered as promising resources for developing CO2-free energy. In this work, the objectives were: (i) to develop an optical system for measuring method hydrate dissociation in situ, (ii) to measure change of occupancy ratio during MH dissociation and (iii) to develop a method for correlating occupancy ratio that can be used in large scale simulation systems. During the MH dissociation process, occupancy (θ) in each cage (θM or θS) changes based on degree of progress for dissociation. For analyzing the cage occupancy of MH, Raman spectroscopy was used as an in-situ technique to determine methane hydrate dissociation characteristics. MH films were synthesized with pure water and methane gas. The procedure used allowed MH films to form on the lower surface of the high-pressure optical cell sapphire window, which eliminated noise associated with the C-H stretching vibration of bulk methane gas. The changes in the relative cage occupancy ratio (3θM/θS) in the methane hydrates were monitored at equilibrium conditions and during changes of pressure in which dissociation occurred. The cage occupancy ratio (3θM/θS) in MH decreased with increasing pressure at equilibrium conditions due to increasing amounts of methane present in the S-cage. For an occupancy ratio (3θM/θS) of 3.37 (273.8 K, 5.0 MPa) the uncertainty in occupancy ratio obtained with procedures developed in this work was ca. 0.09 compared with a literature value of ca. 0.71. The Kihara potential parameters used in the model were redetermined to provide reliable correlation of the data. For depressurization conditions, (275.65 K, 7.60 MPa → 5.94 MPa), the cage occupancy ratio in MH increased up to 240 h monitoring time. The trend of the cage occupancy ratio with pressure and model will be useful for developing large-scale simulations of actual methane hydrates.

O316 Phase behavior for the polydisperse polyethylene + hexane + ethylene system at high pressures and temperature: Effect of molecular weight and polydispersity
Rizqy Romadhona GINTING, Kazunori HIMEMURA, Yutaro OGAWA, Ikuo USHIKI, Shin-ichi KIHARA, Shigeki TAKISHIMA
1 Hiroshima University, Higashi-Hiroshima, Japan

In recent years, several studies have reported the possibility of reducing energy consumption during the solution polymerization process of polyethylene by the introduction of a liquid-liquid (LL) separator. Besides temperature and concentrations, molecular weight (Mw) and polydispersity index (PI) are important factors for the design of the separation process. Unfortunately, the effect of Mw and PI to the phase behavior of PE + hexane + ethylene system has not been extensively studied. Previously, the LL phase behavior for PE + hexane + ethylene system was studied using polydisperse PE (PE30: Mw 30.0 kg/mol, PI 4.2) at 473 K. The addition of 1wt% of ethylene to the binary PE + hexane system increased the phase separation pressure by 1 MPa at almost the same magnitude over all feed PE weight fraction (wF,PE) range.
This study aims to provide experimental data and investigate the effect of Mw and PI to the phase behavior of PE + hexane + ethylene system. The experiments were conducted using polydisperse PE (PE4: Mw 4.0 kg/mol, PI 2.4) at 473 K with wF,PE ranging from 0.02 to 0.20 using a variable-volume optical cell equipped with a hand pump and a recording system. Comparing with PE30, the LL phase separation pressure of PE + hexane system for PE4 was about 3.0 MPa lower, and the addition of 1wt% of ethylene only increased the phase separation pressure by 0.8 MPa. The phase separation pressure increased as the Mw increased, and the addition of ethylene shifted the LL phase boundary to higher pressure. The results provided from this study could complement previous understanding for the design of the separation process.

O317 [Keynote] New activity coefficient model for correlation and prediction of phase equilibria
Yoshio IWAI
Kyushu University, Fukuoka 819-0395, Japan

The author proposed a new activity coefficient model [Y. Iwai, Fluid Phase Equilibria 465 (2018) 24-33]. The new model was derived from Guggenheim quasi-chemical theory with Taylor series. The formula of the new model is similar with that of regular solution theory. However, new idea in the new model is the surface area parameters, which account for the number of interactions between molecules, were assumed to vary depending on partner molecules and the concentration of mixtures. The new model can describe an exceptionally high value or convex behavior of activity coefficient in the dilute region. The liquid-liquid equilibria for ternary systems and the vapor-liquid equilibria for constituent binary systems can be correlated well with the same parameter sets.
The following results will be shown in this presentation.
(1) The new model is applied to calculate the activity coefficients for the systems which are difficult to correlate by widely used models. The target systems are as follows.
The systems of activity coefficients show convex behavior.
The systems of activity coefficients sharply increase or decrease in dilution region.
The systems of partially miscible.
(2) The new model is expanded to a group contribution method. Some results of the group contribution method will be presented.

O321 [Keynote] Phase Equilibria of diethyl carbonate (DEC) mixtures with alcohols and hydrocarbons related to gasoline property
Gede WIBAWA, Rendra Panca ANUGRAHA
Department of Chemical Engineering, Faculty of Industrial Technology, Sepuluh Nopember Institute of Technology (ITS), Kampus ITS Sukolilo Surabaya, 60111, Indonesia

Diethyl carbonate (DEC) is one of the most promising compound that may be used as co-additive with ethanol/alcohols in gasoline blends because its higher octane number, lower vapor pressure and lower miscibility with water than ethanol. To apply DEC as gasoline additive, there are some aspects to be concern because blending process could change its physical properties such as vapor pressure and water miscibility. In order to know the physical properties of DEC-gasoline fuel mixture, the phase equilibria of DEC mixtures with several alcohols and hydrocarbons related to gasoline are required. Therefore, in this study, we reported the phase equilibria of DEC mixture with alcohols and hydrocarbons in binary and ternary systems at temperature range of 303.15 K – 323.15 K. From the isothermal vapor–liquid equilibrium (VLE) data, the vapor pressure of DEC mixtures with alcohols and hydrocarbons in binary and ternary systems were obtained. DEC is found to successfully decrease the vapor pressure in binary mixtures with hydrocarbons (isooctane, n-heptane, toluene) and alcohols (ethanol). In ternary mixtures, DEC is found to successfully decrease the vapor pressure of hydrocarbon + alcohol mixtures as well. The binary isothermal VLE data were well correlated using Wilson, nonrandom two-liquid (NRTL) and universal quasi-chemical (UNIQUAC) models with average absolute deviation (AAD) less than 2%. The binary parameters obtained from binary mixtures give good accuracy prediction results for ternary mixtures with AAD less than 5%. For the liquid-liquid equilibrium (LLE) containing of DEC and water, the water miscibility of DEC + alcohols + hydrocarbons mixtures were obtained. From the liquid-liquid equilibrium data of DEC + water + ethanol/ 1-propanol ternary mixtures, the presence of DEC in ethanol/ 1-propanol decrease the content of water. The LLE data for these ternary mixtures were well correlated using NRTL and UNIQUAC models with root mean square deviation less than 0.005.

O323 Prediction of CO2 solubility in ionic liquids using BWR equation of state
Hideo NISHIUMI1, Daisuke KODAMA2
1 Hosei University, Koganei, Tokyo, Japan
2 Nihonn University, Koriyama, Fukushima, Japan

When the critical properties of a pure substance are known, it is possible to predict thermodynamic properties based on the corresponding state principle using an equation of state. However, we can hardly find experimental values of critical properties of complex molecules such as ionic liquids. Extending the Joback method, I succeeded in predicting the critical temperature of complex molecules [1]. Moreover the critical volume of [hmim][Tf2N] was determined to fit the density of ionic liquid.
To calculate a mixture properties, especially phase equilibria, a binary interaction parameter, mij , should be determined. Changing mij values of glymes, TCMs and [hmim][Tf2N], the solubility of CO2 in the ionic liquids were best fitted.
In 1977, we reported that the optimal mij values for the modified generalized BWR equation of state were found to belong to several family groups expressed as a function of the ratio of critical volumes [2,3]. This time, recalculation brought a simpler correlation. As shown in a following figure for the CO2 containing family group, the above three kinds of ionic liquids were found to be on the same correlation curve. It means that polarity of complicated substances plays small role. It shows that the correlation of binary interaction parameter for the CO2-nonpolar substances can also apply to more complicated polar systems, such as ionic liquids.
[1] H. Nishiumi, Fluid Phase Equilibria, 420 (2016) 1–6
[2] G.H. Hudson, J.C. McCoubrey, Trans. Faraday Soc., 56 (1960) 761
[3] H. Nishiumi, S. Saito, J. Chem. Eng. Japan, 10 (1977) 176–180

O324 Development of Helmholtz-type equations of state for chemical hydrogen storage mediums
1 Toyama Prefectural University, Toyama, Japan
2 Kyushu Sangyo University, Fukuoka, Japan
3 National Institute of Standards and Technology, Boulder, CO, USA

Hydrogen reforming technologies, which combine hydrogen with toluene or naphthalene and store/transport it as methylcyclohexane or decalin, are expected to be widely used in the future due to the ability to safely transport the fuel with the highest concentration of hydrogen possible.
A reference database of equations of state is essential for the optimal selection of substances and the development of international technical standards. To add to this database, we started the development of highly accurate equations of state for these organic substances and their mixtures. We adopted the Helmholtz-type functional form, as with all other international standard equations of state for water and alternative refrigerants.
Throughout the fitting process, we used three types of input information for correlation. The first is the appropriate ranges of values of exponents and coefficients in the equations of state, the second is the numerical information on the shape of the thermodynamic state surface, and the third is the published measurement information for each substances. The present fitting program, which was developed by Lemmon [1], includes these three elements in the objective function effectively, and therefore we carefully controlled the behavior of each compound while simultaneously fitting the experimental data.
In our presentation, we will report the current status on the development of the equations of state being developed for the pure components used in the aforementioned hydrogen reforming technologies.
[1] E.W. Lemmon, “Equation of State Fitting with the REFPROP Program”, National Institute of Standards and Technology, Boulder, CO USA (2019).

O325 Effect of Methylene Spacer Number between Charged of Sulfobetaine and Its Copolymerization with Thermosensitive Polymer on Gel Adsorption Properties
Eva Oktavia NINGRUM1, Shuji SAKOHARA2, Takehiko GOTOH3, Suprapto1, Nurlaili HUMAIDAH1
1 Department of Industrial Chemical Engineering, Faculty of Vocational Studies, Institut Teknologi Sepuluh Nopember, Kampus ITS Sukolilo, Surabaya, 60111, Indonesia
2 National Institute of Technology Niihama College, Yagumocho, 7-1, Niihama-shi, Ehime Prefecture 792-8580
3 Department of Chemical Engineering, Graduate School of Engineering, Hiroshima University, Kagamiyama 1-4-1, Higashi-Hiroshima, 739-8527, Japan

In the past few years, the use of the combination between zwitterionic ion chromatography (ZIC) and the interaction liquid chromatography (HILIC) [ZIC–HILIC] in identifying specific substances has been developed and considered to be the best technique in identifying certain substances in a solution. A zwitterionic betaine polymer is known to be able to convey whole neutral charge since it contains both anionic and cationic active groups which are sulfonate and quaternary ammonium groups in the same polymeric repeat unit. This study was conducted aiming to develop gel with the characteristic of reversible thermosensitive in adsorbing heavy metal ions from its solution. There are three gels used in this study to adsorb heavy metal ion from salt solution provided Zn(NO3)2; copolymer gel consisting of zwitterionic betaine N,N-dimethyl(acrylamidopropyl)ammonium propane sulfonate (DMAAPS), N,N-dimethyl(acrylamidopropyl)ammonium butane sulfonate (DMAABS), and DMAAPS copolymerized with thermosensitive N-isopropylacrylamide (NIPAM) gels. These gels were used to investigate the adsorption ability and its swelling degree which was synthesized by free radical polymerization before being affected by methylene spacer number, copolymerization, and temperature given. This research found that as the temperature increases, the ability of the gel in adsorbing the ions decreases. In the case of DMAAPS and DMAABS gel, the swelling degree value increases when the temperature also increases. Meanwhile, sulfobetaine which has larger spacer has higher adsorption ability but not with its swelling degree. In spite of having more spacer than DMAAPS, DMAABS found to have the smallest swelling degree value. In addition, NIPAM-co-DMAAPS was found to have both the highest adsorption ability and swelling degree value. Eventhough copolymer has less amount of sulfobetaine than DMAAPS and DMAABS gels', the copolymer gel was found to have higher ability of adsorption as many as ten times of other gels.

O326 Mechanical properties of polyvinyl alcohol-nanokenaf-nanoMMT composite
Tiam-Ting TEE1, Siew-Wai PHANG2, Ting-Sin LEE1, Soo-Tuan BEE1, Bee-Ling MAH1
1 Universiti Tunku Abdul Rahman, Kuala Lumpur, Malaysia
2 Taylors University, Kuala Lumpur, Malaysia

Polyvinyl alcohol (PVOH) is widely used in many applications due to its biodegradable properties. Cellulose and MMT are the most common organic and inorganic material used as reinforcing filler. Kenaf is one of the candidates of natural nanocellulose. Three compounds (PVOH-kenaf nanowhisker-MMT) were blended, cast and analysed. Kenaf nanowhisker loading was varied from 0 phr to 8 phr while MMT loading was varied from 1 phr to 5 phr. Mechanical properties, thermal properties and microstructure were analysed. In overall, the tensile strength exhibited highest value at 5 phr of MMT and modulus exhibited the highest value at 3 phr of MMT loading although increasing MMT loading could reduce the elongation at break. Increment of kenaf nanowhisker loading would increase the tensile strength, elongation and modulus until a maximum point where beyond the mechanical properties decreased. Among all, nanocomposites with 5 phr of MMT with no addition of kenaf nanowhisker had the highest tensile strength.

O401 Measurement of the glass transition temperature of pharmaceutical polymers with solid co-solvent under carbon dioxide pressure
Shiho ISONO, Hiroaki MATSUKAWA, Masakazu NAYA, Atsushi SHONO, Katsuto OTAKE
Tokyo University of Science, Tokyo, Japan

Glass transition temperature (Tg) of pharmaceutical polymers could be depressed by the pressurization with CO2. This phenomenon could be utilized for the formulation of pharmaceutical polymers in a short time and at mild temperature. However, there are some problems of the safety and cost under high pressure. Addition of organic solvent in CO2 could depress the Tg of polymers. Organic solvent is harmful to human, so addition of small amount of harmless solid co-solvent might be useful to lower the pressure. In this study, effects of solid co-solvent on the Tg of pharmaceutical excipients were examined with a visual method using the transmitted light intensity.
The Tg of Ethyl cellulose (EC)/CO2/ solid co-solvent systems was measured. For example, Tg of EC under atmospheric pressure was depressed by physical mixing with Vanillin (VAN) or l-Menthol (MEN) as solid co-solvent. Tg of EC with VAN or MEN wasn't depressed much under CO2. On the other hand, Tg of EC wasn't depressed by physical mixing of Xylitol (XYL). Therefore, it could be concluded that there are combinations of EC and solid co-solvent which can depress the Tg of EC and the Tg could be depressed by only addition of suitable solid co-solvent without CO2 pressure.
The state transition of EC with solid co-solvent was easily observed visually. It could be considered that Tg of EC was depressed by melted VAN or MEN dissolving into EC and wasn't depressed by melted XYL. From these facts, affinity between EC and solid co-solvent was examined by the solubility parameter (δ) which is an index of affinity between substances. The solubility parameters estimated by the group contribution method reported by Fedors [1] successfully explained that the affinity of polymers and solid cosolvent controls the Tg depression.
[1] Robert F. Fedors, Polymer Engineering and Science, Vol. 14, No. 2, California, (1974)

O402 Mechanistic insights into the acid-catalyzed depolymerization of cellulose and fucoidan
Jonas Karl Christopher N. AGUTAYA, Elaine G. MISSION, Armando T. QUITAIN, Mitsuru SASAKI, Tetsuya KIDA
Kumamoto University, Kumamoto, Japan

Biomass is a renewable and abundant resource that can reduce our dependence on the dwindling fossil fuel reserves. In particular, sugars are simple molecules that can be converted to biofuels and a wide array of platform chemicals. As found in plants and other organisms, fermentable sugars commonly exist as the repeating units in polysaccharides, which further form a complex network among themselves. Presently, one of the major challenges is to extract these sugars from these networks in an efficient and cost-effective way. The cleavage of the glycosidic bonds present in the polysaccharide structure is an important step in the process and understanding its mechanism can provide the insights necessary to develop better technologies to obtain the sugar monomers.
In this study, we used quantum calculations to determine a mechanism of the production of sugars from the acid-catalyzed hydrolysis of two model compounds, namely, cellulose and fucoidan. Glucose is the monosaccharide produced from the former and fucose from the latter. In both cases, our simulations showed that the process involves four steps. First, the oxygen in the glycosidic bond is protonated by an acid. Then, the C–O bond is broken, yielding a carbocation of either glucose or fucose. Next, the oxygen of a water molecule bonds with the positively charged carbon in the intermediate structure. Finally, the molecule is deprotonated, yielding the desired sugar monomer. Consistent for both cellulose and fucoidan, the initial step (i.e., protonation) is the rate-determining step because it requires the highest activation energy. Furthermore, our calculations showed that the depolymerization of cellulose via acid-catalyzed hydrolysis is less energy demanding than that of fucoidan.

O403 Kinetic study on the esterification of free fatty acids in coconut oil fatty acid distillate (COFAD) using sulfuric acid as catalyst
Jayhiel MALILA, Ian Dominic TABAÑAG
University of San Carlos - Department of Chemical Engineering, Cebu City, Philippines

Because of the insufficient supply of refined coconut oil as a raw material for biodiesel production in the Philippines, an exploration on the potential use of oil refining by-products, particularly coconut oil fatty acid distillate (COFAD), as an alternative feedstock has been done. The main problem encountered in the use of COFAD is its high free fatty acid (FFA) content. A pretreatment step via esterification using methanol as a solvent is needed in order to reduce the FFAs present by converting it to fatty acid methyl esters (FAME). In this study, the conversion of FFA in COFAD to FAME was done via homogeneous esterification using sulfuric acid as catalyst. The effect of catalyst loading (0.5, 1, 5 wt.% sulfuric acid) and methanol-to-COFAD molar ratio (3, 6, 10) were studied first in order to determine the best process conditions that would lead to a maximum FFA conversion and FAME content. It was found that a low catalyst amount (1 wt.%) and a high methanol-to-COFAD molar ratio (10:1) at a time of 30 minutes is a favorable combination to reduce the FFA from ~70% to ~1%. A kinetic study was further done using the best process conditions for esterification and the results were found to fit in the kinetic model having a pseudo-homogeneous first-order in the forward direction and second-order in the reverse direction. The effect of temperature on the rate of reaction was also determined by fitting the kinetic data to the Arrhenius Equation. The results of this study suggest that COFAD can be a suitable alternative feedstock for the production of biodiesel in the Philippines.

O404 Solid-Liquid Equilibria for Ternary Systems Containing Diphenyl Carbonate
Hiroyuki MATSUDA, Akari MITSUISHI, Masaki NASU, Kiyofumi KURIHARA, Katsumi TOCHIGI
Nihon University, Tokyo, Japan

Polycarbonates (PCs) have excellent features such as transparency, impact resistance, thermal stability, dimensional stability, and flame resistance. A non-phosgene process for PC production from carbon dioxide, ethylene oxide, and bisphenol A, has been developed. This process provides an effective use for carbon dioxide, which is a greenhouse gas and an abundant carbon resource, and has attracted much attention in terms of greener and more sustainable chemistry. Diphenyl carbonate (DPC) is an important intermediate material in these non-phosgene processes. The DPC purity directly affects the downstream PC quality. High-purity DPC is important in the production of PC for optical media applications. One of the options for DPC purification is crystallization. Knowledge of solid–liquid equilibrium (SLE) data is crucial in the design and development of crystallization processes. Our group determined the SLE of several binary systems containing DPC. However, more experimental SLE data for systems containing DPC are still needed.
The object of this work was to obtain SLE data for ternary systems containing DPC. We investigated the SLE of two ternary systems, i.e., methanol + DMC + DPC and phenol + DMC + DPC in the reaction involved in the non-phosgene PC process. Two ternary SLE data were experimentally determined by a synthetic, visual technique designed in our laboratory. In the measurements of ternary systems, DPC free basis mole fraction of methanol or phenol “α” was changed from 0.3 to 0.9, and changes of SLE behaviors were discussed with an increase of α. The SLE predictions for two ternary systems were compared with the experimental SLE data on the basis of the NRTL parameters obtained from the constituent binary SLE data. Also, the National Institute of Standards and Technology (NIST)-modified universal functional activity coefficient (UNIFAC) group contribution model was also used for the prediction of two ternary systems.

O405 Oxidation mechanism of HCOOH on LaCoO3 (1120) surface: A DFT study
Quantum and Molecular Engineering Laboratory, Department of Chemical Engineering, Indian Institute of Technology Kharagpur, Kharagpur 721302, India.

Direct oxidation of formic acid is prominent in fuel cells. We recently reported the catalytic
activity of LaCoO3 for this reaction [Electrochem. Commun., 99, 1-4, 2019]. For the first time, density functional theory (DFT) calculations are used for analyzing the mechanism of this reaction. We sampled a different number of HCOOH adsorption configurations as adsorption plays a crucial role in oxidation. Similarly, proton adsorption in different oxygen environments of the surface was analyzed. By considering the electro-oxidation environment of HCOOH, comparison of decomposition was done with and without water. This study is expected to aid the understanding oxidation of HCOOH on noble-metal free material LaCoO3.

O406 Density functional theory-based study of O2 adsorption on S- and P-doped graphitic carbon nitride/graphene layer
Wilbert James C. FUTALAN1, Koichi KUSAKABE2, Allan Abraham B. PADAMA3, Joey D. OCON1
1 Department of Chemical Engineering, University of the Philippines, Diliman, Quezon City, 1101, Philippines
2 Graduate School of Engineering Science, Osaka University, 1-3 Machikaneyama-chou, Toyonaka, Osaka, 560-8531, Japan
3 Institute of Mathematical Sciences and Physics, University of the Philippines, Los Banos, Laguna, 4031, Philippines

Graphitic carbon nitride, whose activity is due to the electronegativity difference between the carbon and nitrogen atoms, has gained popularity among metal-free catalysts. Experiments with graphitic carbon nitride have shown that addition of a conductive carbon support to GCN improves its activity towards oxygen reduction reaction (ORR) 1, 2. Following previous studies on doped GCN, substitution of nitrogen or carbon with heteroatoms such as sulfur and phosphorus can further enhance GCN's ORR activity 3, 4. In this work, we investigate through a density functional theory-based calculation the effect of substitutionally doping sulfur and phosphorus on the graphitic carbon nitride/graphene layer in terms of adsorption energies and charge transfer extent upon oxygen adsorption. The results of the calculations suggest that sulfur doping provides higher adsorption energy compared to phosphorus doping. In terms of doping location, the calculations reveal that doping along the edge sites gives the most energetically favorable structure for oxygen adsorption. Moreover, this work considers the possible relationship between the oxygen-GCN/graphene separation distance and the oxygen bond length as an indicator of the interaction of molecular oxygen as it adsorbs onto the GCN/graphene surface.
1 S. Lyth et al. J. Phys. Chem. C 113, 47, 20148-20151 (2009).
2 S. Yang et al. Angew. Chem. Int. Ed 50, 23, 5339-5343 (2011)
3 Y. Zheng et al. J. Am. Chem. Soc. 133 50, 20116-20119 (2011)
4 Q. Han et al. J. Mater. Horiz 4, 832-850 (2017)

O413 Prediction of solubilities of acetylacetonate-type metal precursors in supercritical carbon dioxide using the PC-SAFT equation of state
Hiroshima University, Higashi-Hiroshima, Hiroshima, Japan

Deposition of metal particles into porous supports such as mesoporous silica using supercritical carbon dioxide (scCO2) has attracted much attention to prepare supported catalyst because of its ability to disperse metal particles into pore structures [1, 2]. Prediction methodology of the solubility of metal precursors in scCO2 is important to efficiently design the supported catalyst using the scCO2 deposition method.
In this work, the prediction of solubilities of various acetylacetonate-type metal precursors in supercritical carbon dioxide was performed using a thermodynamic model with the PC-SAFT (perturbed-chain statistical associating fluid theory) equation of state [3]. Pure component parameters for the metal precursors (segment number, segment diameter, and dispersion energy) were determined with correlations to solubility data of the metal precursors in various organic solvents, which were newly measured in this study. The pure component parameters of the metal precursors determined with the correlations were applied to predict literature data of solubilities of the metal precursors in scCO2 [4, 5] using the PC-SAFT equation of state. The PC-SAFT equation of state could reproduce the solubilities over wide temperature and pressure ranges for various precursors under almost all conditions without kij.
[1] J. Morere et al., RSC Adv., 5 (2015) 38880-38891.
[2] S.B. Barim et al., Microporous Mesoporous Mater., 245 (2017) 94-103.
[3] J. Gross, G. Sadowski, Ind. Eng. Chem. Res., 40 (2001) 1244-1260.
[4] M. Haruki et al., Fluid Phase Equilib., 297 (2010) 155-161.
[5] M. Haruki et al., J. Chem. Eng. Data, 56 (2011) 2230-2235.

O414 Solvation effect of water on alanine condensation in high temperature and high pressure conditions via molecular simulation and experiment
Tetsuo HONMA1, Akira HASEGAWA1, Tomohiro FURUSATO2, Mitsuru SASAKI3
1 National Institute of Technology (Kosen), Hachinohe College, Hachinohe, Japan
2 Nagasaki University, Nagasaki, Japan
3 Kumamoto University, Kumamoto, Japan

Alanine condensation in high temperature and high pressure water were performed by molecular simulation and flow-type experiment to investigate catalytic role and solvation effect of water. Relative energies of the species consisting alanine condensation and corresponding transition structures were optimized by geometry optimization with B3LYP/6-31+G(d,p) level of theory. We considered four selected reaction mechanisms of alanine condensations such as anionic, zwitterionic, cationic, and non-ionic form. We also calculated a water molecule participation onto non-ionic reaction mechanisms to quantify the catalytic role of water. Activation energies considered reaction mechanism were ranged 117 kJ/mol to 190 kJ/mol, while alanine condensation by zwitterionic mechanism showed a lowest activation energy. Activation energies in solution were calculated by the sum of the activation energy from DFT calculation and the solvation free energy from Monte Carlo simulation with the theory of energy representations by Matubayasi and Takahashi. Solvation free energy difference between reactant and transition state indicated that the alanine condensation with zwitterionic mechanism was promoted by high temperature and high pressure water, on the other hand, the alanine condensation by anionic mechanism was inhibited by water as reaction media. This solvation effects by solvation free energy difference did not have great influence on activation energy due to the solvation effect contributed around 10% to activation energy. The temperature dependence of alanine condensation by means of the flow-type experiments was indicated the second-order reaction and the activation energy was 48.5 kJ/mol. Future investigations on ionic mechanism of alanine condensation are needed to elucidate the catalytic role of water molecule and solvation effect of water as reaction media. The solvation effect of high temperature and high pressure water on alanine condensation should be responsible for the preferential solvation around reaction species, which would be shown by the analysis of solution structure in the presentation.

O415 Advanced Molecular Force Fields of Ionic Liquids for Transport Property Analysis: Development on the Basis of First-Principles DFT Calculation
Yoshiki ISHII, Nobuyuki MATUBAYASI
Osaka University, Toyonaka, Osaka 560-8531, Japan

We developed non-polarizable force field for ionic liquids by using first-principles calculations based on density functional theory(DFT). The cation is 1-alkyl-3-methyl-imidazolium, N-metyl-N-proylpyrrolidinium, and N-butyl-N,N,N-trimetylammonium. The counter anions are chloride, tetrafluoroborate, bis(fluorosulfonyl)amide, and bis(trifluorosulfonyl)amide. The DFT calculations were implemented with the QUICKSTEP of CP2K[1]. The PBE-type generalized gradient approximation was employed for the exchange-correlation functional. The atomic charges assigned in the nonpolarizable force field were evaluated with the Blöchl method[2]. The initial van der Waals parameters were set to OPLS model developed by Lopes et al.[3], and they were optimized to reproduce the intermolecular forces obtained with DFT calculation. We performed the molecular dynamics calculations in the framework of the optimized molecular force fields, and evaluated transport coefficients with Green-Kubo formulae.
The calculated transport coefficients with only the update of atomic charges remain less accurate. The accuracy is also imbalanced between viscosity and electrical conductivity. In contrast, the fully-optimized force field including van der Waals parameters provides good agreements for them with the experimental data, and moreover, the obtained accuracy is consistent over the various ionic liquids. Therefore, it turns out that the suggested optimization scheme of non-polarizable force field is useful to predict transport properties of various ionic liquids. In this oral presentation, the detail strategy of force-field development and the calculated structural/transport properties will be explained.
[1] CP2K, version 4.1, The CP2K Foundation, Zürich, 2014.
[2] P. E. Blöchl, J. Chem. Phys. 103, 7422 (1995).
[3] N. C. Lopes, J. Deschamps, A. H. Padua, J. Phys. Chem. B 108, 2038 (2004).

O416 (canceled) <101259-1>
O417 [Keynote] Gas absorption property and mechanism of ionic liquids
Takashi MAKINO
National Institute of Advanced Industrial Science and Technology, Sendai, Miyagi 983-8551 Japan

Ionic liquids are salts with melting points below ambient temperatures. They are nonvolatile and nonflammable and solve various chemicals by chemical modifications. Ionic liquids have attracted much attention as potential gas absorption media. In order to use ionic liquids for the chemical processes involved with gas absorption, the understanding of the gas absorption property and mechanism is of primarily importance. This talk presents some of highlight data on gas absorption in the ionic liquids.
CO2 absorption property and mechanism were investigated for ionic liquids based on the cations 1-ethyl-3-methylimidazolium ([emim]+), N,N-diethyl-N-methyl-N-heptyl-ammonium ([N1227]+), N,N-diethyl-N-methyl-N-(6-hydroxy)hexyl-ammonium ([N122,6OH]+), and dodecyltributylphosphonium ([P444,12]+) and the acetate anion ([AcO]-). Each ionic liquid absorbed CO2 chemically and desorbed it reversibly. The largest CO2 solubility and temperature dependency at 313.2 K were observed in [emim][AcO] and [N122,6OH][AcO], respectively. The 13C NMR spectra revealed that CO2 was absorbed in ionic liquids with different absorption mechanisms, namely, the CO2-carbene ([emim][AcO]), CO2-alkoxide ([N122,6OH][AcO]), CO2-acetate ([N1227][AcO]), and CO2-phosphineylide ([P444,12][AcO]) complexes.
We measured high-pressure CO2 solubilities in [emim]+ ionic liquids with [AcO]-, 2-methoxyethoxyacetate ([C1OC2OC1CO2]-), and 3-(2-methoxyethoxy)propionate ([C1(OC2)2CO2]-) to investigate the effect of ether modification on the CO2 physical and chemical absorption. We success fully deconvoluted the high-pressure CO2 solubility into the contributions of physical and chemical absorption. The validity of this numerical analysis was quantitatively confirmed by the NMR spectra for the [emim][[AcO]+CO2 mixtures at high pressures, which can separately identify the chemical and physical species. According to the deconvolution results, the 2-methoxyethoxy group improved the physisorption (in mole fraction) and worsened the chemisorption compared to the unmodified acetate, whereas the negative effects on both the absorptions (in mole fraction) were observed by the 2-methoxyethoxymethyl modification.
I will talk also about the NH3 and water vapor absorption in the ionic liquids in the presentation.

O421 Phase equilibria for ethylene + ethanol + vinyl acetate + poly(ethylene-co-vinyl acetate) systems
Yoshiyuki SATO1,2, Azusa FUNABASHI1, Hiroshi INOMATA1
1 Tohoku University, Sendai, Japan
2 Tohoku Institute of Technology, Sendai, Japan

Poly(ethylene-co-vinyl acetate) (EVA) has been used as a commodity material because of the controllability of its properties such as rubber elasticity, adhesiveness, or transparency by changing comonomer vinyl acetate (VA) content in EVA. Since EVA polymers are commercially produced by a solution polymerization method in EVA solution including monomer VA and diluent alcohol, phase equilibria of the EVA solutions at EVA production conditions are important.
This study has conducted the measurements of the phase equilibria for ethylene + ethanol + VA + EVA quaternary system at temperatures from 313 K to 403 K and at pressures up to 25 MPa. In the measurement, the EVA composition in the solution was kept at 10 wt% while ethanol/VA ratio was changed. Vapor-liquid equilibria were observed in lower pressure region and liquid-liquid equilibria appeared in higher ethylene concentration. It was also observed that increasing ethanol/VA ratio causes bubble point pressure (BP) increase and cloud point pressure (CP) decrease at higher temperatures. In addition, experimental results were compared with ethylene + methanol + VA + EVA quaternary systems [1]. It was found that BP and CP for ethanol systems were lower than that of methanol systems.
PC-SAFT [2] was applied to represent the phase equilibria of the quaternary system. Vapor-liquid equilibria of each binary system were correlated with the PC-SAFT to determine binary interaction parameters. Prediction results of phase equilibria for the quaternary system are shown in Fig. 1, showing relatively good results for PB but shift to higher pressures for CP at given composition.
[1] T. Nakamura et al., Fluid Phase Equilibria, 429 (2016)98.
[2] F. Tumakaka, G. Sadowski, Fluid Phase Equilibria, 217(2004) 233.

O422 Density, Viscosity, CO2 Solubility in Deep Eutectic Solvents Composed of Halogenated Onium Salt and Carboxylic Acids
Daisuke KODAMA1, Ayaka TANIGUCHI1, Masaki WATANABE1, Takashi MAKINO2, Mitsuhiro KANAKUBO2, Cornelis J. PETERS3
1 Department of Chemical Biology and Applied Chemistry, College of Engineering, Nihon University, 1 Nakagawara, Tokusada, Tamura-machi, Koriyama, Fukushima 963-8642 Japan
2 Compact System Engineering Group, Research Institute for Chemical Process Technology, National Institute of Advanced Industrial Science and Technology (AIST), 4-2-1 Nigatake, Miyagino-ku, Sendai, Miyagi 983-8551 Japan
3 Center for Hydrate Research, Chemical and Biological Engineering Department, Colorado School of Mines, 1500 Illinois St., Golden, Colorado 80401, USA

Deep eutectic solvents (DESs) are now widely acknowledged as a new class of solvents like ionic liquids (ILs) because they share many characteristics and properties with ILs. DESs generally have low vapor pressure and non-flammability, and their physicochemical properties are optimized. Then, DESs can be conveniently prepared by simply mixing a hydrogen bond donor (HBD) and acceptor (HBA) with a suitable composition. CO2 solubilities in DESs as reported in literature have been limited to hydrophilic ones and, to the best of our knowledge, hydrophobic DESs have not been systematically studied as potential solvents for CO2 capture [1].
In the present study, we have investigated the density, viscosity, and CO2 absorption behaviour of deep eutectic solvents (DESs), composed of halogenated onium salt (tetrabutylphosphonium bromide) and carboxylic acids (hexanoic acid or octanoic acid) at a 1 : 3 molar ratio (TBAC3HA or TBAC3OA). The densities and viscosities were determined at temperatures from 273.15 to 363.15 K and at atmospheric pressure. The CO2 solubilities in DESs and their saturated densities were measured at 313.15 K and pressures up to 8 MPa. The molarity of the CO2 solubilities were calculated from the experimental results. The experimental density was correlated by a quadratic equation. The viscosity data were represented fairly well by the Vogel-Fulcher-Tammann (VFT) equation. The CO2 solubilities increased with increasing pressure as observed for the typical physical absorption behaviour. The TBAC3HA and TBAC3OA gave higher CO2 solubilities than the ethylene glycol-based DES (TBAC3EG).
[1] L. F. Zubeir et al., J. Chem. Eng. Data, 63, 913-919 (2018).

O423 Theoretical studies for effective thermal conductivities of hexagonal boron nitride/polyimide composite materials
Masashi HARUKI, Jun TADA, Hajime ONISHI, Yukio TADA
Faculty of Mechanical Engineering, Institute of Science and Engineering, Kanazawa University

Polymers have many excellent properties such as light-weight, electrical insulation and flexibility. Therefore, they are widely used as important parts in the industrial fields, especially, electronic industry. Recently, the thermal management inside the advanced electronic devices becomes more important because downsizing of the device proceeds with remaining high performances. However, thermal conductivities of polymers are generally quite low. Therefore, the addition of high thermal conductive fillers into the polymer matrix is often carried out to increase the thermal conductivity of the polymer materials. In addition to experimental works, theoretical studies are important to obtain the values in a wide range of the condition and to understand the fillers' configuration inside the polymer matrix. In the present study, the theoretical studies were carried out mainly using Hamilton-Crosser model to investigate the aggregation and orientation behaviors of the fillers. We focused on the hexagonal boron nitride/polyimide composites. By adjusting the configuration parameter in the Hamilton-Crosser model, the relationship between the effective thermal conductivity and possible configuration of the boron nitride particles was obtained.

PO201 Magnetically controllable random laser action in dye-doped ferromagnetic nematic liquid crystals
Takuya NARUTA1, Takuya AKITA1, Yoshiaki UCHIDA1, Darja LISJAK2, Alenka MERTELJ2, Norikazu NISHIYAMA1
1 Osaka University, Osaka, Japan
2 Jožef Stefan Institute, Ljubljana, Slovenia

Random laser action, resulting from the multiple scattering of light, can be observed in dye-doped nematic liquid crystals (NLCs). The intensity of random laser emission can be controlled by electric, thermal and magnetic stimuli, however, the magnetic control needs very strong magnetic field because the magnetic anisotropy of LC molecule is low. Recently, ferromagnetic NLCs (FNLCs) was reported; ferromagnetic nanoplatelets (MNPs) dispersed in an NLC are oriented in the same direction as the nematic director, which can be reoriented by very weak magnetic field by virtue of the ferromagnetism. Here, we report magnetic-field-induced change of the random laser action in dye-doped FNLC (DDFNLC). Dye-doped NLCs (DDNLCs) were prepared by doping nematic liquid crystal, E7, with 0.3 wt% of Pyrromethene 597 as a laser dye. A suspension of 0.6 wt% MNPs in 1-buthanol was mixed with DDNLCs. The mixture was kept at 70 °C for 24h to evaporate 1-buthanol to give DDFNLCs with 0.1 wt% of MNPs. DDNLCs and DDFNLCs were injected into homeotropic alignment cells. The samples were optically pumped by pulsed laser at 532 nm and the emission spectra were measured at different magnetic field intensities. Without any magnetic fields, no random laser action occurred. Laser action started from about 10 mT and 140 mT of magnetic fields parallel to the cell surface for DDFNLCs and DDNLCs, respectively (Figure). The random laser is likely to emit perpendicularly to the nematic director; in fact, in a magnetic field parallel to the cell surface, the nematic director in a homeotropic in an alignment cell rotates to the direction parallel to the cell surface and the random laser emission is switched on. Moreover, we can conclude that the addition of MNPs lowers the threshold magnetic field of the random laser action to about one tenth.

PO202 Quantum chemical study on adsorption of hydrogen chloride with Zn-doped carbon materials
Hokkaido University, Sapporo, Japan

Studies on chloric behavior in high temperature processes (such as pulverized coal firing, waste burning and iron ore sintering) are important because volatile noxious compounds can be generated. For example, when heating coal to achieve burning and gasification, pyrolysis occurs first, volatile components are released and chlorine in coal is reported to be desorbed as HCl in this process. In addition, HCl is generated by the incineration of waste and then reacted to generate dioxins and chlorinated benzene. For blast furnace pig iron, some chlorine is captured into the solid-phase coke during the process of exhaust gas treatment at low temperatures. Our research group has previously studied the adsorption of HCl by Zn-doped O2-activated resins at 100 and 300 °C. It was clarified that a Zn-doped carbon compound adsorbs HCl much more than a carbon compound at 100 and 300 °C. However, the kind of reaction site and influence of metal on carbon active site have not been clarified with respect to the metal-doped carbon active site and the adsorption stability of HCl. Also, no research has focused on this point. In this study, electronic states of three carbon active site models (Armchair, Zigzag and Tip sites) before and after Zn doping were calculated by molecular orbital calculation (RHF/6-31G*). Calculation results of molecular orbital method for molecular models of carbon and Zn-doped carbon materials suggested that the presence of Zn may increase the number of chemisorbed sites for HCl molecules. In addition, it was estimated that ZnO does not contribute to the adsorption stability of HCl on the Zigzag sites. It has also been clarified that ZnO greatly affects the electronic state of the whole carbon material. In the future, this study makes it possible to propose a method to inhibit the generation of volatile hazardous compounds in high temperature processes.

PO203 Preparation of spherical liquid crystalline elastomers using a flow focusing device
Kosuke KANEKO1, Tsuyoshi GUSOKU1, Daiki FUJIOKA1, Kazuo KOJIMA1, Kiyomi FUCHIGAMI1,2, Tomonori HANASAKI1
1 Ritsumeikan University, Kusatsu, Japan
2 Shofu Inc., Kyoto, Japan

Liquid crystalline (LC) elastomers are very promising functional materials providing unique properties by coupling of "dynamic property of polymer networks" and "anisotropy of LC phases (such as orientation order of LC molecules)" [1-3], and thereby these materials are applicable to artificial muscles and soft actuators in the field of a variety of robotics. In this study, we demonstrate the spherical LC elastomers responsive to an electric field as micro size actuators. In addition, the creation of the spherical LC elastomers containing dual frequency LCs of which the dielectric anisotropy can be controlled by the frequency of AC field was newly investigated by using a flow focusing device (Figure 1). Then, the influence of the amounts of the LC molecules and the crosslinkers in the precursors on the deformation amounts of the elastomers was also discussed at the given frequencies of the applied AC fields.
The phase transition behavior of the elastomers was identified by polarized optical microscopy and differential scanning calorimetry. The results revealed that the elastomers exhibited a LC phase below 60 °C.
This work was financially supported by the Kyoto Technoscience Center and Murata Science Foundation.
1. T. Ikeda, J. Mamiya, Y. Yu, Angew. Chem. Int. Ed., 2007, 46, 506-528.
2. H. Yang, A. Buguin, J.-M. Taulemesse, K. Kaneko, S. Méry, A. Bergeret, P. Keller, J. Am. Chem. Soc., 2009, 131, 15000-15004.
3. K. Urayama, E. Kohmon, M. Kojima, T. Takigawa, Macromolecules, 2009, 42, 4084-4089.

PO204 Dynamic formation/deformation behavior of liquid crystals in aqueous solutions of amphiphiles having oxyethylene and mesogen units
Shota SUHARA1, Tsuyoshi NARUMI1, Hitomi OSHIYAMA1, Atsushi YOSHIZAWA1, Julian EASTOE2, Masanobu SAGISAKA1
1 Graduate School of Science and Technology, Hirosaki University
2 School of Chemistry, University of Bristol

Amphiphiles having different hydrophobic chains (such as fluorocarbons and hydrocarbon chains) often exhibit unusual interface properties and liquid crystal behavior. To generate a new drug release function of liquid crystals, this study synthesized amphiphiles having oxyethylene units and thermotropic liquid crystal mesogens (i.e. cyanobiphenyl and biphenyl groups) in the hydrophobic two chains (CB-B2ES and HB-B2ES, respectively) and a CB-B2ES analogue without oxyethylene units (CB-DeS). Then lyotropic liquid crystal behavior of the amphiphiles in water was investigated as functions of temperature and elapsed time. Figure 1 shows chemical structures of amphiphiles and polarized micrographs for 30 wt% amphiphile / water mixtures at 30 °C at different elapsed times after preparation. Mixtures containing CB-DeS, CB-B2ES and HB-B2ES displayed maltese cross textures, suggesting formation of a lamellar liquid crystal. Lamellar liquid crystals in the CB-DeS / water mixture were stable and showed no morphology change without applying external forces or change in experimental condition. However, in CB-B2ES and HB-B2ES / water mixtures, lamellar aggregates displayed dynamic formation/breakdown behavior with elapsing time at a constant temperature. Namely, after preparation of fresh mixtures, population of maltese cross textures gradually increased but suddenly all the textures disappeared in a few min. The time to start the maltese texture breakdown for CB-B2ES was ~30 min at 30 °C, longer than that for HB-B2ES. It probably results from the higher stability of CB-B2ES lamellar LCs by additional electrostatic interaction between cyanobiphenyl groups. In addition, there were no change in 1H-NMR spectra before and after the texture breakdown. It suggested that the texture breakdown was not caused by decomposition of the surfactants. The dynamic liquid crystal behavior of the texture breakdown was expected to happen by phase transition from lamellar to another isotropic phase with elapsing time.

PO205 Observation of memory effect in TBAB supercooled aqueous solution
Hironobu MACHIDA1, Takeshi SUGAHARA2, Izumi HIRASAWA3
1 Panasonic Corporation, Osaka, Japan
2 Osaka University, Osaka, Japan
3 Waseda University, Tokyo, Japan

Clathrate hydrate of tetra-n-butylammonium bromide (TBAB) is expected as a cold storage material for air conditioning, but supercooling is a problem for practical use. The supercooling, widely known, is the state of maintaining the liquid phase even if it is cooled below freezing point, but the detailed mechanism is not clarified. For the purpose of visualization of the supercooling phenomenon, both the structures of TBAB clathrate hydrate and TBAB aqueous solution were observed. In general, although scanning electron microscope (SEM) is widely used in the observation of micro- or nano-size objects, it had not been possible to observe such as a solution or a gel directly since the inside of the SEM is under a high vacuum. Therefore, SEM observation was performed by a freeze fracture replica method. Freeze fracture replica method is utilized not only in medicine and biology fields but also in various fields since it is possible to obtain both of the information of a solution itself and the state of particles having a microstructure simultaneously. Specifically, cut-surface of the quenched sample was prepared and thin film is fabricated on the cut-surface. And by soaking it in an appropriate solvent, the thin film and the sample were separated to recover a replica film reflecting the morphology of quenched cut-surface. Finally, the replica film was observed by SEM.
In this study, we tried to observe the solution structure in the process of crystallization and melting of TBAB supercooled aqueous solution. Further, in actual use of a cold storage material, a hysteresis phenomenon (called a memory effect) accompanying a thermal history often becomes a problem. The memory effect was also investigated in relation to the solution structure by another analysis methods other than the freeze fracture replica method. The characteristics of the memory effect were clarified according to various analysis methods. We are going to discuss the results.

PO206 Phase equilibria of methane hydrate containing organic inhibitors and ammonium chloride
Ki Hun PARK, Dawoon JUNG, Minjun CHA
Kangwon National University, Korea

Here, we investigated the phase equilibria of the methane hydrate containing organic inhibitors (methanol; MeOH and ethylene glycol; MEG) and ammonuium chloride (NH4Cl). Conventional isochoric trace method to identify the equilibrium temperatures and pressures for methane hydrates with mixed inhibitor system was used, and two groups of mixed inhibitor solutions: (1) 5 wt% NH4Cl + 10 wt% MEG, 5 wt% NH4Cl + 20 wt% MEG, 10 wt% NH4Cl + 10 wt% MEG, 10 wt% NH4Cl + 20 wt% MEG aqueous solutions, and (2) 5 wt% NH4Cl + 10 wt% MeOH, 5 wt% NH4Cl + 20 wt% MeOH, 10 wt% NH4Cl + 10 wt% MeOH, and 10 wt% NH4Cl + 20 wt% MeOH aqueous solutions, were prepared. The phase equilibrium conditions of methane hydrates containing MEG/MeOH and NH4Cl solutions are located at lower temperature and higher pressure conditions than those of pure methane hydrate. In addition, as the concentration of MEG/MeOH and NH4Cl increase, the hydrate equilibrium conditions of methane hydrates are further shifted into left regions (lower temperature and higher pressure conditions). The hydrate inhibition performance of our mixed inhibitor system is in the following order; (10 wt% NH4Cl + 20 wt% MeOH/MEG) > (5 wt% NH4Cl + 20 wt% MeOH/MEG) > (10 wt% NH4Cl + 10 wt% MeOH/MEG) > (5 wt% NH4Cl + 10 wt% MeOH/MEG). After all, we calculated the dissociation enthalpies of methane hydrates containing mixed inhibitor solutions using the Clausius-Clapeyron equation, which fits well with the experimental data.
KEYWORDS : methane hydrate, phase equilibria, thermodynamic hydrate inhibitor, ammonium chloride

PO207 Dissociation behavior of methane hydrates by hydrate inhibitors
Ryosuke EZURE1,2, Hideo TAJIMA1, Yoshitaka YAMAMOTO2, Sanehiro MUROMACHI2
1 Graduate School of Science and Technology, Niigata University
2 Research Institute of Energy Frontier (RIEF), National Institute of Advanced Industrial Science and Technology (AIST)

Methane hydrates vastly deposit in deep sea around Japan, and expected as one of unconventional natural gas resources. The depressurization method is being developed for methane gas production from subsea methane hydrates. Methane hydrates are only stable at high pressure and low temperature conditions. In the depressurization method, a pipe equipped with depressurization pump is inserted into the subsea methane hydrate layer. When the methane hydrate layer is depressurized by the pump, the methane hydrates dissociate to gas and water. When the well pressure returned to be seawater head pressure by an accident or during operation stop, the methane hydrates may reform and plug the flow channel in the well. As a solution to dissociate the hydrate blockage, injection of a thermodynamic hydrate inhibitor (THI) into the well is effective, because the THI can melt the methane hydrates by shifting equilibrium curve toward lower temperature, in other words, freezing point depression. In this study, as a part of a Japanese National hydrate research program (MH21, funded by METI), we demonstrate methane hydrate dissociation by injection of urea which is expected for environmentally-friendly THI. In combination with urea, we used kinetic hydrate inhibitors (KHIs) or promoters such as polyvinylpyrrolidone (PVP) and sodium dodecyl sulfate (SDS). The experiments were carried out in the rocking cell equipped with three glass windows. The cell was rocked to facilitate mixing of the fluids and solids inside the cell. Methane hydrates were first formed at 13 MPa and 278 K in the cell. A THI solution was stepwise injected into the cell to dissociate the hydrates. The dissociation behavior was recorded by a CCD camera. We tested a couple of different solutions of THI and the kinetic inhibitors/promoters. The present results suggest that there is a synergetic effect on the hydrate dissociation by combinations of urea and inhibitors/promoters.

PO208 Relationship between TBAB Hydrate Crystal Morphology and Slurry Flow Characteristics
Nobuyuki SAKAMOTO, Hiroyuki KOMATSU*, Hideo TAJIMA, Kazuaki YAMAGIWA
Graduate School of Science and Technology, Niigata University, Niigata 950-2181 JAPAN

Separation and recovery technologies for carbon dioxide (CO2) are needed to address global warming. Semi-clathrate hydrates (SCH) with tetra-n-butyl ammonium bromide (TBAB) are attractive as CO2 separation media, because they can be simply regenerated and reused. Although SCH as slurries can possibly be applied to continuous separation processes, the reasons for their rheological properties being Bingham fluid or pseudo-plastic fluids are unknown and are important for their practical application. In this work, the objective was to investigate the relationship between the SCH crystal morphology and flow characteristics of SCH hydrate slurries so that the fundamental basis for their rheological properties can be understood. The shape of SCH crystals in the slurries was changed by time maintained super-cooling after crystal formation, defined as the overcooling time. Initial TBAB concentration was 10.4 wt% in the TBAB aqueous solution before the hydrate slurry formation and experimental temperature was 278.5 K. The solid fraction (v/v) in the slurry was 0.12. The viscosities of the SCH slurries were measured with a rotational viscometer and results were analyzed with Herschel-Bulkley's model. Least-squares and mathematical optimization were used to determine viscosity index, fluid consistency coefficient and yield shear stress. Size and shape of SCH crystals were characterized with microscopy and particles were found to be needle-like and granular without overcooling time, and were only granular with an overcooling time of 30 min. The fluid behavior of the SCH slurry was only Bingham fluid with an overcooling time of 30 min. Therefore, the shape of the SCH crystals in the slurry was found to influence the rheological behavior of the slurries and their flow characteristics.

PO209 Relationship between CO2 Absorption Behavior and Formation of Semi-clathrate Hydrate during Gas Contact
Hideki OKOSHI, Hiroyuki KOMATSU*, Hideo TAJIMA, Kazuaki YAMAGIWA
Graduate School of Science and Technology, Niigata University, Niigata 950-2181, JAPAN

Biogas is a resource that has been proposed to provide carbon neutral energy and reduce CO2 emissions. However, biogas typically contains numerous impurities such as carbon dioxide, water and hydrogen sulfide, and these impurities must be removed before processing the mixtures with present technologies. Semi-clathrate hydrates (SCH) are attractive as gas separation media in biogas systems, because they are unaffected the presence of most impurities, however, there are issues related to their theoretical loading (adsorption amount). For tetra-n-butyl ammonium bromide (TBAB) semi-clathrate hydrates, it has been reported that CO2 absorption amount was much lower than theoretical values at TBAB concentrations above 1.5 mol%. The hypothesis explored in this work is that CO2 is not sufficiently absorbed in SCH slurries due to SCH crystal aggregation. The objective of this work was to investigate how to increase CO2 absorption amount in TBAB SCH slurries through experiments with a bubble column reactor. SCH slurries were loaded in the column, and gas mixtures were flowed through a filter from the bottom of the column. Loaded TBAB concentration was 0.55 mol%, experimental temperature was 278.2 K and experimental pressure was 0.8 MPa. Gas mixtures of He and CO2 were used in which initial CO2 composition was 0.20. The CO2 absorption amount was 1.86 mmol-CO2/mol-H2O. Occupancy of CO2 in SCH estimated from this result was 0.04. However, theoretical CO2 occupancy with a thermodynamic model was estimated to be 0.13, which indicates that the CO2 was not sufficiently absorbed by the SCH. The amount of hydrate in the slurry increased gradually as CO2 was absorbed into the slurry and CO2 tended to be enclathrated mainly in the inner cages of initial SCH particles. Thus, SCH formation in the initial stages of gas absorption is important for increasing the amount of gas absorbed into the slurry.

PO210 Observation of tuning behavior on Trimethylene Oxide + CH4 hydrate via thermodynamic and spectroscopic analyses
Dongju SEO, Seokyoon MOON, Youngjune PARK*
School of Earth Sciences and Environmental Engineering, Gwangju Institute of Science and Technology (GIST), 123 Cheomdangwagi-ro, Buk-gu, Gwangju 61005, Republic of Korea

Natural gas is a growing energy source due to the less emission of carbon dioxide than other fossil fuels such as coal and oil. Various materials and methods have been investigated so far for effective separation, transportation, and storage. Among the options, gas hydrate has recently been received great attention due to its theoretically promising storage capacity and separation function. To evaluate the potential of gas hydrate as natural gas storage media, however, the fundamental thermodynamic properties should be fully investigated, particularly elucidating its distinct characteristics of cage occupation behavior of natural gas molecules. In this study, we investigated the binary gas hydrate containing trimethylene oxide (TMO) and CH4 molecules focusing on the distinct host-guest interactions between water cages (host) and guests (TMO and CH4). Pressure-temperature phase equilibria were measured. In addition spectroscopies such as synchrotron High Resolution Powder Diffraction (HRPD), Dispersive Raman, and 13C solid-state Nuclear Magnetic Resonance (NMR) were employed. The results indicated that the thermodynamic stability of TMO + CH4 hydrate was higher than that of pure CH4 hydrate. Particularly, structure II type gas hydrate was mainly formed at the concentrations of TMO below 5.56 mol%. When the ratio of water to TMO was 17: 1, abnormal tuning phenomenon was also observed. The cage occupancy of CH4 molecules in TMO + CH4 hydrate was significantly enhanced.

PO211 First-principles studies on structure and hydrogen release properties of light perovskite-type hydrides
Yuanyuan LI, Sung Gu KANG, Jin Suk CHUNG
University of Ulsan

Light perovskite-type hydrides show great potential for hydrogen storage. Using density functional theory (DFT) modeling, all possible perovskite-type hydrides ABH3 (alkali metals A = Li, Na, K, Rb, or Cs, alkaline metals B = Be, Mg, Ca, Sr, or Ba) have been investigated to explore the structural stability and hydrogen release properties. The formation enthalpies and reaction enthalpies for hydrogen release were calculated based on the optimized experimental and hypothetical structures. The most favorable dehydrogenation pathways were obtained for all ABH3 systems studied. In addition, NaCaH3 was screened to be as one of the most promising material to store hydrogen among these perovskite-type hydrides. To facilitate the hydrogen release of NaCaH3, the dopants including alkali metals (Li, K, Rb, or Cs) and alkaline metals (Be, Mg, Sr, or Ba) were introduced to replace the Na and Ca sites in NaCaH3 structure, respectively. The reaction enthalpies of doped-systems were calculated by different dehydrogenation pathways. Among all dopants examined, the Cs was the most beneficial dopant for the dehydrogenation of NaCaH3 with the lowest energy required. However, there is no useful on hydrogen release using alkaline dopants in NaCaH3 system. Overall, for future experiment and theoretical work, these studies can provide valuable model to design new promising perovskite-type hydrides for hydrogen storage.

PO212 Study on measurement method of ultrafine bubble using ultrasound
Naoya YAMAWAKI1, Hayato OKUMURA2, Shigenori AKAMATSU2, Yusuke NISHIUCHI2, Takashi HATA2
1 Advanced Course of Material Engineering, National Institute of Technology (Kosen), Kochi College, Nankoku, Kochi, Japan
2 Department of Social Design Engineering, National Institute of Technology (Kosen), Kochi College, Nankoku, Kochi, Japan

In this study, investigated the evaluation of ultrafine bubble (UFB) with diameters of 1 μm or less, which are important among fine bubble (micro / nano bubble) studies, using hydroxy (OH) radicals and sonoluminescence generated by the collapse of UFB when ultrasonic waves are applied to UFB. First, electron spin resonance (ESR) and potassium iodide (KI) techniques were used for the evaluation of OH radicals. From the measurement results of ESR, it was confirmed that OH radicals were generated by the collapse of UFB. Also, since the KI method stabilizes iodine dissociated from KI as I3- with an absorption wavelength of 355 nm when OH radicals are present, the generated OH radicals can be evaluated by measuring the absorbance of this I3- with a spectrophotometer. However, when air is used as an internal capsule gas, the observation of OH radicals generated by the collapse of UFB has been difficult to evaluate by the KI method because the difference in absorbance is very small. Therefore, distinct absorbance differences could be confirmed by increasing the amount of OH radicals generated by the collapse of UFB by using ozone as the inclusion gas. Furthermore, it was confirmed that the higher the frequency of ultrasound, the greater the difference in absorbance (Fig). On the other hand, sonoluminescence measurements confirmed the luminescence phenomenon with respect to UFB collapse by ultrasound, and further confirmed that the luminescence intensity of water with the addition of the same number of inorganic particles as UFB was smaller than that of UFB water. Since differences in experimental results were confirmed by the presence or absence of UFB in these multiple experiments, evaluation of UFB using OH radical as an index using ultrasound can be expected.

PO213 Development of a novel molecular dynamics method for modeling of friction behavior between solid surfaces
Takuya HIRAMOTO, Hiromitsu TAKABA
Kogakuin University, Tokyo, Japan

Friction is fundamental phenomena in various mechanical process. Therefore, better understanding of friction behavior from atomistic scale is significantly important. Conventionally, a flat metal surface has been used in the molecular dynamics for investigation of friction behavior. However, in the realistic system, a irregular morphology of the surface plays an important role for friction dynamics. Such surface modeler requires a lot of computational power in the molecular modeling, which becomes issue for application of molecular dynamics. In this paper, a novel molecular dynamics method will be presented for the modeling of friction behavior with less computational time.

PO214 Wettabilities of different faces of quartz
Yajun DENG, Qianhong WU, Hailong LU
Peking University, Beijing, China

Quartz is an important crystalline solid and its wettability plays an essential role in affecting various production processes. However, less attention has been paid to the crystal face related wetting behavior. In the present work, with the contact angle goniometer and the atomic force microscopy (AFM), the wettabilities of different faces of quartz were studied by measuring the contact angles between several solid-liquid pairs at both macroscopic and microscopic scale. The solid substrates investigated include (001), (100) and (110) faces of quartz, and the test liquids are water, glycerol and phosphoric acid (85 wt%). The results obtained show that the solid-liquid contact angles, which were measured by optical goniometer and AFM, are nearly identical, indicating that both methods are reliable, although the optical goniometer measured the contact angle at macroscale and the AFM yielded results at nanoscale. For the three faces of quartz tested, the contact angles become greater in the order of (001), (110) and (100), although the change in contact angle of phosphoric acid is more obvious than those of water and glycerol. In order to explain the effect of the crystal faces on the contact angles, the molecular dynamic simulations were conducted to investigate the wetting characteristics of water droplets on (001), (100) and (110) faces of quartz. The simulation results demonstrate that the surface densities of unsaturated silicon atoms and the first-layer water molecules on the crystal faces are all in accordance with the order of (001) > (110) > (100), which is in the exact opposite order of the contact angles that were obtained in the experiments. Therefore, it can be inferred that the differences in the surface atomic arrangements and the surface density of unsaturated silicon atoms are the intrinsic causes of the wettability differences between quartz faces.

PO215 Structural properties of Platonic Micelle constructed by calix[4]arene-based lipids
Tadashi OKOBIRA1, Efstratios MYLONAS2, Naoto YAGI3, Shota FUJII4, Kazuo SAKURAI4
1 National Institute of Technology, Ariake College, Omuta, Japan
2 Institute of Molecular Biology and Biotechnology, Crete, Greece
3 Japan Synchrotron Radiation Research Institute (JASRI/SPring-8), Sayo-gun, Japan
4 The University of Kitakyushu, Kitakyushu, Japan

Supramolecules such as micelles are used as various functional materials. These functionality is dependent on the amount and/or type involved in the interaction of supermolecules, it is mainly expressed in the aqueous solution. Therefore, we have to understand the 3D structure of supramolecule in aqueous solution, and their information play important role to create a novel functional material. In our recent study, we reported about the analysis of calix[4]arene-based micelle by using various experimental methods. Calix[4]arene-based surfactants showed that they are monodisperse with a defined aggregation number whose values are chosen from the face number of Platonic solids. We named it “Platonic Micelle”. Small-angle X-ray scattering (SAXS) provides nanoscale information about size and shape for disperse particle. However, it is difficult to understand a detail of the 3D configuration of the aggregate of the molecule forming the Platonic Micelle with only SAXS. Then, we considered that the 3D configuration of Platonic Micelle is able to understand by combination of the computational chemistry method and SAXS. The Platonic Micelle consisting calix[4]arene-based surfactant having four alkyl tails and four head groups were examined by SAXS and computational chemistry methods mainly using molecular dynamics (MD) simulation, molecular orbital method and CRYSOL program. CRYSOL program is able to provide a theoretical value about scattering. On the hands, a dynamics of Platonic Micelle can be analyzed with MD simulation. 3D configuration of Platonic Micelle was estimated by comparison between SAXS result and theoretical curve calculated in CRYSOL program by using 3D coordinates obtained in the process of MD simulation.

PO216 Transport properties of imidazolium-based ionic liquid+2-propanol mixtures
Takuya SHIMOMURA1, Yuki KOHNO2, Mitsuhiro KANAKUBO2
1 Graduate School of Engineering, Muroran Institute of Technology, Muroran, Hokkaido 050-8585, Japan
2 Research Institute for Chemical Process Technology, National Institute of Advanced Industrial Science and Technology, Sendai 983-8551, Japan

Several investigations have been reported on the phase behavior of ionic liquid (IL)+alcohol mixtures. For example, a 1-ethyl-3-methylimidazolum bis(trifluoromethanesulfonyl)amide ([C2mim][TFSA])+2-propanol mixture shows upper critical solution behavior. The critical temperature and critical mole fraction (xIL) of IL for the [C2mim][TFSA]+2-propanol mixture are 292.2 K and xIL = 0.149, respectively. However, the transport properties of IL+2-propanol mixtures, such as viscosity, electrical conductivity, and self-diffusion coefficient, have not been investigated systematically.
In the present study, the self-diffusion coefficients of [C2mim]+ (D+), [TFSA]- (D-), and 2-propanol (D2-pro) for the [C2mim][TFSA]+2-propanol mixtures were measured using PFGSE NMR spectroscopy together with the density, viscosity, and electrical conductivity. In Fig. 1, D+/D-, D2-pro/D-, and D2-pro/D+ ratios for [C2mim][TFSA]+2-propanol mixtures at various temperature are plotted as a function of xIL. The D+/D- and D2-pro/D- ratios decrease with decreasing xIL, where the decrease in D2-pro/D- is more remarkable than D+/D-. On the other hand, the D2-pro/D+ ratio does not considerably change. Then, the increase in D- with decreasing xIL is significant compared with D+ and D2-pro. This is probably because [C2mim]+ interacts with 2-propanol more strongly than [TFSA]- in the mixtures. We will give the detailed discussion about intermolecular interactions in the [C2mim][TFSA]+2-propanol mixtures based on the results of the density, viscosity, and electrical conductivity measurements in the presentation.

PO217 Transport Property Analysis of Ionic Liquids and Their Mixtures by using MD simulation with Advanced Non-Polarizable Force Field
Yoshiki ISHII, Nobuyuki MATUBAYASI
Osaka University, Toyonaka, Osaka 560-8531, Japan

In order to investigate the transport property of ionic liquids, we performed molecular dynamics (MD) simulation by using the non-polarizable force field developed with first-principles DFT calculations. The DFT calculations were implemented with the QUICKSTEP of CP2K[1]. The PBE-type generalized gradient approximation was employed for the exchange-correlation functional. Further information for the optimization scheme will be presented in the oral presentation. The cation is 1-alkyl-3-methyl-imidazolium, N-metyl-N-proylpyrrolidinium, and N-butyl-N,N,N-trimetylammonium. The counter anions are chloride, tetrafluoroborate, bis(fluorosulfonyl)amide, and bis(trifluorosulfonyl)amide. All the MD simulation were implemented by using Gromacs package[2]. Self-diffusion coefficients was evaluated with the Einstein equation and the modification of periodic boundary condition. Viscosity and electrical conductivity were evaluated with the Green-Kubo formulae. The calculated transport coefficients are in good agreements with the corresponding experimental data. Even for several systems based on the same cation or anion, since the molecular charges were updated via first-principles calculation at each thermodynamic states, the effective charges and van der Waals parameters were assigned for the MD simulation. Thereby, the MD simulation in the framework of the present molecular force field is useful to predict transport properties of various ionic liquids. In this poseter presentation, the calculated structural and transport properties will be discussed over the various compositions of ionic liquids including the ternary mixtures.
[1] CP2K, version 4.1, The CP2K Foundation, Zürich, 2014.
[2] Gromacs, version 2016.5, The GROMACS development teams, Sweden 2017.

PO218 Molar enthalpy of CO2 solution and solubility of CO2 in diglyme and [Li-diglyme][TFSA]
Daisuke KODAMA1, Yuta KOMATSU1, Toshiya SUGAWARA1, Takashi MAKINO2, Mitsuhiro KANAKUBO2
1 Department of Chemical Biology and Applied Chemistry, College of Engineering, Nihon University, 1 Nakagawara, Tokusada, Tamura-machi, Koriyama, Fukushima 963-8642 JAPAN
2 Compact System Engineering Group, Research Institute for Chemical Process Technology, National Institute of Advanced Industrial Science and Technology (AIST), 4-2-1 Nigatake, Miyagino-ku, Sendai, Miyagi 983-8551 JAPAN

Ionic liquids (ILs) generally have negligibly small vapor pressure and high thermal and chemical stability. They show higher solubilities of acidic gases such as CO2, H2S, NOx and SOx than neutral gases like N2, H2, and O2. The mixtures of diglyme (i.e. diethylene glycol dimethyl ether) and lithium salts show unique the physico-chemical behavior resembling ILs [1], therefore, they are called as “solvate ionic liquids (SILs)”. Since Aki et al. [2] reported that [TFSA]- is the best anion in the imidazolium salts for CO2 absorption, [Li-diglyme][TFSA] was expected to have the excellent CO2 absorption capacity. The CO2 solubility and calorimetric data are required for the development of the CO2 separation process using SILs.
In the present study, we have investigated the enthalpies of CO2 solution in diglyme and [Li-diglyme][TFSA] (LiTFSA: 10 wt%) at 313.2 K and up to 7.0 MPa using a flow calorimetric technique. The experimental values of the enthalpies were consistent with the calculated ones based on the Henry's constants [3]. Furthermore, the CO2 solubilities were derived from the experimental calorimetric data for diglyme and [Li-diglyme][TFSA]. The CO2 solubilities determined by the present calorimetric approach agreed fairly well with the synthetic approach [4].
[1] K. Ueno et al., J. Phys. Chem. B, 116, 11323-11331 (2012)
[2] S.N.V.K. Aki et al., J. Phys. Chem. B, 108, 20355-20365 (2004)
[3] D. Almantariotis et al., Int. J. Greenh. Gas Con., 10, 329-340 (2012)
[4] D. Kodama et al., Fluid Phase Equilib., 302, 103-108 (2011)

PO219 A study of solubility and diffusivity of CO2 in poly(methylmethacrylate(MMA)-co-ethylacrylate(EA)) to design controlled release material
Yoshiki OBONAI1, Yoshiyuki SATO1,2, Hiroshi INOMATA1
1 Tohoku University, Sendai, Japan
2 Tohoku Institute of Technology, Sendai, Japan

Polymers have been widely used for controlled release materials in various fields such as fragrances and medicines. In this work, we have focused on copolymers as controlled release carriers with respect to their controllability of solubility and diffusivity of released solutes by changing copolymer composition as well as by tuning operation conditions. Regarding a solute, CO2 was selected by considering its potential antioxidant effect. We have conducted measurement and correlation the solubility and diffusivity of CO2 in poly (methyl methacrylate (PMMA)) and poly (methyl methacrylate (MMA) / ethyl acrylate (EA)) copolymer. This copolymer shows glass transition temperature, Tg, at 70–130 °C depending on EA content. In addition, Tg is reduced to near room temperature by CO2 dissolution, of which feature is very useful for controlled release design since solubility and diffusivity change drastically around glass transition. The measurement conditions were the temperatures of 10, 25 and 40 °C close to supposed practical conditions of the controlled release material. The measurement results of the CO2 solubility in PMMA increased with increasing pressure, and decreased with increasing temperature. These results indicated that the dissolution of CO2 in this copolymer could be governed by the condensability of CO2. In addition, it would be noted that the CO2 solubility data were correlated fairly well with the Dual-Mode-Sorption [1] in conjunction with the SL-EOS [2, 3].
Now measurements of Tg of this copolymer under high pressure CO2 are on-going with aiming the improvement of solubility/diffusivity correlation near glass transition by introducing Tg value to the correlation model.
[1] N. H. Wang, et al., Kagaku Kougaku Ronbunshu, 2, 226 (1996).
[2] I. C. Sanchez and R. H. Lacombe, J. Phys. Chem., 80, 2352 (1976).
[3] I. C. Sanchez and R. H. Lacombe, Macromolecules, 11, 1145 (1978).

PO220 (canceled) <101307-1>
PO221 Estimation of the Density of CO2/Toluene system using Three Equations of State
Hiroaki MATSUKAWA, Masakazu NAYA, Atsushi SHONO, Katsuto OTAKE
Tokyo University of Science, Tokyo, Japan

Recently, attention has been focused on a mixed fluid in which carbon dioxide (CO2) is dissolved in an organic solvent, a so-called CO2 expansion liquid. Since this mixed fluid can widely change the solvent characteristics only by pressure operation, its application as extraction of natural products and generation of fine particles has been studied. The equilibrium and/or transport properties such as density, dielectric constant, and viscosity of the mixture change greatly depending on the composition of CO2. So, for industrial process design, it is important to grasp the physical properties of the CO2 and organic solvent mixture. However, the measured data is insufficient at present because physical property measurements under high pressures need a special device and a long time. Therefore, the estimation of physical properties is greatly needed. In this study, the density of uniform fluid mixture under high pressure was focused on, which is the property greatly affected by composition. The density of CO2 and toluene uniform fluid mixture was measured, and the applicability of the three mainstream equations of state to density estimation was evaluated. The density of CO2 and toluene uniform fluid mixture was measured with a high pressure vibration type density meter equipped with a circulation pump and a variable volume viewing cell. The calibration of the density meter was conducted with water and cyclohexane. The measurement was conducted at temperatures from 313.2 K to 353.2 K and pressures up to 20 MPa. CO2 compositions were changed from 0 (pure toluene) to 80 mol%. In density estimation, the Peng-Robinson equation of state as a representative of the van der Waals types, the Sanchez-Lacombe equation of state as a representative of the lattice fluid theory types, and the PC SAFT equation of state as a representative of the statistical associating fluid theory types were used.

PO222 Supercritical carbon dioxide extraction of vitamin K2 from freeze-dried natto
Tasuku MURATA1, Tetsuo HONMA1, Hiroyuki SUMI2, Kazuhide ARAKI3
1 National Institute of Technology (Kosen), Hachinohe college, Hachinohe, Japan
2 Kurashiki University of Science and the Arts, Kurashiki, Japan
3 Aoimori Kobo Co., Ltd., Tokyo, Japan

Vitamin K is essential for osteogenesis, and vitamin K deficiency causes osteoporosis leading to hip fracture and coronary disease. Menaquinone-7 (MK-7), one of vitamin K subtypes, is abundantly contained in Japanese traditional fermented food natto. Supercritical carbon dioxide extraction of freeze-dried natto was investigated at 293 K and 313 K at 100 atm, by means of semi-batch flow-type equipments. The extraction rate of the oil from freeze-dried natto was defined as a ratio of the extraction yield to a traditional hexane extraction yield. To improve an oil recovery during the extraction, the collection trap was cooled with brine bath. The extraction yield at lower temperature condition was improved due to an increase of oil solubility. The maximum yield of extracted oil was 158.4% at 293 K and 10 MPa. The qualitative analysis for the extracted oil by UPLC/Q-Tof was performed to identify elemental composition of valuable compounds. The elemental composition analysis was revealed that that the menaquinone-1, 2, 3, isoflavone, and linoleic acid were identified by comparing monoisotopic masses between theoretical and measured values. The time profile of the extraction rate was indicated that the amount of extraction oil increased with the cosumption of carbon dioxide. The time profiles of extraction rate were fitted by simple mathematical model. The time constants of the mathematical model were 0.15 at 293 K and 0.12 at 313 K. The time profile of the mathematical model is comparable with that of supercritical carbon dioxide extraction. The maximum extraction rate would be 180% at 293 K with 23 g/g of carbon dioxide.

PO223 Measurement and prediction of diffusion coefficients of phenol in mixture of carbon dioxide and methanol under high pressure condition by Taylor dispersion method
Norihiro ONODERA1, Junichi SAKABE1, Toshitaka FUNAZUKURI1, Chung Yi KONG2
1 Chuo University, Kasuga 1-13-27, Bunkyo-ku, Tokyo 112-8551, Japan
2 Shizuoka University, 3-5-1 Johoku Naka-ku, Hamamatsu 432-8561, Japan

A mixture fluid of CO2 and an organic solvent is expected as a new reaction solvent [1] because its properties can be varied by changing pressure, temperature and/or composition. To use the mixture fluid for industry, fundamental property data in wide pressure and entire composition range are needed. However, reports on diffusion coefficients D1m in mixtures of CO2 and organic solvent are limited [1]. Furthermore, high accurate prediction models for D1m in mixture fluids are not well established. In this research, D1m's of phenol in a mixture fluid of CO2 and methanol under high pressure conditions were measured by the Taylor dispersion method. Moreover, the D1m data measured experimentally were compared to D1m values calculated by the Blanc's equation [1]. Each fluid (CO2 and methanol) was separately supplied by each syringe pump at a constant flow rate to the diffusion column. A methanol solution of phenol was loaded via the injector to the diffusion column. A response signal was obtained at the exit of the diffusion column with a UV-Vis photodiode-array detector. The D1m and velocity u were simultaneously determined such that fitting error, ε, defined by eq. (3), was minimized by changing D1m and u values. D1m decreased with increasing methanol molar fraction because fluid viscosity increased as methanol molar fraction increased. D1m's were predicted by the Blanc's equation defined by eq. (4). The prediction performance for all the data points was lower than 11% in relative deviation Herein, m is the amount injected, R and L are the radius and length of diffusion column, respectively, t is the time, and exp and cal designate experimental and calculation, respectively. x is the molar fraction, and D1A is the binary diffusion coefficient for phenol in A solvent.
[1] T. Funazukuri et al., Fluid Phase Equilib., 164, 117 (1999).

PO224 Cocrystal Formation of Norfloxacin with CO2 under High Pressure
Yingquan HAO, Yusuke SHIMOYAMA
Tokyo Institute of Technology, Tokyo, Japan

We mainly focus on the cocrystal formation of poorly soluble drug with CO2, targeting on the enhancement of drug solubility and improvement of drug dissolve behavior. In this work, norfloxacin was used as target drug, which have a very limited solubility about 0.28mg/g water at 25 °C. To form the cocrystal of Norfloxacin with CO2, we treat put Norfloxacin anhydrate in hyper-pressure cell in a temperature-controlled (30 to 60 °C) thermostatic oven and pressurize the CO2 into the cell until determined pressure (5 to 25MPa) is reached. Then the pressure and temperature are controlled as a constant for 2h. After this, the hyper-pressure cell is depressurized at 0.1MPa/min. And the solid (mixture of Norfloxacin and Norfloxacin CO2 cocrystal) remained in hyper-pressure is collected, we call it Norfloxacin Sc-CO2. After the experiment, the Norfloxacin Sc-CO2 is characterized mainly by powder XRD for semi-quantification of new formed cocrystal, and solubility test to check the dissolve behavior change. As results, we find out the higher pressure and higher temperature are preferred for cocrystal formation. Moreover, as can be seen in Figure, more cocrystal is formed, higher solubility of Norfloxacin we can get. In this research, the highest solubility is achieved at 25MPa, 40 °C, 0.64mg/g water at 25 °C, about 2 times higher than raw Norfloxacin. We also use the FT-IR to characterize the chemical change before and after Sc-CO2 treatment, and find two new peaks at 1650 cm-1 which may indicate the C=O vibration of CO2, and 990cm-1 which is still unknown. And TGA test give a mass loss around 189 °C corresponding with new heat absorbance in DSC test, which suggest the release of CO2 from the cocrystal.

PO225 Solubility Representation of Dyestuffs in Supercritical CO2 by Neural Network
Kazuhiro TAMURA
School of Natural System, College of Science and Technology, Kanazawa University, Kanazawa, Japan

Supercritical carbon dioxide (scCO2) is considered as a green and environmental friendly solvent. scCO2 has been widely used for dyeing for textile and polymer processing. In the design and development of scCO2 process, solubility is one of the important and fundamental property. So far there are many calculation models developed for fitting and prediction of the solubility of dyestuffs. For example, Chrastil, Mendez-Santiago – Teja, Bartle et al., Kumar – Johnston, Garlpati – Madra, Sung – Shim, Adachi – Lu, and Ch – Madras proposed scCO2 density-based models to correlate the solubilities of solid compounds. Also the equations of state like Peng – Robinson and Soave – Redlich – Kwong were used to fit and predict solubility of solid compounds in scCO2. Recently the solubility calculation was performed by the equation of state combined with gE model. In these calculations of fitting and prediction of the solubility, we encountered some inconveniences in an accurate representation of the models to the whole range of the experimental results and in dependence of the functional flexibility for the model used. To overcome these shortcomings, the neural network was applied to represent the solubility. In the present work, we examined to correlate and predict accurately the solubility of anthraquinone and the derivatives in scCO2 by the neural network.

PO226 Measurments of viscosity, density, and bubble-point pressure of CO2 + methanol system
Chisato YONEYAMA1, Yoshiyuki SATO1,2, Hiroshi INOMATA1
1 Tohoku University, Sendai, Japan
2 Tohoku Institute of Technology, Sendai, Japan

Recently, VOC (Volatile Organic Compounds) emission to environment has become a serious problem. In particular, the paint industry is the largest VOC emission source in Japan, because large amounts of VOC are used as diluents in paint. As a new alternative technology, a CO2 painting system [1], which replaces a part of solvent (diluent) with high pressure CO2, has attracted an attention, because it can reduce VOC emission and drying cost. The fluidity of paint is important in the painting process, however viscosity data of CO2 + organic solvent + polymer system are rarely reported. In this work, viscosity, density, and bubble-point pressure of CO2 + methanol system were measured at 40 and 80 °C. To ensure the measurements at one phase, our pressure conditions were set at 0.2 MPa higher than the saturation. Figure shows experimental viscosity data of CO2 + methanol system at 40 °C. Viscosity tends to decrease with increasing CO2 composition and increase with increasing pressures. Estimated saturated viscosity data of this work were smaller than that of Sih et al. [2], and the deviation were 4.5 ~ 8.9 %. However, viscosity data at 0.1 MPa in pure methanol which were obtained by extrapolation from experimental data were in good agreement with the reliable literature values [3]. Free Volume Theory proposed by Allal et al. [4] was applied for the viscosity correlation and prediction. The predicted results of CO2 + methanol viscosity at 40 °C could well represent the experimental data.
[1] S. Kawasaki et al., J. Jpa. Soc. Colour Mater., 86, 163 (2013).
[2] R. Sih et al., J. Supercrit. Fluids, 41, 148 (2007).
[3] H. W. Xiang et al., J. Phys. Chem. Ref. Data, 35, 1597 (2006).
[4] A. Allal et al., Phys. Rev. E, 64, 011203 (2001).

PO227 Polymorphic solubility ratio of pharmaceutical drugs in various solvents
Yoshihiro TAKEBAYASHI, Kiwamu SUE, Takeshi FURUYA, Satoshi YODA
Research Institute for Chemical Process Technology, AIST, Tsukuba, Japan

Most pharmaceutical drugs have several crystal polymorphs, i.e., solid phases with different crystal structures. The polymorphs have different properties with each other, such as the solubility, stability, and particle shape, therefore affecting the bioavailability and the separation efficiency. It is thus required in pharmaceutical industry to selectively crystalize a target polymorph with desirable property. Solubility data of the polymorphs are essential information for the selective crystallization. Here we measured the solubility of famotidine, a histamine H2 receptor antagonist, in various solvents at 298.15 K. Famotidine has the two polymorphs, a stable form A and a metastable form B. For both polymorphs, the solubility increased in the order of ethyl acetate < water < acetonitrile < ethanol < acetone < methanol. In all the solvents, the solubility of form B was larger than that of form A. The solubility ratio B/A varied with the solvent from 1.09 to 1.32 in the order of ethyl acetate < ethanol < acetone < acetonitrile < methanol < water. The experimental solubility ratio was smaller than that estimated (1.48) from the melting temperature and the molar enthalpy of fusion for the polymorphs. The solvent effects on the polymorphic solubilities and the solubility ratio are discussed in comparison with those for other pharmaceutical drugs.

PO228 Correlation and prediction of kinematic viscosities for liquid mixtures using excess free energy model
1 Nihon University, Tokyo, Japan
2 Chuo University, Tokyo, Japan
3 GNA University, Phagwara, India

Kinematic viscosity is one of the important transport properties, and is required for designing chemical process as well as estimating transport parameters via dimensionless numbers such as Reynolds number, Schmidt number, Prandtl number etc. [1]. In some models for calculating kinematic viscosities, some excess free energy models based on the local composition idea with Eyring equation will be useful from a practical of point.
This paper reviews the models for calculating kinematic viscosity using modified Eyring and excess free energy models.
1. Kinematic viscosity at normal pressure
1.a. Correlation of kinematic viscosity for binary system [2]
1.b. Prediction of kinematic viscosity for multi-component system [2]
1.c. Prediction of kinematic viscosity using ASOG-VISCO [3]
2. Kinematic viscosity at high pressure
2.a. Prediction of high-Pressure viscosity from viscosity data at normal pressure [4]
2.b. Prediction of kinematic viscosity at high-pressure using ASOG-VISCO [5]
1) B.E. Poling, J.M. Prausnitz, J.P. O'Connell: The Properties of Gases and Liquids, 5th ed., McGraw-Hill, New-York (2001)
2) H. Matsuda, K. Tochigi, K. Kurihara, T. Funazukuri, V. K, Rattan: accepted for Fluid Phase Equilibria
3) K. Tochigi, K. Yoshino, V. K. Rattan: Int. J. Thermophysics, 26, 413-419 (2005)
4) K. Tochigi, T. Okamura, V. K. Rattan: Fluid Phase Equilibria, 257, 228-232 (2007)
5) H. Matsuda, K. Kurihara, K. Tochigi, T. Funazukuri, V. K. Rattan: Fluid Phase Equilibria, 470, 188-192 (2018)

PO229 Measurement and correlation of Solid- Liquid equilibra for three binary mixtures of Dodecanoic acid with n-octadecane, n-eicosane, and n-docosane
Jung-Chin, Tsai
Department of Chemical Engineering, Ming Chi University of Technology, New Taipei City 24301, Taiwan

Solid–liquid equilibria (SLE) for three binary mixtures of Dodecanoic acid with n-octadecane, n-eicosane, and n-docosane were measured using differential scanning calorimetry (DSC).Simple eutectic behaviors for all three systems were observed. The eutectic point of the (Dodecanoic acid + n-octadecane) system is at 300.15 K and 0.302 mole fraction of Dodecanoic acid, that of the (Dodecanoic acid + n-eicosane) system at 306.60K and 0.558 mole fraction of Dodecanoic acid and that of the (Dodecanoic acid + n-docosane) system at 311.15 K and 0.661 mole fraction of Dodecanoic acid.

PO230 Dielectric properties for dimethyl ether + propanol and propane + propanol liquid mixtures at 303.2 K
Shohei KOIZUMI1, Taka-aki HOSHINA1, Masaki OKADA1, Tomoya TSUJI2, Toshihiko HIAKI1
1 Department of Applied Molecular Chemistry, College of Industrial Technology, Nihon University, 1-2-1, Izumicho, Narashino, Chiba 275-8575, Japan
2 Department of Chemical Process Engineering, Malaysia-Japan International Institute of Technology (MJIIT), Universiti Teknologi Malaysia (UTM), Off Jalan Sultan Yahya Petra 54100 Kuala Lumpur, Malaysia

Dimethyl ether (DME) and propane are easily liquefied because they have relatively low vapor pressure among liquefied gases and used for aerosol propellant. A new solvent has been proposed to synthesize nanoparticle by using the mixture of liquefied propellant and alcohol. Therefore, the polarity and the volatility can be controlled by the composition of the solvent. In our research group, the dielectric properties has been already measured for liquefied DME + ethanol and liquefied propane + ethanol mixture. In this study, the complex dielectric spectra of liquefied DME + propanol (1-propanol and 2-propanol) and propane + propanol (1-propanol and 2-propanol) mixture were measured at 303.2 K. The complex dielectric spectra of DME + 1-propanol and DME + 2-propanol liquid mixture were measured by frequency domain method with the network analyzer (HP8720C). Coaxial probe was used for the dielectric spectra measurement in the frequency range of 0.5 ~ 18 GHz. Frequency dependence of the complex dielectric spectra was fitted by single-phase Debye equation, and the static dielectric constants and the dielectric relaxation times of DME + propanol and propane + propanol liquid mixture at 303.2 K were determined. The static dielectric constants of all mixtures studied decreased with increasing liquefied gas concentration. The dielectric relaxation times of DME + propanol liquid mixture decreased with increasing DME concentration. For propane + propanol liquid mixtures, however, the propane composition dependence of dielectric relaxation time show maximum. The excess dielectric constants and the excess inverse relaxation times were calculated from the static dielectric constants and dielectric relaxation time studied. These excess values disclose the hydrophobic interaction between liquefied gas and alkyl chain of propanol plays important role of the liquefied gas dependence of dielectric properties for all mixtures studied at 303.2 K.

PO231 Thermodynamic Modeling and Process Design and Evaluation of Methylcyclohexane (MCH) Synthesis for Hydrogen Organic Agents
Hiroyuki MIYAMOTO1, Tomoya TSUJI2, Shigeo OBA3
1 Toyama Prefectural University, Toyama, Japan
2 Universiti Teknologi Malaysia (UTM), Kuala Lumpur, Malaysia
3 Applied Thermodynamics and Physical Properties, Co., Ltd (AT-PP), Chiba, Japan

As a part of the development of the Hydrogen Organic Career, Hydrogen+Methyl-cyclohexane (MCH) system VLE model is developed for evaluation of MCH production process. Thermodynamic model using Peng-Robinson Equation of state which modified by Boston, Mathias is correlated using VLE data by Tsuji (2005) and Peter(1960). The conceptual MCH synthesis process is modeled using Aspen plus to evaluate the process performance and energy consumption.

PO232 All-atom analysis of adsorption free energy of amino-acid analogs to polymer/water interface
Osaka University, Osaka, Japan

The performance of polymer as biocompatible or separation material can be governed by its ability of adsorbing biological molecules. Considerable efforts have been devoted to characterize the polymer/water interface with the purpose of predicting the adsorption tendency, while the adsorption free energy is the direct measure of the extent of adsorption of an adsorbate of interest. In this study, the adsorption free energy was calculated by extending the energy-representation method to the polymer/water interface. We focused on the adsorption of amino-acid analogs onto poly(2-methoxyetyl acrylate) (PMEA), poly(butyl acrylate) (PBA), and poly(methoxyetyl acrylate) (PMMA). The MD simulation of the polymer/water systems was performed with GROMACS 5.1.4 in the NPT ensemble at a temperature of 300 K. The TIP3P model was used for water, and the polymer and amino-acid analog were described by potential functions that are based on the general AMBER force field (GAFF). The free energy of adsorption on the polymer/water interface was computed by the energy-representation method by viewing the polymer and water as a mixed solvent with a restraint on the adsorption depth. p-Cresol is one of the amino-acid analogs examined, and Figure shows its adsorption free energy ΔG onto each polymer at the Gibbs dividing surface. ΔG is favorable (negative) and p-cresol binds favorably to the polymers examined. The equilibrium content of water is larger in PMEA than in PBA and PMMA, while ΔG is in the order of PMEA ≈ PBA < PMMA. Thus, the adsorption free energy does not necessarily correlate with the interaction of polymer with water.

PO233 Measurement of flow properties for human blood using Falling Needle Rheometer and their of evaluation
Takafumi YABUTA1, Yusuke NEGI1, Kimito KAWAMURA2, Hideki YAMAMOTO1
1 Kansai University, Osaka, Japan
2 R&D Center, Asahi Group Holdings, Ltd., Ibaraki, Japan

In recent years, Blood viscosity considered to be important from the viewpoint of prevention and treatment of cardiovascular diseases in a medical field. Measurement of blood viscosity is difficult due to its coagulation property and measurement method of blood viscosity has not been established yet. We developed a compact sized Falling Needle Rheometer which is able to measure the blood viscosity almost immediately after collection. A Falling Needle Rheometer can measure the viscosity of a liquid with high accuracy ±0.1% in a short time and a viscosity measuring method is simple and anyone can get highly precise data easily. The blood is withdrawn from the body flowing into vacuumed plastic tubes coated with an anticoagulant. On the other hands, blood was withdrawn with non-Coated with anticoagulant vacutainer tubes and measured within 30 seconds. The blood always remained inside the vacutainer vessel and the viscosity was measured via a falling needle with a distinctive mass. We observed the effect of human blood viscosity on the addition of anticoagulants. We chose EDTA and heparin as anticoagulants. As a result, the human blood with anticoagulant shows higher viscosity than that without anticoagulant. We succeeded in measuring the flow characteristics of human blood using Falling Needle Rheometer.

PO234 Calculation of Hansen solubility parameter of mixed solvent and examination of estimation formula considering non-ideality
Kansai University, Osaka, Japan

The Hansen solubility parameter (HSP) is one of the index for affinity of materials with some solvents. The basic principle of HSP has been ‘like dissolves like'. HSP values over 1200 kinds of pure solvents have been reported by Hansen in the data base of HSPiP program 2004. Furthermore, HSP value is used for various research fields, such as an evaluation of the solubility of solid in solvent, a compatibility and an affinity of polymers in solvent and a dispersibility of fine particles in solvent. The other side, one of the methods of HSP for a liquid or its mixture is able to measure from physical properties of the solvent (such as refractive index, surface tension, permittivity and dipole moment). In the case of solvent mixture, the non-ideality of the solution is so important for practical use, however, non-ideality of Hansen solubility parameter for solvent mixture has not been elucidated so far. In this research, the comparison between the HSP value calculated from the physical properties (δt is calculated from surface tension, δd is refractive index, δp is permittivity, δh is calculated from solvent polarity parameter) and the HSP value calculated from the volume fraction ideal was carried out, and the non-ideality of solvent mixture were discussed and confirmed. In addition, this non-ideality created the estimation equation by the activity coefficient used in creating the estimation equation of the mixture.

PO235 Measurement and correlation of bubble point pressure for ethanol with three types of earth friendly spray propellant (propane, dimethyl ether, HFO-1234ze(E))
Misaki NAKAZAWA1, Taka-aki HOSHINA1, Tomoya TSUJI2, Toshihiko HIAKI1
1 Nihon University, Japan
2 Universiti Teknologi Malaysia, Malaysia

Ethanol has been widely used in our daily life as a solvent for deodorizer, medicine, cosmetics and pesticide because of its bacterial killing and human friendly natures. The knowledge of miscibility and solubility with some propellants is important for designing their spray cans. In this study, bubble point pressure of the three binaries, containing ethanol with conventional or new propellant, were measured by use of a static apparatus at the three isotherms, 293.15, 303.15 and 313.15 K. The propellants employed were two conventional ones, propane and dimethyl ether, and new one, (E)-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)). These are expected as alternatives of CFC-12 and HFC-134a. The glass cell, with the inner volume of 37 cm3, was equipped in the apparatus, and the detail equipment has been reported elsewhere. The experimental temperature was measured by a thermistor thermometer with the estimated uncertainty, u(T)=0.04 K. The pressure was by the three pressure sensors with the different maximum capacities, 10 MPa(gauge), 1MPa(gauge) and 200kPa (abs.). The estimated uncertainty is u(P)=0.5 kPa for P > 100 kPa, and u(P)=0.06 kPa for P<100 kPa, respectively The three binaries showed the non-ideality in the solution, and the positive deviations from Roult law was observed in the whole range of the experimental temperature. The non-ideality in propane + ethanol and HFO-1234ze(E) + ethanol seemed to be larger than that in dimethyl ether + ethanol. The bubble pointy pressure was correlated with non-random two liquid (NRTL) model. The calculation showed good reproducibility Then.the average absolute relative deviations were 0.70, 0.62 and 1.68 % for ethanol with propane, dimethyl ether and HFO-1234ze(E), respectively.

PO236 Ab initio moleculer dynamics simulation of H2 and HF diffusion in FLiBe molten salts
Guoda HE, Jie FU
Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai, China

FLiBe(2LiF-BeF2)molten salts are expected to serve as the coolant and the thorium-uranium fuel dissolver in molten salt reactors, with the advantage of low pressure operation, good stability under radiation, high solubility of uranium and thorium fuel, and low corrosion to structural materials. In order to purify and obtain the high quality salts, a mixture of H2 and HF is used to remove oxygen impurity from FLiBe molten salts.
In this study, Car-Parrinello molecular dynamics simulations with BLYP method were performed to investigate the structure, transport properties of H2, HF diffusion through liquid FLiBe(2LiF-BeF2) in the range of 773–973K. Radius distribution functions and first-shell coordination numbers of the molten salt obtained by Ab initio molecular dynamics calculations reproduce the data of experimental measurement. The structure of the melts reveals the existence of a network of BeF42-, Be2F73-,Be3F104-. The self-diffusion coefficients extracted from mean square displacements of F-, Li+ and Be2+ are in accord with values found in literatures. The diffusion coefficients of H2 and HF were obtained within error allowed. The results show that the diffusion coefficient of HF is a little higher than that of F- ion, because the F- in HF molecular easily stays bonded to Be2+ like other F- while the H+ of HF moves quickly.
Through the work, the diffusion coefficient of HF was obtained to calculate the basic data of gas-liquid mass transfer, and provide basis for reactor design and scale up the FLiBe purification process.

PO237 Investigation of Entropic Packing Effect of Ternary Suspended NOHM on Thermal Properties and Swelling behavior via Thermal and Spectroscopic Analyses
Soyoung CHOI, Seokyoon MOON, Youngjune PARK*
School of Earth Sciences and Environmental Engineering, Gwangju Institute of Science and Technology (GIST), 123 Cheomdangwagi-ro, Buk-gu, Gwangju 61005, Republic of Korea

Nanoparticle Organic Hybrid Material (NOHM) is a new green platform material which is self–suspended liquid–like material consisted of inorganic core and organic canopy. This new platform, NOHM, has been evaluated to have high potential for various energy and environmental applications such as CO2 sorptive materials, electrolytes, and lubricants with a low vapor pressure and promising thermal stability at high temperature over 200 °C. More importantly, NOHM has a great tunability on both entropic and enthalpic designs by introducing tailored core and linkage with specific functionalities. In particular, the entropic property which related to the intramolecular interactions between core and canopy structure could influence on the system's thermal, chemical, and electrical properties. In this investigation, it was designed to evaluate the entropic packing effects of NOHM systems on thermal properties and swelling behavior. The four different NOHM systems with varying the core size and the suspension system were synthesized (single 7, 12, 22 nm suspension and ternary suspension) and their thermal properties and swelling patterns were investigated via thermal analysis and spectroscopic analyses including ATR FT-IR and DOSY NMR. Through the investigation, the entropic packing effects by core size were identified. In addition, the ternary suspended NOHM system were evaluated to have high potential for thermal fluid application.

PO238 Machine Learning of Molecular Classification and Quantum Mechanical Calculations
Jie-Jiun CHANG1, David Shan-Hill WONG1, Cheng-Hung CHOU1, Jia-Lin KANG2, Hsuan-Hao HSU3, Chen-Hsuan HUANG3, Shang-Tai LIN3
1 Department of Chemical Engineering, National Tsing Hua University, Hsinchu, Taiwan
2 Department of Chemical and Material Engineering, Tam Kang University, New Taipei City, Taiwan
3 Department of Chemical Engineering, National Taiwan University, Taipei, Taiwan

In this paper, a machine learning method is proposed to extract molecular features as floating-point numbers in a high dimensional space by mapping a language-like description Simplified Molecular Input Line Entry Specification (SMILES) to a molecular fingerprint known as Molecular ACCess System (MACCS) which represent the molecular features as an one-dimensional array of molecular features. Two neural network models are build to predict the “sigma-profile”, the charge distribution of the molecule near a perfect infinite conductor, which is calculated by quantum mechanics. The sigma-profile can be used in the COSMO-SAC model for predicting thermodynamic properties such as activity coefficient. One uses MACCS as direct input, and the other uses the high dimensional space representation as input. Preliminary results showed that an accurate neural work model that uses the high dimensional space representation is much better than the one using MACCS. The results indicate that projection of molecular features into a high dimensional space with spatial features and distance metric is a much better representation of molecular features and potentially be a better predictor of thermodynamic properties.

PO239 Insights into methane dry reforming over Ru-substituted La2O3
Parag A. DESHPANDE1, Phanikumar PENTYALA1, Bhanu P. GANGWAR2, Sudhanshu SHARMA2
1 Quantum and Molecular Engineering Laboratory, Department of Chemical Engineering, Indian Institute of Technology Kharagpur, Kharagpur 721302, India.
2 Department of Chemistry, Indian Institute of Technology Gandhinagar, Palaj, Gandhinagar, Gujarat 382355, India.

Dry reforming of methane (DRM) is important in the reduction of greenhouse gases and their conversions to useful products. Substituted metal catalysts have emerged as a new category of oxide catalysts making an intensive impact on environmental catalysis. Density functional theory (DFT) is the powerful technique for finding the active nature of new catalytic material. Hence, in this study, we have extensively used DFT calculations to design and probe a novel DRM catalyst. We selected Ru and La2O3 due to their hindered nature towards carbon formation making it a potentially non-deactivating catalyst. Vacancy formation energy decreased on Ru substitution when compared to that observed with La2O3, thereby improving the reducibility of the substituted catalytic material. Carbonates play a crucial role in DRM reaction on basic supports and hence, so we probed different types of carbonates present over Ru-substituted La2O3. Our theoretical calculations were successfully verified with experiments. Reducibility of Ru-substituted La2O3 was probed using temperature programmed reduction profiles (TPR). DRIFTS was carried out to determine the importance of carbonates during DRM reaction. Both theoretical and experimental studies proved Ru-substituted La2O3 a good catalytic material for DRM reaction.

Session 2. Fluid and particle processing

B202 Discuss efforts against sustainable productivity by using computational fluid dynamics —A case of Japanese chemical company—
Kazutaka TAKI1, Kei SAKAKURA2, Yasushi ISHIBA3, Atsushi KAWADA4, Takeshi SUEMASU5, Shunichi KAWANAKA6, Naoki SHIMADA7
1 TOSOH Corp.
2 Idemitsu Kosan Co. Ltd.
3 Mitsubishi Chemical Corp.
4 Mitsui Chemicals Incorp.
5 Ube Industries Ltd.
6 Kuraray Co. Ltd.
7 Sumitomo Chemical Co. Ltd.

Recently, researchers and engineers in chemical companies are facing a huge variety of flows such as multiphase flows, non-isothermal flows and flows with moving boundaries. In other hand, high quality computing becomes more important. Some member in Japanese chemical companies formed a workshop for workers on the first wave of computational fluid dynamics (CFD) in 2008, which is called as chemical company workshop on CFD (CCW)(Ishiba et al., 2010, Ishiba et al., 2013 and Kawada et al. 2017).
In this presentation, we introduce our activities and current state of affairs. As regards the quality improvement of CFD, we compared numerical results in some problems:
(a) Turbulent flow in an agitation vessel
(b) Flow in a fluidization bed
(c) Vortex generation in a swirling flow
(d) A dispersed liquid-liquid two phase flow
(e) Heat transport in packed column
We have discussed that “how do CFD engineers provide better precisions for designing chemical reactors” and “what is useful for guidance of CFD” in the last decade. We need not only development of hard ware and software, but also development of qualified engineers to keep better productions. We expect that the discuss efforts of CCW is contributing sustainable productivity by using CFD.

B203 Machine learning-based framework of descriptor selection for porous material design
Tomoki YASUDA1, Shinichi OOKAWARA1,2, Shiro YOSHIKAWA1, Hideyuki MATSUMOTO1
1 Department of Chemical Science and Engineering, School of Materials and Chemical Technology, Tokyo Institute of Technology, Tokyo, Japan
2 Department of Energy Resources, Egypt-Japan University of Science and Technology, Alexandria, Egypt

Nowadays an internal 3D structure of porous material is noninvasively analyzed with sub-micron resolution using X-ray micro-CT technology for understanding of internal phenomena. It is then expected that the important properties such as reaction efficiency, effective diffusion coefficient, permeability, thermal conductivity, mechanical strength will be predicted and designed based on the relation between the microstructure and these properties. However, a geometrical descriptor, which is an index to quantify the microstructure, can be arbitrarily defined, and hence, its appropriate selection to serve the material design is challenging and needs expert knowledge.
Therefore, this study proposed a machine learning-based framework to select the descriptors of microstructure for predicting specific material properties. For its validation, the relation between the descriptors and one specific material property of more than 1000 porous material samples were analyzed. The values of defined 62 geometrical descriptors were calculated using CT scan images. The specific porous material property was obtained by numerical simulations.
The framework employed RReliefF algorithm as filter method and support vector machine as wrapper method. Although the wrapper method is computationally expensive, its numerical load was reduced using RReliefF based on a descriptor ranking of importance to the specific material property. The framework selected 8 descriptors to minimize the prediction error for permeability. Among them, the conventional descriptors such as porosity, specific surface area, tortuosity, and hydraulic radius were also included, which validated the framework. Other selected descriptors were related to chord lengths of pores in three directions, which implied that the three-dimensional shape of pores caused the difference in the permeability of porous material with similar conventional parameters' values. It should be emphasized that the proposed framework is applicable to the identification of descriptors for predicting any specific material properties, which might not be related to the microstructure of porous material in the past.

B204 Determination of mass transfer coefficient with sparged bubble analysis in stir tank bioreactors
Yusuke TOMIOKA1, Takao ITO1, Chinatsu MINAGAWA2, Koichi KAMEKURA2
1 Merck Ltd., Tokyo, Japan
2 IHI Plant Engineering Corporation, Tokyo, Japan

Stir tank bioreactors are widely used for mammalian cell culture process for biomanufacturing. From the process development to manufacturing, various size of bioreactors are used. To enable successful scale-up, Number of factors are critical to efficient cell growth and substance production. Regarding process parameters of bioreactor, liquid mixing and gas transfer efficiency are well understood for the key process parameter and evaluate those of parameter are applied as an indicator to scale up to larger process. Volumetric mass transfer coefficient (kLa) is widely used to determine gas transfer capacity of bioreactor. kLa is affected by the bioreactor design such as impeller, vessel height and diameter, gas sparger shape and capacity. The kLa have been correlated as following equation.
kLa of bioreactors that used for process development to commercial scale has been determined by the equation. Many of engineering approach are discussed to determine kLa. Bioreactors have multiple sparger to supply oxygen for various culture condition, the generated bubbles also have different diameters and size distribution. It affects the specific interfacial area, but the size of bubble and distributions has not been verified well.
In this study, we discuss about kLa determination approach with bubble diameter and size distribution analysis regarding for the series of MobiusR bioreactor. The bioreactor family is single use bioreactors by configured flexible film-based bag for all liquid contact surface as single time usage. The bioreactor series has five tank sizes, 3L vessel for early process development, 50-200L for pilot-scale manufacturing, 1000-2000L for clinical scale manufacturing. kLa performance that of the bioreactor series are already published, but the correlation of engineering parameters from modeling are not well characterized yet. We verified kLa performance of the bioreactors with general mechanical models and analyze correlation between kLa to sparged bubble specifications. also discuss the unique sparger design and characterization.

B205 [Keynote] Hard-sphere / Pseudo-particle Modeling of Reaction-Diffusion Coupling
Wei GE1,2, Chengxiang LI1
1 State Key Laboratory of Multiphase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences
2 School of Chemical Engineering, University of Chinese Academy of Sciences

While understanding the intrinsic reaction kinetics is a perpetual pursuit of chemical science, the effective reaction kinetics most frequently faced in chemical engineering is typically significantly different from it. The coupling of reaction and diffusion is a major cause of this difference and is hence a common topic for both chemistry and chemical engineering. It is, however, a challenge topic owning to its multi-scale nature with reaction at atomistic scales and diffusion ranging from micro- to macro-scales. By simplifying the particle-particle interactions in molecular dynamics (MD) with hard sphere (HS) models and improving its scalability in parallel computation with pseudo-particle modelling (PPM), the HS-PPM approach has been demonstrated effective for bridging the scales involved in reaction-diffusion coupling and advantageous over traditional MD or continuum-based simulation methods. The presentation will introduce the theories, models, algorithms, implementation and applications of this approach with example from petrochemical and coal-chemical industries.

B213 [Keynote] Energy recovery from sewage sludge by combined hydrothermal pretreatment and CO2 gasification
Ye SHEN1, Chi-Hwa WANG2*
1 NUS Environmental Research Institute, National University of Singapore, 1 Create Way, Singapore, 138602
2 Department of Chemical and Biomolecular Engineering, National University of Singapore, 4 Engineering Drive 4, Singapore 117585

Management and disposal of sewage sludge (SS) is drawing great attraction due to its large quantity and potential environmental concern. On one hand, SS contains relatively high heating value that could be recovered through further thermal treatments such as incineration and gasification. On the other hand, high nitrogen content leads to potential NOx emission during the thermal treatments. Hydrothermal carbonization (HTC) pretreatment could enhance fuel quality and remove unwanted pollutants like nitrogen and sulfur. Thus, it is popularly applied in the field of SS disposal. In this study, an integrated HTC pretreatment and CO2 gasification system was proposed and studied. Cold gas efficiency (CGE), carbon conversion factor (CCF) and ammonia emission were evaluated as key performance indicators. Nitrogen transformation behaviour from HC was studied from 400 °C to 900 °C indicating that the release of NH3 was mainly because of the decomposition of amide group. Meanwhile, gasification products from SS and hydrochar (HC) showed that NH3 (NOx precursor) emission could be reduced by 57% through HTC pretreatment although CGE and CCF were inhibited. However, this could be improved through co-gasification of HC with horticulture waste (HW). The preferred experimental condition was found to be 1:1 HC/HW mix ratio that CGE could reach 66%. The synergetic effect was believed due to the presence of calcium compounds in the HW. It was also observed that calcium element could improve both nitrogen removal efficiency during HTC and CGE during gasification.

B215 Mixing Behaviors in Mini-Fluidized Beds
Eldin Wee Chuan LIM
National University of Singapore

Fluidized beds are used extensively in the petrochemical, metallurgical, food and pharmaceutical industries. Although a rich literature focusing almost entirely on large scale fluidized bed systems has been developed, little is known about gas fluidization in mini-channels. Such mini-fluidized beds have the potential to provide large interfacial areas, high transport rates, large wall surface area for heat exchange and may find important applications for various chemical and biological processes. However, the behaviors of mini-fluidized beds differ from their large scale counterparts and correlations that have been developed for the latter have been observed to be inadequate for predicting bubbling and slugging behaviors in mini-fluidized beds. In this study, the Discrete Element Method combined with Computational Fluid Dynamics (CFD-DEM) was applied for studies of solids mixing in a mini-fluidized bed. The effects of different operating conditions, such as superficial gas velocity, continuous and pulsating flow at the inlet, interparticle van der Waals interactions, on the efficiency with which mixing takes place were investigated through the simulations.

B216 Experimental and Numerical Studies of Particle Mixing in a Rotating Drum with an Inner Particle Motion Blocking Plate
Xuan WANG1, An-Ni HUANG1,2, Wan-Yi HSU1, Hsiu-Po KUO1,2
1 Department of Chemical and Materials Engineering, Chang Gung University, Taoyuan 33302, Taiwan
2 Department of Otolaryngology-Head & Neck Surgery, Linkou Chang Gung Memorial Hospital, Taoyuan 33305, Taiwan

Small white glass particles (0.84 – 1.00 mm) and large black glass particles (1.19 – 1.41 mm) are mixed in a 40% fill, 20 rpm drum which is 100 mm in length and 98 mm in diameter. An inner particle axial motion blocking plate is placed in a rotating drum and the effect of its position on the particle mixing is studied. The plate has 78 mm inner diameter and blocks 34% particles' axial motion. The experimental results show that the degree of mixing increases by the blocking plate shearing. The shearing changes the dynamic angle of repose of the particles and the location of the plate affects the degree of mixing and segregation patterns. The particle motion in this system is realized by DEM simulation. It is found that the plate blocks particle motion deep in the bed, but enhances axial motion at the bed surface. The plate inserting increases the particle plate crossing number, the average particle axial velocity and the particle axial moving distance per revolution.

B217 Application of eulerian granular model to evaluate solid-liquid agitation
Yasuhiro SHOJI, Kentaro OTAWARA
Kureha Corporation, Ochiai 16, Nishiki-Machi, Iwaki-shi, Fukushima, Japan

The dispersion of solid particles plays an important role in solid-liquid agitation. For example, “moderate” agitation is necessary in crystallization. Insufficient agitation causes crystals to stay at the bottom of the tank; thereby particles stick together or stick to the wall of tanks. This poses handling problems such as clogging of bottom lines and insufficient quality by coarse lumps. On the other hand, overpowering agitation causes crystals to break into small particles due to a strong shearing force, causing malfunction in subsequent processes, such as, a filtration process. Thus, it is extremely important to design both a proper apparatus and proper agitating speed to obtain desirable dispersion in solid-liquid agitation.
Designing solid-liquid agitated tanks, just suspension speed NJS and segregation state are important. To estimate NJS, Zwietering's empirical formula is widely adopted. The formula requires a geometrical constant which depends on the shapes of apparatus: The geometrical constant is often unavailable so that it needs to be obtained experimentally for each apparatus which has a lot of factors such as the shape of the agitating blade, the shape of the tank, the number of blades, and the blade position, thereby taking cost and time. Thus, NJS has been estimated with Computational Fluid Dynamics (CFD) instead of experiment. In addition, the extent of segregation has been evaluated at NJS based on particle concentration distribution obtained with CFD.
NJS, obtained with CFD simulation and experiment have been found to be adequately consistent with each other. Furthermore, the shape of apparatus has been found to affect the state of segregation at NJS.

B218 Aggregation Process of Silica Micro Particles in a Two Dimensional Chaotic Mixing Field
Yusuke OCHI1, Takafumi HORIE1, Yoshiyuki KOMODA1, Kuo-Lun TUNG2, Naoto OHMURA1
1 Kobe University, Kobe, Japan
2 National Taiwan University, Taipei, Taiwan

Processes using particle coagulation are one of prominent parts of many branches of industry. With growing interest in unsteady operations, they have been applied to agglomeration processes. Coagulates produced from unsteady operations tend to have unique properties and, in terms of industrial applications, more understanding of the relationship between unsteady flow and particle agglomeration is needed. As an unsteady flow, laminar chaotic mixing induced by adding periodical perturbation has attracted a lot of attention. In fact, it has been eagerly investigated to enhance mixing efficiency and to apply to industrial processes since 1980s. There is, however, no reports on particle aggregation behavior in a chaotic mixing field. Therefore, aiming at the development of a novel coagulation process, this study investigated particle aggregation in a simplified two-dimensional chaotic flow.
A schematic of the model flow in this study is shown in Figure 1. In this model, the system consists of two rotating cylinders. The motion of cylinders can be divided into three units protocols (protocol 1a, 1b and 2). In protocol 1a and 1b, one cylinder rotates for fixed time T. On the other hand, both cylinders rotate in protocol 2. This periodic operation is supposed to perturb the fixed point which locates at the center in between the two cylinders in protocol 2 and to induce chaotic mixing.
The temporal evolution of the number of aggregates can be described using an exponential model equation. Aggregation rate constant k showed less dependency on rotation rate of cylinders ω and higher k was obtained when T was shorter. These results indicate that chaotic agitation decreases the effect of breakage and promoted coagulation. The smaller ω or T where the system has higher unsteadiness, the larger aggregates were obtained.

B221 Mixing performance of inner baffle in shear thinning fluid
Haruki FURUKAWA, Yoshito MIZUNO, Yoshihito KATO
Nagoya Institute of Technology, Nagoya, Aichi, Japan

A mixing performance of an inner baffle was investigated in shear thinning fluid. The inner baffle was placed with a clearance between baffle and vessel wall. A traditional two-bladed paddle impeller was used. Four planar baffles was vertically placed in two ways: 1) standard baffle condition 2) baffle condition with a clearance between baffle and vessel wall. A mixing pattern was visualized by decolorization method based on an oxidation-reduction reaction with sodium thiosulfate and iodine. Flow field for shear thinning fluid in mixing vessel was measured by particle image velocimetry and was shown as stream line. An isolated mixing region (IMR) like doughnut ring formed under standard baffle condition, however, IMR dissipated when baffles were placed with a clearance between baffle and vessel wall. As a result, mixing time was drastically decreased. This study suggested that inner baffle promoted mixing in shear thinning fluid.

B222 Gelation behavior of shear-thinning hydrogels fabricated via a Kenics static mixer
Athira Sreedevi MADHAVIKUTTY1, Seiichi OHTA2, Taichi ITO1,2
1 Department of Chemical System Engineering, The University of Tokyo
2 Center for Disease Biology and Integrative Medicine, The University of Tokyo

Injectable hydrogels are widely used for minimally invasive therapy. Among injectable hydrogels, shear thinning hydrogels have received much attention recently, as their viscosity decreases with increase in shear rate making it suitable for flow through long channels. Static mixers enable efficient mixing without an external energy source, and thus have been used for the fabrication of injectable hydrogels, such as dental impression materials. However, gelation behavior of shear thinning hydrogels in static mixers is still unknown. In this research, we study the shear-thinning behavior of hydrogels formed by physically cross-linking natural polysaccharides, such as xanthan gum and locust bean gums using a Kenics Static Mixer.
Mixtures of 1 wt% xanthan gum and 1 wt % locust bean gum in pure water formed hydrogel by mixing in static mixer with 16 elements at axial velocity of 100 mm/s. The mechanical strength of the formed hydrogels was measured using a rheometer. G' value for xanthan gum to locust bean gum ratio of 1:1 was found to be 18 Pa. The mechanical strength can be increased by increasing ionic strength. The pressure drop dependence on mixing conditions and hydrogel composition at different polymer ratios was characterized using the static mixer. An increase in axial flow velocity and number of mixing elements showed an increase in average pressure drop due to hydrogel formation. Furthermore, the viscosity of formed hydrogels decreased with increasing shear rates from 1.9 to 383 s-1 and was fitted to the power law model for non-Newtonian fluids. These results indicated shear-thinning property of hydrogels, which would be owed to the nature of physical crosslinkings. Pressure drop dependence of the above parameters will be discussed using non-dimensional Deborah number defined as the ratio of time taken by materials to adjust to applied stresses to characteristic time scale of an experiment.

B223 Direct numerical simulation of shear-thickening in dilute suspensions in a viscoelastic fluid
Yuki MATSUOKA1,2, Yasuya NAKAYAMA1, Toshihisa KAJIWARA1
1 Kyushu University, Fukuoka, Japan
2 Sumitomo Bakelite Co., Ltd., Shizuoka, Japan

Particle suspensions in viscoelastic fluids such as polymer solutions or polymer melts are broadly used in industrial products. Understanding the rheology of them is essential for proper manufacturing operations. Among viscoelastic fluids, so-called Boger fluids are widely utilized for separately examining the effect of elasticity of the fluids due to the constant shear viscosity. In past experimental studies, suspensions in Boger fluids are reported to show the shear-thickening in the apparent suspension viscosity even at dilute suspensions[1]. To clarify the mechanism of this thickening, numerical studies were reported[2].
We studied unclear effects of fluid elasticity on the shear-thickening in dilute suspensions using newly developed direct numerical simulation based on Smoothed-Profile Method[3]. Oldroyd-B model, which represents the shear flow rheology of Boger fluids well, is utilized in our calculations. The fluid elasticity is quantified by the Weissenberg number (Wi) and the viscosity ratio between the solvent and polymer (beta). A small beta corresponds to a high polymer concentration or a high-molecular-weight polymer (strong elasticity of fluid).
We clarified that the modulation of the velocity field of the host fluid due to the polymer stress, which is more pronounced in lower beta conditions, relax the level of the polymer stress concentration, resulting in the non-trivial weakening of Wi-dependency of the shear-thickening in the normalized suspension viscosity observed in a high Wi region in the figure. This result indicates that the two parameters measuring the fluid elasticity has counter-acting effects on the suspension rheology and are essentially important for suspension phenomena in moderate or strong viscoelastic fluids such as non-dilute polymer solutions or polymer melts.
[1] R. Scirocco et al., J. Rheol. 49, 551 (2005)
[2] M. Yang and E. S. G. Shaqfeh, J. Rheol. 62, 1363 (2018)
[3] Y. Nakayama et al., Eur. Phys. J. E 26, 361 (2008)

B224 Quantification of the flow pattern ahead of and behind stirring blades from laminar, transitional to turbulent regime.
Yokohama National University, Yokohama, Japan

In the mixing operation, the flow pattern in the turning space of the stirring blades affects the circulation flow in the tank and is directly linked to the success or failure of the mixing operation. However, the flow pattern in the turning space is not clarified because measurement in the turning space is difficult. Especially in the transitional regime, the effect of vessel size and fluid viscosity have not been understood. Although computational fluid dynamics (CFD) is very useful technique to predict fluid flow, validation with experimental data is essential.
In this study, the three-dimensional flow velocity distribution in the turning space of the six-blade paddle in a non-baffled vessel from laminar, transitional to turbulent regime was quantified by CFD using ANSYS Fluent 18.0. Laminar, transition-SST, and LES model were used for each flow regime. In addition, the velocity distribution in the turning space was quantified by two-dimensional particle image velocimetry (2D-PIV) with the transparent impeller. The flow velocity data were converted from a Cartesian coordinate system into a rotational cylindrical coordinate system synchronized with the rotation of the blades. The flow velocity distribution of CFD results were validated by PIV data.
As a result, it was found that the discharge flow of the fluid shifted from the front side to the back side of the blade as the flow regime change from laminar, transitional to turbulence. Moreover, the fluid velocity faster than the rotational speed of the blade was observed in the back space of the blade in the transitional regime, and it was found that a negative pressure area was formed. The organized vorticity motion was formed in the back space of the blade not only in the turbulence but also transitional regime.

B225 CFD analysis of solid particle concentration distribution in solid-liquid stirred tank with various particle property and stirring condition
Shunnosuke IMAI, Ryuta MISUMI, Meguru KAMINOYAMA
Yokohama National University, Yokohama, Japan

Solid-liquid mixing is widely used in crystallizer and chemical reactor with catalysis. In these processes, there is a problem that solid particles aggregate and collide with a stirring blade. The particle collision causes particle breakage and abrasion. Furthermore, when scaling up to the scale of industrial equipment, the particle dispersion state usually becomes insufficient. It is important to quantify the solid particle concentration distribution in the tank and grasp the dispersion state to solve these problems. However, it is difficult to measure the detailed particle concentration in the tank under many conditions. So, in this study, Euler-Lagrangian simulations were performed with various particle diameter, particle density, impeller speed N, Impeller diameter D, and tank diameter to quantify the vertical distribution of solid particle concentration in the vessel and identified the factor that determines the dispersion state.
The Euler-Lagrangian approach, which tracks all particle motion, was adopted. Turbulent flow in the vessel was represented by LES. The interactions of particle–particle and particle–solid surfaces were modeled using the distinct element method. Analysis was performed by changing the vessel diameter, impeller speed, particle diameter and particle density to 3 conditions respectively. The fluid was presumed to be water. The standard deviation of particle concentration in the vertical direction, σc, was calculated and time averaged σc, σc,av, was used as the evaluation index of dispersion state in the vessel.
It was found that σc,av/Cav was correlated with the value ut/ND0.8 obtained by dividing terminal velocity of single particle ut by impeller speed N and D0.8. This result showed that the uniformity of particle concentration in the vertical direction can be ordered by the ratio of ND0.8 to ut regardless of the particle property, impeller speed and vessel size.

B226 Turbulence Modeling in Side-Entry Stirred Tank Mixing Time Determination
Suci MADHANIA, Ni'am Nisbatul Fathonah, Tantular NURTONO, Sugeng WINARDI
Chemical Engineering Department, Institut Teknologi Sepuluh Nopember, Kampus ITS Sukolilo, Surabaya, 60111, Indonesia

Mixing is one of the critical processes in the industry. One of the operating units used in the mixing process is a stirred tank. The efficiency of the stirred tank is greatly influenced by several factors including stirred tank design, operating conditions, and working fluid properties. The side-entry stirred tank is widely applied in the industrial process of crude oil in the refinery industry, water-molasses mixing in the bioethanol industry, pulp stock chest in the pulp and paper industry, and anaerobic digester for biogas reactors. Mixing time is one of the key parameters used in the design of a stirred tank. This research will model mixing time in a flat bottom cylindrical side-entry stirred tank with dimensions D = 40 cm and T = 40 cm using CFD ANSYS 18.2 by applying the RKE and SKE turbulence models. The stirrer used is three-blade marine propeller d = 4 cm which is an axial type impeller. The phenomenon of mixing in a side-entry stirred tank, qualitatively described through computational prediction results in the form of flow profiles and tracer density change contours locally. Moreover, quantitatively indicated by mixing time validated using experimental data carried out by the conductometry method. The simulation results show that the mixing time modeled with the SKE turbulence model shows a similarity level of 68.16%, while the RKE turbulence model shows 31.94%.

B301 Evaluation of agglomeration and disruption for fine powder in vibrating fluidized bed
Tomonori FUKASAWA, Akihiro YAMANE, Toru ISHIGAMI, Kunihiro FUKUI
Hiroshima University, Higashi-Hiroshima, Japan

The recycling and utilization of powdery waste are becoming increasingly important for not only ensuring a sustainable environment but also decreasing the cost of waste disposal. In our previous work, focusing on the fact that the cohesion differs depending on the powder components, we report that it is possible to concentrate and separate specific components from binary mixed powders by using a vibrating fluidized bed. In order to apply this concentration and separation technology to various powders, systematically understand the aggregation and fracture characteristics of each powder in the vibrating fluidized bed are essential. In this study, the gas fluidization of three fine powder, viz. ZnO, TiO2 rutil, and TiO2 anatase were studied in a mechanically vibrating fluidized bed. The effects of the powder particle components and vibration amplitude on agglomeration and disruption in the fluidized bed were investigated. The temporal change of apparent agglomerate size was evaluated using the Ergun equation from the temporal change of bed height and pressure drop. Furthermore, the effects of powder species and vibration amplitude on aggregate size during aggregation-disruption equilibrium were evaluated based on a energy equilibrium model.

B302 Defluidization Investigation on Bubbling Fluidized Bed Particle against Alkaline Addition during Pyrolysis Process
Gunma University, Kiryu, Gunma, Japan

Bubbling fluidization process enables to enhance performance thermal conversion reaction between bed particles and raw material like biomass inside a bed column supported by gas distribution from the particle distributor at the bottom side. However, some unwanted inorganic materials like alkaline compounds contained inside biomass have the potency to create a slagging formation with oxide compounds from either inside or outside the bed column. The pyrolysis process was selected reaction to ensure the oxide compounds that were only coming from all particles placed first inside the bed column that easily associated with alkaline compounds at the high-temperature condition. The +88-125 μm silica sand and clay (bentonite) were the bed particles of Bubbling Fluidized Bed (BFB) pyrolysis process against Potassium Chloride (KCl) addition at 700oC as the use of biomass representation under superficial-N2-velocity condition. An agglomeration formation was confirmed by the decrease of average ΔP by the experiment which will theoretically should to increase by KCl additions, while the defluidization condition was initiated by the stuck up the whole particle movement that already stop moving completely even after getting more some KCl additions. Investigation on 0.05 gr and 0.1 gr encapsulated KCl addition variables within 40 samples x 15 minutes interval reaction time showed that the silica sand has a faster tendency to form initial agglomeration than clay started from 0.1136 gr KCl addition (by 0.174% of total silica sand weight). Meanwhile, the clay has more tendency to achieve defluidization formation easily than silica sand particle on variable 0.5 gr KCl addition by the rate of ΔP decrease 0.230% and 0.213% respectively. The endurance of silica sand to maintain fluidization in a longer time than clay indicates that silica sand could be considered as the better particle to be applied in this process.

B303 Dry separation of particulate mixture based on density-segregation in a vibro-fluidized bed
1 Okayama University of Science, Okayama, Japan
2 Kyushu Institute of Technology, Kitakyushu, Japan

Separation is one of the important unit operations for industry. Wet separations such as froth flotation are utilized for particulate mixture. However, the conventional wet separations, which require large amount of water, are not convenient in dry districts. In particular, the lack of water is becoming a critical issue in mining areas with drought due to global warming. Therefore, the development of dry separations to replace the commonly used wet separations is in great demand. A gas-solid fluidized bed is one of the candidates for dry separation. When a particulate mixture having density difference is fluidized, lighter particles move up and heavier particles move down in the fluidized bed. This phenomenon is called “density-segregation”. Recently, we found that the density-segregation is enhanced when vibration is added to the fluidized bed. The vibro-fluidized bed is effective to separate particulate mixtures with small density difference. Here we investigated the dry separation of particulate ore with small density difference using the vibro-fluidized bed. We found that the density-segregation does not occur using only the fluidized bed without vibration regardless of fluidizing air velocity. In contrast, the vibro-fluidized bed enables us to separate the lighter mineral and heavier mineral based on the density segregation. The fluidizing air velocity is an important key factor to enhance the density-segregation by adding the vibration to the fluidized bed.

B304 Metallic and Bimetallic Incorporated Hydroxyapatite Catalysts Prepared via Drip Thermal Treatment Using a Fluidized Bed for Oxidative Dehydrogenation of Propane
Tsutomu NAKAZATO, Yukinori KUMEDA, Takami KAI
Kagoshima University, Kagoshima, Kagoshima, Japan

Hydroxyapatite-supported metal catalysts (M/HAp) has attracted attention in recent years especially in the oxidative dehydrogenation of light alkanes because hydroxyapatite (HAp) is a promising carrier with adjustable acid-base characteristics, high stability, and various metal substitutions. In the literature, HAp itself had shown very small catalytic activity in the oxidative dehydrogenation of propane (ODHP). Recently, we found that our heat treatment method, drip thermal treatment using a fluidized bed (DTFB), could improve the catalytic activity of nickel-incorporated hydroxyapatite (Ni-HAp) catalysts in partial oxidation of methane. In this study, HAp, metallic and bimetallic incorporated HAp (M-HAp or M1-M2-HAp) were prepared via DTFB under different atmospheres, and their catalytic activity in ODHP was investigated in a fixed bed reactor at different stoichiometric ratios of gas reactants. It was found that DTFB improved the catalytic activity of HAp itself in ODHP, and that metal species such as Co, V, and Mo were useful for metallic and bi-metallic incorporated HAp catalysts.

B305 [Keynote] Fluidization-based Reaction-decoupling Fuel Conversion Fundamentals and Technologies
Guangwen XU1,2, Zhennan HAN1,2, Xi ZENG2, Junrong YUE2
1 Shenyang University of Chemical Technology, Shenyang, 110142, China
2 State Key Laboratory of Multi-Phase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Beijing, 100190, China

Thermochemical conversion of fuels via pyrolysis / carbonization, cracking, gasification and combustion has to involve a number of individual reactions called attribution reactions to form an intercorrelated reaction network for any conversion process. By separating one or some attribution reactions from the others to decouple their interactions existing in the reaction network, the so-called reaction decoupling enables a better understanding of the complex thermal conversion process and further the optimization of the conditions for attribution reactions as well as the entire conversion process to realize advanced performances. By far, numerous research works have been conducted about the application of reaction-decoupling method on gasification and combustion process in our research team. Some interesting findings were obtained: (1) catalytic cracking and reforming of tar on the surface of char is critical to deeply remove tar in gasification process, and there exists a loop between deactivation and regeneration of catalytic activity of char for tar removal; (2) tar generated from fuel pyrolysis has the highest activity and also capacity of NO reduction than char and pyrolysis gas do. Based on these fundamental findings, processes of fluidized bed two-stage gasification (FBTSG) and fluidized bed decoupling combustion (FBDC) have been proposed and commercially developed to break through the problems of tar generation for gasification and NOx emission reduction for combustion, respectively. After a series of tests at laboratory and pilot scales, two industrial demonstration plants with treating capacities respectively of 10000 t/a for gasifying herb residue and 60000 t/a for burning distilled spirit lees have been designed and built to verify the technical advantages of the proposed new processes. The results show that the FBTSG technology enables tar content below 50 mg/Nm3 in product gas and the FBDC technology lowers NO emission in flue gas to about 150 mg/Nm3 even burning fuel with 4 wt.% N (dye base). This report will summarize the fundamental finding, technical innvation, pilot test and industrial demonstration for both such technologies based on reaction decoupling.

B313 Reduction of particle stiffness in DEM simulation considering attraction force
Ryosuke YAMAGAMI, Kimiaki WASHINO, Ei L. CHAN, Takuya TSUJI, Toshitsugu TANAKA
Osaka University, Suita, Japan

Discrete Element Method (DEM) has been widely used to simulate powder behavior for the past several decades. DEM has many advantages compared to the continuum model; it is possible to include attraction forces such as liquid bridge, electrostatic and van der Waals forces and it accurately predicts the motion of individual particles in a system. One of the major drawbacks of DEM is the large calculation cost. Many of the particles used in industry are stiff and the contact time is short during collisions, which may require significantly small time step (in the order of micro to nanoseconds) in simulation. This makes it difficult or even impossible to complete simulations within acceptable time scale. Therefore, in order to increase the time step and reduce calculation cost, the particle stiffness is often reduced from the original material property. Although this approach is widely accepted for dry and relatively coarse particles where only contact force is dominant, it is reported that the particle behavior changes drastically when attraction forces are exerted on particles; particles with reduced stiffness become more “cohesive” than original particles. Hence, attraction forces are sometimes reduced to counter-balance this effect. In the present study, the effectiveness and limitations of this method are further discussed.

B314 Numerical simulation of particle motions in cascade impactor and human respiratory system
Osaka Prefecture University, Osaka, Japan

Dry powder inhalations (DPIs) is a dosage form for delivering powdered medicine to the lungs by an inhaled air flow of a patient, which is mainly used as a treatment for respiratory diseases such as bronchial asthma and chronic obstructive lung disease. The site of the human respiratory system where the powder inhalation formulation reaches depends on the size of the particle. Recent researchers actively conducted the design of DPIs for effective transportation in the human respiratory system, and they generally evaluated the lung reachability using a cascade impactor. Understanding particle motions and deposition behavior in not only a cascade impactor but also a respiratory system is necessary to improve the efficiency of DPI.
In the present study, we proposed the usage of a numerical calculation model combining computational fluid dynamics (CFD) and discrete element method (DEM). We constructed a cascade impactor model and a simple lung model to calculate the behavior of the fluid and particle transportation with CFD-DEM simulations. CFD-DEM simulations using a cascade impactor model demonstrated the experimental data of transportation ratios to each stage by adjusting the adhesion based on JKR theory. Furthermore, we investigated the effect of particle properties (particle sizes and particle densities) and the inhalation patterns (healthy and patient patterns) on the lung reachability of particles. As a result, we revealed that the relationship between the aerodynamic size and the lung reachability depends exponentially. The obtained relationship is essential knowledge for the design guide of DPIs because it enables ones to estimate the lung reachability of particles from the aerodynamic size.

B315 In-line particle size monitoring and control of the jet mil by laser diffraction analyzer
Hideyuki IKEDA1, Fumiaki SATO1, Takayuki HIRA2, Ryohei IKEDA2
1 Malvern Panalytical Division of Spectris Co., Ltd.
2 Seishin Enterprise Co., Ltd.

Jet mil is widely used for the process for dry powder milling. It has advantage of milling the sample without heating up the sample, because of its adiabatic expansion feature. However, in order to maximize the throughput, keeping the particle size small enough, optimizing the milling conditions is necessary. Conditions such as inlet pressure of the air, and feeding rate must be optimized by many trials before running the process for production. Those trials take lots of time and workload. Even after determining the optimized conditions, the size of the milled particles and throughput change with the variation of the lot of the materials to be milled. The flowability of the material also changes with time, which effects to the feeding rate of the feeder, and the particle size after the milling. To solve those problems. we propose real time measurement of the particle size of the milled powder, and discuss about the feed back control of the particle size.
2.Experimental method
We put a laser diffraction particle size distribution analyzer “Insitec” (Malvern Panalytical Ltd.), at the exit of a jet mill “STJ-200” (Seishin Enterprise Co., Ltd.). We used lactose for the milling sample. The inlet pressure of the jet mill was fixed to 0.6 MPa, and changed the feeding rate of the material.
We could see the increase of the particle size, when we increased the feeding rate. This is caused by the insufficient milling force due to the too many particles in the mill. Therefore, we could change the particle size and the throughput, by just changing the feeding rate. We tried to optimize the feeding rate, using the real-time measurement data of the particle size analyzer. By using technology, the optimization of the jet mill process is possible, regardless the particle size and hardness of the materials to be milled.

B316 Suppression of re-entrainment of particles captured on medium-performance filter media by loading with atomized APA solution
Norikazu NAMIKI1, Kazuma YOSHIMURA1, Ryoichi NAKAYAMA1, Takeshi IKEDA2, Hideo KUNITOMO2, Shunsuke KOBAYASHI2
1 Kogakuin University, Hachioji, Japan
2 ESPO Chemical Co., Ltd., Chiba, Japan

The entry of micrometer-sized outdoor particulate matters into indoor spaces via the re-entrainment of these particles from their sediment layer formed on medium-performance filter media used in air handling units of office buildings might have been of a certain concern. In the present study, we investigated the effect of loading of the medium-performance filter media, where micrometer-sized particles were deposited, with APA solution on the suppression of their re-entrainment by exposing to intermittent fast air-flow blowing.
We selected two types of unwoven and charged filter media as test media, the single-layer media composed of mixed fine fibers and coarse ones and the binary-layer ones composed of upper coarse fiber layer and lower fine one separately. The test media in sheeted or pleated form were loaded with Kanto loam particles at a given loading density, and then 10 ppm of APA solution at its given density. After one day for drying the test media, the media were exposed to intermittent blowings of fast air-flow at a given face velocity to count a number of particles released from the test media. For comparison the number of released particles from test media without APA solution loading or with DI water loading were counted in the same manner.
Fig. 1 compares the percentages of decrease in number of released particles from the binary-layer or single-layer filter media in sheeted or pleated form loaded with APA solution. It was found that the single-layer media had better performance on preventing re-entrainment of particles by APA-solution loading than the binary-layer ones. In addition, the pleated media were less effective in lowering the numbers of released particles from themselves compared to the sheeted ones. It was caused by the discrepancy of loading density between test particles and APA solution in the pleated media.

B321 CFD-DEM analysis of PM filtration due to adhesion force using fluidized bed
Kento YOKOO1, Tsuyoshi YAMAMOTO1, Hideki MATSUNE1, Masahiro KISHIDA1, June TATEBAYASHI2
1 Kyushu University, Fukuoka, Japan
2 Advanced Technology Institute Inc., Kobe, Japan

Particulate matter (PM) is a well-known air pollutant and most of them are soot emitted from fossil fuel combustion. PM diameter has been decreased with improvement of combustion technology. Especially, the concentration of PM2.5 (diameter less than 2.5 μm) has increased. Fine PM affects serious damage on human body. However, it is difficult for conventional method (e.g., bag filter, diesel particulate filter, and electrostatic precipitator) to remove PM from exhaust gas of combustor. In our research group, fluidized bed is used as a PM removal device. This device collects PM2.5 at high collection efficiency by adhesion force, which is dominant for small particle. On the other hand, the performance of this device strongly depends on fluidization state. Void fraction and gas-solid drag force is large at large flow rate. High void fraction makes PM difficult to approach to bed particle. PM separates from bed particle by large drag force. Thus, it is important for development of this device to understand the mechanism of PM collection.
In this paper, numerical simulation of this device has been performed based on combined computational fluid dynamics (CFD) and discrete element method (DEM) to calculate the trajectory of each individual bed particle and PM. PM is inlet with gas from the bottom side of fluidized bed and transferred upward with gas in fluidized bed while getting adhesion force such as van der Waals force, and separation force such as gas-solid drag force. When PM approaches to bed particle and adhesion force between PM and bed particle becomes larger than separation force, PM adheres to and is held on bed particle. CFD-DEM analysis also shows that adhesion force becomes dominant for PM diameter less than several tens μm at range of superficial velocity 0.3-0.5 m/s.

B322 MLA and DEM study of enhancement of copper liberation using high pressure grinding roll
1 Waseda University, Shinjuku, Tokyo, Japan
2 National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba, Ibaraki, Japan
3 Furukawa Industrial Machinery Systems Co., Ltd., Tochigi, Tochigi, Japan
4 Furukawa Co., Ltd., Tsukuba, Ibaraki, Japan
5 Nittetsu Mining Co., Ltd., Nishitama, Tokyo, Japan

As the demand of copper has been rapidly increasing, the concentration of copper in raw ores has been decreasing, which has become a major issue for copper production. To meet a strong demand for copper production, it is highly anticipated to develop a new process which can efficiently separate copper minerals from gangue minerals. Among the available comminution techniques, high pressure grinding roll (HPGR) is expected to achieve high mineral liberation with relatively low energy consumption. It is known that HPGR grinding can selectively break grain boundary phases which have mechanical weakness. However, the mechanism of HPGR grinding is still unclear and the effect of HPGR grinding is limited.
The objective of this study was to investigate the effect of HPGR grinding on enhancement of liberation. To achieve this objective, HPGR grinding tests were conducted. The effects of operating conditions such as pressing force, feed amount and an initial roll gap, were investigated. After HPGR grinding, liberation of copper minerals was evaluated by a mineral liberation analyzer (MLA) and image analysis of pictures obtained from MLA was conducted to measure crack size and shape in grinding products. Experimental results indicated that liberation was enhanced because of the increase of cracks by HPGR grinding. These approaches also revealed how many cracks were generated and how the cracks penetrated through an ore or a boundary phase. To support experimental results, a numerical simulation was performed to evaluate forces acting on ores during HPGR grinding. The discrete element method (DEM) coupled with T10 breakage model was applied to reproduce a HPGR grinding. Simulation results suggested that the increase of force acting on ores led to the increase of crack in an ore. Therefore, experimental and simulation results revealed that the increase of the cracks in ores during HPGR grinding enhanced liberation.

B323 [Keynote] Understanding and controlling particle mixing and de-mixing
Hsiu-Po KUO1,2, An-Ni HUANG1,2
1 Department of Chemical and Materials Engineering, Chang Gung University, Taoyuan, 33302, Taiwan
2 Department of Otolaryngology—Head & Neck Surgery, Linkou Chang Gung Memorial Hospital, Taoyuan 33305, Taiwan

Particle de-mixing may occur when particles of different physical properties are mixed. When mixing particles of different sizes, segregation bands and segregation cores may occur in the axial direction and radial direction in a rotating drum, respectively. Although theories and mechanisms of particle segregation have been proposed, a clear understanding of the underlying physics is still lacking. In this talk, size-induced particle segregation phenomena in rotating drums are reported. The mechanism of the segregation structure formation, the three-dimensional segregation patterns observed by experiments and by simulation, the control of the segregation intensity and the application of the segregation patterns will be systematically discussed.

B325 Numerical investigation of combustion process in an industrial pulverized-coal boiler
An-Ni HUANG1,2, Wan-Yi HSU1, Hsiu-Po KUO1,2
1 Department of Chemical and Materials Engineering, Chang Gung University, Taoyuan 33302, Taiwan
2 Department of Otolaryngology-Head & Neck Surgery, Linkou Chang Gung Memorial Hospital, Taoyuan 33305, Taiwan

The flow field, temperature distribution and species-in-phase distributions in a 13 MW pulverized-coal boiler are numerically studied using computational fluid dynamics (CFD). The gas phase is modelled using Eulerian frame, and the trajectories of the pulverized coal particles are described by the Lagrangian scheme. As the result, the predicted exhaust temperature and components are well agreed with the experimental data. The regions of the lower oxygen fraction locate approximately at the regions of higher temperatures. The secondary air injection mostly passes to the ceiling of boiler with very short residence time, and the trajectories of coal particles are similar to the secondary air paths. CFD technique successfully predicts the pulverized-coal combustion process in an industrial boiler.

B326 Poly (sodium 4-styrenesulfonate) decorated hydrophilic carbon black particles from waste pyrolysis process
I-Feng WU1, Guan-Ting PAN2, Jeff CHEN3, Ying-Chih LIAO1
1 Department of Chemical Engineering, National Taiwan University, Taipei, Taiwan
2 Department of Chemical Engineering, National Taipei University of Technology, Taipei, Taiwan
3 SeaWay Technology Co., Ltd.

In the past few decades, plastic products from polymers have been extensively used in daily life. In company with the convenience brought by plastic materials, plastic wastes become a critical issue for human society. One practical method to deal with used plastic products is pyrolysis process, which can turn plastic materials into short chain hydrocarbon and solid residues. Carbon black, the major residue material after plastic pyrolysis, has been widely adopted in many industrial applications. However, surface modification treatments are usually required for the recycled carbon black before used in various industrial applications, such as coating or filtration. Among various surface modification techniques, ball milling process has already been proved as a straightforward and easy mechanochemical treatment to modify surface properties of carbon black.
In this study, recycled hydrophobic carbon blacks from waste tire after pyrolysis process are used, and PSS-decorated carbon blacks are prepared through planetary ball milling. The shear force from milling process not only can decorate poly(sodium 4-styrenesulfonate) (PSS) onto carbon black, but also breaks the carbon aggregates into small fragments. The PSS-decorated carbon blacks become hydrophilic, and can be well-suspended in water. Effects of process parameters, such as milling time and solvents, on the surface properties and morphologies of PSS-decorated carbon black will be carefully examined via various analytical techniques, such as FTIR, SEM and thermogravimetric analysis. Dispersion stability tests will also be performed to prove the feasibility of making black pigment ink. Moreover, the printing quality of these inks will be examined to evaluate the possibility of applying recycled materials for printing and painting technology. In summary, this research offers general guidelines for reusing waste materials and pave the way for combining recycled materials with advanced technologies.

B402 Simulation of polymer melt flow in a channel by using a hieratical approach
Takashi TANIGUCHI, Yuji HAMADA, Takeshi SATO
Department of Chemical Engineering, Kyoto University, Kyotodaigaku-Katsura, Nishikyo-Ku, Kyoto 615-8510 Japan

We have successfully applied a multiscale simulation (MSS) method [Murashima and Taniguchi, Europhys. Lett., 96, 18002 (2011)] to flows of a mono-dispersed linear entangled polymer melt in a contraction-expansion channel and in concentric cylinders. In our MSS method, a macroscopic model is coupled with a microscopic model through the velocity gradient tensor and the stress tensor. As the macroscopic model, the Smoothed Particle Hydrodynamics (SPH) method is employed, on the other hand, as the microscopic model, a slip-link model is employed. By using our MSS method, two-dimensional flows in a 4:1:4 contraction-expansion channel and axial flow in concentric cylinders are examined. From our multiscale simulations, we have evaluated detailed microscopic information that comes from the polymer chain dynamics, such as the local orientation of polymer chains, the average number of entanglements and the number density of entanglements along a polymer chain. In addition, we found that the number of entanglements generally decreases in the middle section of a polymer chain under flows. To explain this behavior, an equation for the entanglement density on a primitive path is proposed. These microscopic insights will bring us a stepping stone to design a polymer melt that has a specific property.

B403 (canceled) <100095-1>
B404 Flow characteristics of drag-reducing surfactant solution
Takashi SAEKI, Aya KAIDE
Yamaguchi University

It is well known that certain cationic surfactant solutions with a counter ion cause significant drag reduction. In comparison with the coherent structure of the normal turbulence, vortex motion of drag-reducing flow can be restrained by the rheological property of surfactant solutions; consequently flow pattern might be greatly changed. The objective of this study is to clarify the flow characteristics of drag-reducing flow and to discuss the mechanism of the phenomenon.
The surfactant and counter ion we used were Ethoquad O/12 (C18H35N+(CH3)(C2H4OH)2Cl- and sodium salicylate (HOC6H4COO- Na+), respectively. Drag reduction rate (DR%) was measured by using PVC pipeline system having the diameter of 25 mm. We also measured the flow characteristics of the surfactant solutions with different concentrations and temperatures by using particle image velocimetry (PIV). From the experimental results, DR% at average velocity of 2.0 m/s increased from zero to 73% with the increase of the temperature from 10 to 50 °C at constant concentration of the surfactant (300 mg/L). From the velocity contour plot obtained from PIV, we found that the thickness of the lower velocity region of the drag-reducing flow was thick at 10 °C, while vortex motions seems controlled at 30 °C. On the contrary, the lower velocity region thickened with the increase of the concentration of the surfactant with constant temperature. Even if the same level of drag-reducing effects are taking place, we expected that the flow patterns are quite different depending on the concentration and temperature.

B405 Investigation of the effect of nanoparticles on microscopic wetting behavior of a nanoparticle suspension droplet on a substrate using phase-shifting ellipsometer
Eita SHOJI, Tatsuya YONEMURA, Takahiro KANEKO, Masaki KUBO, Takao TSUKADA, Atsuki KOMIYA
Tohoku University, Sendai, Japan

A nanofluid is a suspension of nanoparticles in a liquid and has attracted attention in diverse engineering fields, e.g. the nanofluid is expected as nano-ink for printed electronics. In such a situation, the knowledge of the effect of nanoparticles on wetting phenomena of nanofluid on a substrate is required. Therefore, the objective of this study is to investigate the effect of nanoparticles on wetting behavior in microscopic view using a phase-shifting ellipsometry we developed.
In this study, polydimethylsiloxane (PDMS) was used as a solvent, and PDMS-modified SiO2 nanoparticles were added within 3 wt% in the solvent. The particle size distributions of the nanoparticle suspension were evaluated using dynamic light scattering method, and consequently aggregates with a micrometer size were observed although the mean diameter was approximately 600 nm. In experiment, a droplet of pure PDMS or SiO2 nanoparticle suspension was put on a silicon substrate, and the microscopic wetting behavior near the contact line was quantitatively visualized by the phase-shifting ellipsometer. The phase-shifting ellipsometer can measure the two-dimensional thickness distribution of a liquid film at the nanoscale. Relations of the contact angle and the length of precursor film with a nanometer-scale thickness ahead of the contact line with capillary number were evaluated from the obtained thickness distributions to analyze the effect of nanoparticles.
The large difference in contact angle between the pure PDMS and the suspensions at the same capillary number was observed though the viscosity change with adding the nanoparticles is small. On the other hand, there was little difference in the precursor film lengths of both fluids at the same capillary number. These results indicate that the nanoparticles did not affect the precursor film region.

B406 Evaluation method for emulsification capacity using maximum shear rate distribution of liquid given by emulsification device
Shiseido Co., Ltd.

Most milky lotions and creams as cosmetics are emulsions and non-Newtonian liquids. In the emulsifying process of these manufacturing, a rotor-stator type emulsifying device is widely used. Each emulsifying device has a different shape of the rotating blades and stators. The size of the emulsified particles of the resulting emulsions varies depending on the device and its rotational velocity of the blades. The higher the shear rate produced by the emulsifying device, the smaller the size of emulsified particles produced. That is, it is considered that the size of the emulsified particles is greatly affected by the maximum value of the shear rate that the liquid receives as it passes through the emulsifying device. The emulsifying device is designed to generate a high shear rate. But the shear rate that the liquid receives is distributed because it depends on the route through the device. So far, we have evaluated the capabilities of emulsifying devices by experiments using specific model formulations. Today, we obtain the distribution diagram of the maximum shear rate that the liquid receives by numerical analysis. This distribution diagram can be used as an indicator of the capability of the emulsifying device.
In addition, the emulsifying device works like a pump that sucks and discharges liquid by high-speed rotation of the blades. This discharge amount is the processing capacity of the apparatus itself. When it is used in a mixing kettle, it also contributes greatly to total mixing.
This paper reports the evaluation of the capacity of the emulsifying devices by calculation of their maximum shear rate distributions and discharge amounts by using numerical analysis.

B413 Effects of emulsification parameter on droplet size distribution using SPG membrane emulsification
Ayaka NAKAJIMA, Masakazu NAYA, Hiroaki MATSUKAWA, Katsuto OTAKE, Atsushi SHONO
Tokyo University of Science, Japan, Tokyo

The technology of emulsions is used in various industrial application such as cosmetics, foods and pharmaceutics. It is also well known that mono-dispersed distribution is required stability. We focused on emulsions preparation by Shirasu Porous Glass (SPG) membrane emulsification. Compared to conventional emulsification method, this emulsification method doesn't require strong shearing force to prepare emulsions. It is also noted that the emulsions prepared by SPG membrane has mono-dispersed droplet size distribution and the droplet size. SPG membrane emulsification method requires only less energy input when prepare the same droplet size.
In this study, Oil-in-water (O/W) microemulsions prepared using SPG membrane emulsification method. Soya oil and ion-exchanged water were used as dispersed and continuous phase respectively. Sodium dodecyl sulfate (SDS) was used as anionic surfactant, and it added to ion-exchanged water. Soya oil was forced into continuous phase through SPG membrane (membrane pore size is 5 or 20 μm, and its surface is hydrophilic) using syringe pump. To disperse the oil droplet, the continuous phase was stirred by magnetic bar.
The effect of volumetric flow rate, stirring speed, and concentration of surfactants were examined. In this abstract, only about changing volumetric flow rate is described. In the condition that volumetric flow rate was changed 4 steps from 0.8 ml h-1 to 6.4 ml h-1 average droplet size, average droplet size had no significant change on each condition. Interestingly, these droplet sizes were about 3-4 times as large as membrane pore size (5 μm). On the other hand, coefficient of variation (CV), which is index of mono-dispersed distribution, increased with increasing volumetric flow rate.

B414 Microdroplet generation in microfluidic flow-focusing device
Narin PAIBOON1, Suvimol SURASSMO2, Uracha Rangsardthong Ruktanonchai2, Apinan Soottitantawat1
1 Center of Excellence in Particle and Material Processing Technology, Department of Chemical Engineering, Faculty of Engineering,
Chulalongkorn University
, Bangkok 10330, Thailand
2 National Nanotechnology Center (NANOTEC), National Science and Technology Development Agency 111 Thailand Science Park, Pathumtani 12120, Thailand

Microfluidics, the potentiality of generating monodisperse droplets, is an interesting tool in the encapsulation process due to its capability of microparticles fabrication. Droplet generation which occurs by two immiscible fluid is controlled by providing of flow- or pressure-driven approach. To combining the size of droplet in both physical and operating parameters, using the dimensionless number characterize the flow motions in different systems was studied. The dependence of the droplet size/channel size on the flow rate ratio (Qc/Qd), viscosity ratio (λcd), Reynolds number (Re) and Capillary number (Ca) was investigated for a wide range of fluid properties and flow conditions. The data was collected from the two-channel size of the 100 and 190 μm etch depth of microfluidic flow-focusing devices. An increase of the flow rate ratio resulted in a decrease of the droplet size. The viscosity ratio played an important role in droplet generation. This study also reveals that the droplet size and flow regime could be correlated with the Re and Ca of both phases. A diagram of a changing of flow regime was obtained. Moreover, the results indicated that the monodisperse droplet not only occurs in a dripping regime but also could be produced in a tip-streaming regime.

B415 Preparation of magnetorheological fluid using stabilizing additives
Aya KAIDE1, Makoto KANDA1,2, Takashi SAEKI1, Hiroshi TOCHIGI2
1 Yamaguchi University, Ube, Japan
2 Cosmo Oil Lubricants Co., Ltd., Satte, Japan

Magnetorheological fluid (MRF) attracts attention as a functional fluid of which viscosity can be controlled by magnetic field. Since MRF is a mixture of a base oil and magnetic particles, we often find particle sedimentation and/or oil separation due to the density difference and familiarity of the particles and the base oil. The objective of this study is to increase the sedimentation stability of MRF by using suitable stabilizing additives. Also, we consider the mechanism of stabilization with the connection of the network structure build by the additives and interaction with the magnetic particles.
We selected three stabilizing additives; a fumed silica, a styrene-based polymer, and an organogelator (PMDA-2C8/oleyl) and prepared MRF using such additives. We measured steady state flow characteristics and time-dependency of the viscosity of MRF by using a rheometer; Rheologia A-300, Elquest. Stability test was also conducted using a graduated cylinder. Morphological observation of the stabilizing additives was conducted by using a transmission electron microscope (TEM). From the experimental results, we found thixotropic behavior both for MFR prepared with the fumed silica and PMDA-2C8/oleyl. Particularly, PMDA-2C8/oleyl was expected to build internal structure due to the network formed by self-assembly of molecules. Although the viscosity of MRF increased with the addition of the styrene-based polymer, the MRF displayed no viscosity time-dependency. The styrene-based polymer can increase the yield stress of MRF, consequently prevent the sedimentation of particles. From TEM images, we can observe that fumed silica particles connected alternately, while the self-assembly of PMDA-2C8/oleyl formed network structure in the oil.

B416 Effect of hydrophobic fumed silica on the sedimentation stability of magnetorheological fluid
Makoto KANDA1, Hiroshi TOCHIGI1, Takashi SAEKI2, Aya KAIDE2
1 Cosmo Oil Lubricants Co., Ltd., Satte-shi, Saitama, Japan
2 Yamaguchi University, Ube-shi, Yamaguchi, Japan

Magnetorheological fluid "MRF" is a slurry prepared with an oil and magnetic particles having the average particle diameter of several μm. Since the viscosity of MRF can be reversibly controlled by a magnetic field, MRF is classified as a functional fluid. The quick and large variation of the rheological property of MRF with respect to a magnetic field is convenient to the application such as dampers, brakes, and clutches of automobiles. In order to show good fluidity of MRF under no magnetic field conditions, suitable dispersant is generally added to prevent viscosity increase due to particle aggregation. Moreover, MRF has large difference of density between the oil and particles, consequently shows particle sedimentation and liquid separation of the upper layer. Therefore, the development of the technique to increase the stability of MRF is necessary.
In this study, we focused on the effect of fumed silica as a stabilizer, which is widely used for paint industries. We prepared MRF with oleic acid as a dispersant and several fumed silica additives <see table> with different surface characteristics. The rheological measurements and stability tests were conducted for thus obtained samples. From the results, we found that the degree of hydrophobization and the concentration of silanol groups of fumed silica affected to the rheological properties and stability of MRF. In addition, MRF prepared with hydrophilic fumed silica showed further reduction of viscosity by the addition of oleic acid as compared to hydrophobic fumed silica.

B417 Direct numerical simulation of flow resistivity and oil droplet coalescence on x-ray ct images of nonwoven fabrics filters
Mohammad Irwan Fatkhur ROZY, Masaki UEDA, Tomonori FUKASAWA, Toru ISHIGAMI, Kunihiro FUKUI
Department of Chemical Engineering, Graduate School of Engineering, Hiroshima University, Higashi-Hiroshima, Hiroshima, Japan

In this study, we numerically study and experimentally validate the flow resistivity of commercial nonwoven fabrics filters used for a bag filter system. A numerical method that coordinates the filter structure obtained by X-ray CT imaging with computational fluid dynamics using immersed boundary method is developed to represent a realistic flow field inside the filter during simulation. We investigated the effect of superficial velocity, porosity of the filter domain, and the type of filter then analyzed the results using Darcy's law. The results showed that the calculation results from our numerical method were quantitatively in good agreement with the experimental measurement. We also verify that the Kozeny constant can be estimated by utilizing the solid volume fraction defined by immersed boundary method. These results show that our simulation method can be used to clarify the effects of porosity, fiber arrangement, and fiber shape on the pressure drop. We will discuss the application of this method to coalescence of oil droplets in oil-water separation process.

B418 Flow characteristics of non-Newtonian fluid (non-spinnability fluid)
Katsuhide TAKENAKA1, Yoshihiro YOKOKAWA2, Aya TANAKA2, Koichiro ONISHI1
1 Sumitomo Heavy Industries Process Equipment Co., Ltd., Saijo, Ehime, Japan
2 Shiseido Co., Ltd., Osaka, Osaka, Japan

There are lots of stuff, which is subject to the rheological issue, in a market. Typical examples are grease for mechanical industries, cream and hair gel for cosmetic industries, and gelatin for food industries.
On the other hand, there is few number of the research for mixing dealing with rheology due to complex factors, in spite of facing many of mixing problems in industries. One of the important factors is fluid viscosity. Therefore, as guided by N. Harnby et al. (Mixing in the Process Industries, 2nd edition issued 1997), in case of non-Newtonian fluid, mixing Reynolds number is modified with apparent viscosity, which is converted with coefficient of shearing rate (Kagakukogaku-Binran) proposed each type of impeller.
In this study, comparing with spinnability fluid and non-spinnability fluid (no 1st normal force difference fluid), as non-Newtonian fluid has been done, in terms of flow characteristics.
The mixing power has been measured with similar viscosity, the power for spinnability fluid is proportional to cubic of impeller speed for all type of impeller we have investigated. This is typical behavior in turbulence region. On the other hand, the mixing power for non-spinnability fluid perform differently. Exponent of impeller speed change from approximately 2 to 3, depending on impeller shape. However, flow is not observed, especially at the condition obtained exponent 2 of impeller speed.

B421 Distribution of local viscosity of viscoelastic solutions measured by using optical tweezers
Ruri HIDEMA1, Hikari TAKAHASHI1, Zenji YATABE2, Hiroshi SUZUKI1
1 Kobe University, Kobe, Hyogo, Japan
2 Kumamoto University, Kumamoto, Kumamoto, Japan

Solution containing high-molecular-weight polymer or surfactant forming rod-like micelles show very complex flow behavior. Non-linear flow behavior became prominent especially under high shear rates or high extensional rates. That is due to non-uniform structure of dilute polymer or rod-like micelles solution, which is enhanced under the condition of high strain rates.
In this study, in order to detect non-uniform structure in complex fluids, optical tweezers was used to measure local viscosity of several Newtonian and viscoelastic solutions. Ethylene glycol solution, polyethyleneoxide (PEO, Mw = 3,500,000) solution and cationic surfactant solution were prepared as Newtonian and viscoelastic solutions. The cationic surfactants form rod-like micelles in the solution with the presence of counter ion supplier, which became highly viscoelastic. The average values of the local viscosity of these solutions measured by the optical tweezers were consistent with the viscosity measured by a rheometer. Then, distributions of the local viscosities were also obtained to quantify non-uniform structure of the solution. The local viscosity distributions of viscoelastic solutions were wider than that of Newtonian fluids. Especially, the distribution of rod-like micelles solution was much wider than that of the other solutions. The results suggest that the local viscosity distribution of each solution has non-uniformity information of viscoelastic complex fluids.

B422 Computations of Curtain Coating
Ryota NAKAJIMA1, Takumi CHIBA1, Shunji HOMMA1, Donghyuk KANG1, Hiroyuki HIRAHARA1, Hirokazu UMEMIYA2, Sumihisa ODA2
1 Saitama University, Saitama, Japan
2 Saiden Chemical Industry Co., Ltd., Saitama, Japan

For the production of self-adhesive labels, high speed coating of adhesives is necessary to increase the productivity of labels. It is also required that the coated adhesives is as thin as possible to reduce the use of adhesives. Curtain coating is one of the candidate to achieve high speed and thin coating. However, curtain coating can cause some troubles like air entrapment resulting in the defect of the products. In this study, three-dimensional numerical simulations of curtain coating were carried out in order to investigate the mechanism of entrapment of air to coated films. The OpenFOAM tool box with VOF method was used for the simulation.
Simulation results reproduced four different regimes in curtain coating: coatable, heel formation, air entrainment, and air entrainment with heel formation. They are mapped on the diagram of the curtain Reynolds number versus the velocity ratios between coating speed (substrate speed) and impingement one. We will discuss the mechanism of air entrapment using numerically visualized flow fields.

B423 Flow classification and its application to fluid processing
Kyushu University, Fukuoka, Japan

In fluid processes in engineering fields, flow pattern characters are essential in the process performance, and are largely controlled by the geometric structures of the channel and/or driving element. In melt mixing in polymer processing, various elements, including screw and mixing elements, defines the channel geometry, and the resulting flow patterns are responsible for different mixing characteristics. Analyzing the flow pattern should be useful in understanding the mixing characteristics in connection with the different geometric structures of the mixing elements. Mathematically, the classification of flow field can be analyzed by the eigen-analysis of the deformation rate tensor [1,2]. However, such analysis technique have not been commonly applied in fluid processing. We have developed a simplified flow classification scheme based on the invariants of the strain-rate tensor and the vorticity tensor, which is frame-invariant [3,4] . The spatial distributions of these quantities offer an essential tool in understanding the flow pattern structure, and therefore can be useful to get insights into the connection between the geometry and the process performance.
[1] Tanner, R. I., and R. R. Huilgol, Rheol. Acta 14.11 (1975) 959–962.
[2] Chong, Min S., Anthony E. Perry, and Brian J. Cantwell, Phys. Fluids A 2.5 (1990) 765–777.
[3] Nakayama, Y., et al. AIChE J. 62.7 (2016) 2563–2569.
[4] Nakayama, Y., et al., AIChE J. 64.4 (2018) 1424–1434.

B424 Effect of agitation speed on ice cream properties in batch freezer
1 School of Food and Nutritional Science, University of Shizuoka, 52-1 Yada, Suruga, Shizuoka, Japan
2 Complex Fluid and Thermal Engineering Research Center (COFTEC), Kobe University, 1-1 Rokkodai, Nada, Kobe, Japan

Ice cream is one of the most popular deserts in the world. Its physical and sensory properties depend on the microstructure of ice cream. Ice cream consists of bubble, ice, fat and the freeze-concentrated continuous phase. Because all the phases intricately interact each other, it is quite difficult to construct the precise principle for the control of ice cream properties in the production process. The microstructure of ice cream is determined in freezing process. During freezing process of the ice cream mix in an ice cream freezer, air is whipped into the mix. Air taken in the ice cream is broken down to small bubbles by the shear force. Also, the shear force induces fat globules coalescence which affects ice cream properties. Therefore, it can be considered that the shear force generated by the agitation operation dominates the microstructure of ice cream. In order to control ice cream properties from the perspective of agitation, in this study, the effect of agitation speed on the viscosity of the ice cream and the bubble size in the ice cream was investigated.
The commercial batch ice cream freezer with an impeller was used. During freezing process, the torque was monitored by a torque meter (ST3000II, SATAKE Chemical Equipment MFG. LTD.). Based on the measured torque, the apparent viscosity was estimated. The bubbles size in the ice cream was calculated from the image acquired by a digital micro scope (DMS1000B, Leica Microsystems LDT.).
The apparent viscosity decreased with the increase in the agitation speed. This means the agitation speed has an influence on the sensed creaminess during consumption. Furthermore, it was found that the increase in the agitation speed leads the increase in smaller bubbles with a narrower size distribution. These results imply that the rheological properties can be controlled by the agitation operation.

B425 [Keynote] Bubble dynamics in gas-solid two-phase fluidised beds
Siddhartha SHRETHA, Shibo KUANG, Aibing YU, Zongyan ZHOU
ARC Research Hub for Computational Particle Technology, Department of Chemical Engineering, Monash University, VIC3800, Australia

The gas-solid fluidized beds have been broadly studied, both experimentally and theoretically because they are widely applied in several industrial applications. However, most of the previous studies reported their findings based upon spherical particles while in practice, particles in gas-solid fluidized beds are generally non-spherical. In this study, the combined approach of CFD-DEM (Computational Fluid Dynamics - Discrete Element Method) is used to simulate the gas-solid fluidization process of ellipsoidal particles to analyse the effect of particle shape on bubble dynamics. Simulations for single jet fluidized bed by injecting gas jet only through central orifice showed that the bubbles for ellipsoidal particles are larger in size, have a greater bubble size distribution and higher bubble break-up frequency. The bubbles for ellipsoidal particles have lateral drift, therefore, while rising through the bed they travel away from bed centreline. Simulations for uniform gas injection demarcated that the bubble and solid flow patterns are asymmetrical for ellipsoidal particles compared to spherical particles. The bubble size is smaller and the bubble size distribution is broader for ellipsoidal particles. Both types of simulations exhibited that the difference in particle shape can result in different bubble behaviour, for example, a region of bubble formation, bubble trajectory and bubble properties. Moreover, ellipsoidal particles have preferred orientation which can depend upon the development of bubbles. The ellipsoidal particles align parallel to the fluid flow direction around the bubbles while they align perpendicular to the fluid flow direction at the top of the bubble. The findings deduced from this study can aid in the understanding of particle shape effect on gas-solid fluidized beds.

PB301 Numerical simulation of particle suspension in a stirred tank equipped rigid-flexible impeller
Xia XIONG, Zuohua LIU, Liang WANG, Changyun TAO
School of Chemistry and Chemical Engineering, Chongqing University, Chongqing

Particle suspension characteristics are predicted computationally in a stirred tank with solid concentration of 25% and driven by rigid-flexible impeller. The software of Fluent was utilized to investigate flow field structures in stirred tank. The effects of impeller type, length of flexible material, connect way of flexible material, mixing time were investigated by using the Eulerian–Eulerian two-fluid model and the standard k–ε turbulence model. It turned out that the structure of impeller has an obvious effect on solid particle distribution. The suspension of solid particles in the rigid-flexible impeller system was more homogeneous. It was also suggested that longer flexible material and longer mixing time results in well homogenous distribution of solid particles in the tank equipped with rigid-flexible impeller. On the whole, the rigid-flexible impeller could enhance the suspension of solid particles effectively.

PB302 Numerical simulations of flow and heat transfer in a industrial hydro thermal cracking reactor of residue oil
Zhenxing ZHU, Xiaojin TANG, Zijun WANG
SINOPEC Research Institute of Petroleum Processing, Beijing, China

Hydro thermal cracking process of residue oil is an important technical route in the area of heavy oil processing. Because of a few catalyst loading, low cost, and low blocking probability, the slurry bed is better to be applied in processing residue oil, especially for heavy residue. With the increase of conversion, the stability of residue oil becomes weaker, and some unstable compounds may be crystallized easier. The precipitates will be attached at the surface of catalysts and reactor, which will lead to the deposition of catalyst and blocking. The distribution of velocity and temperature inside the reactor is essential for reducing precipitation of unstable compounds, and preventing reactor from blocking. Based on the results of a pilot plant, an industrial hydro thermal cracking reactor of residue oil was developed. Then, the flowing and distribution of fluid and deposition of catalysts were simulated by CFD. To reduce the deposition of catalysts inside the large slurry bed reactor, the position of inlet of residue oil was optimized. Furthermore, the distribution of temperature inside the reactor was predicted by CFD. It can be found that the distribution of temperature inside the reactor was very uniform, the difference in axial temperature is less than 3K, the difference in radial temperature is less than 1K.

PB303 Study on the Effects of Grinding Factor and Scaling up in Grinding Using Horizontal Dry Bead Mill
Takahiro TAMURA1, Mitsumasa KIMATA2
1 Institute of Fine Particle Technology, Ashizawa Finetech Ltd, Oyama, Japan
2 Yamagata University, Yonezawa, Japan

Though the grinding operation is a unit operation that has been known for a long time, it still often occupies an important position in industry. Thus, various grinders have been evolved and produced in a variety of shapes to meet changing needs. In principle, bead mills can provide grinding conditions under a high packing density and high energy density of the media as well as cover a broad range of output. Therefore, their future application is highly expected to respond to the requirements of various grinding operations by the current industry. However, bead mills have a short history compared to other types of grinders. Especially for dry bead mills, it is hard to say that they are well known. That is why we studied and reported the performance of horizontal dry bead mills in this presentation.
For the experiments, 2 sizes of horizontal dry bead mills with different capacities, lab and manufacturing scale, were used to study scaling up and down. The grinding experiments were performed by changing each typical grinding factor for bead mills, including the agitator peripheral speed, bead packing density, bead diameter, and material feeding speed. This set of experiments was conducted for 3 kinds of materials, silica sand of natural inorganic materials, alumina of synthetic inorganic materials, and activated carbon of organic materials.
As a result, common for all materials, similar rules were found between the particle size and specific energy, the amount of mechanical energy per unit amount of material. In addition, these rules were applicable for the different-size mills, indicating that the scale can be controlled by the rules and specific energy. Also, it is revealed that when using a single type of material, changing the bead diameter changes the energy efficiency, indicating that using small-diameter bead was effective for efficient grinding.

PB304 The facile control synthesis of hexagonal NaREF4 in a continuous microfluidic reaction system
Di LIU, Kai WANG, Yundong WANG
The State Key Laboratory of Chemical Engineering, Departmemnt of Chemical Engineering, Tsinghua University, Beijing 100084, China

In an effort to achieve the highly efficient synthesize upconversion nanoparticles (UCNPs) with controlling over properties, we report for the first time a continuous flow synthesis of hexagonal β-phase NaREF4 NPs using microflow system. The precursor solution was prepared by the reaction of rare earth oleate, sodium oleate and ammonium fluoride, which avoided the production of NaF at room temperature and speeded up the hexagonal nanoparticle growth rates at high temperature. Specifically, the separation of nucleation stage and growth stage was achieved by means of segmented temperature control in the microflow system. The nucleation and growth reaction mechanism were further studied and the experiments of using different temperature, reactant concentration and flow rate were designed to study the influence on the shape and size of β-phase NaREF4. The ultra-small (5-6nm) β-NaYF4:Yb,Er nanoparticles were prepared by Gd3+ doping in the microflow system. And the monodisperse sub-10 nm core-shell nanoparticles β-NaYF4(Gd):Yb,Er@NaYF4 were prepared successfully by mixing the core solution and the shell precursor solution via a continuous microfluidic process. The β-phase nanoparticles exhibit green and red emissions under excitation of laser at 980 nm. Our research opens a door for the synthesis of upconverting nanocrystals in the continuous flow reaction system.

PB305 Growth of a pinhole generated in a thin coated liquid film
Takumi CHIBA1, Ryota NAKAJIMA1, Atsuya TAKADA1, Shunji HOMMA1, Donghyuk KANG1, Hiroyuki HIRAHARA1, Yosuke OKUBO2, Hirokazu UMEMIYA2, Sumihisa ODA2
1 Saitama University, Saitama City, Saitama, Japan
2 Saiden Chemical Industry Co., Ltd, Saitama City, Saitama, Japan

The growth of a pinhole generated in a thin coated liquid film was simulated numerically in order to study the mechanism of dewetting on a thin coated adhesives. Navier-Stokes equations of a one-fluid formulation were solved by projection method and the motion of the liquid-air interface was traced by a VOF method. Rheological properties of the liquid were approximated by a Carreau-Yasuda model. The OpenFOAM tool box was utilized to perform the numerical simulations. Simulated results were in good agreement with experiments where a pinhole was spread on a coated film of adhesives. The growth rate was proportional to the inverse of Ohnesorge number and therefore it decreases when the viscosity of the liquid is high and the surface tension is low.

PB306 Three-dimensional simulations of laminar film condensation
Saitama University, Saitama, JAPAN

Laminar film condensation of saturated vapor on the surface of a low-fin tube was numerically simulated in order to examine the effect of the shape of the tube. Navier-Stokes equations, an energy equation, and a continuity equation including phase change were solved simultaneously. Vapor-liquid interfaces were traced by VOF method. The OpenFOAM tool box was utilized to perform the numerical simulations.
Figure 1 shows an example of the simulation results. When the fin pitch is large, the condensate drips as a tuft from the lower part of the fin. When the fin pitch is small, on the other hand, the condensate falls as a curtain after filing the condensate between the fins.
The rate of condensation was obtained from the numerical simulations. When the fin pitch is small, the rate of condensation increases with the fin pitch. However, the rate decreases with the pitch when the pitch is larger than the certain value. It has thus suggested that there is an optimum fin pitch. Numerical simulations are expected to be able to optimize the shape of low-fin tubes.

PB307 Evaluation of drying process of a droplet considering flow and temperature fields in a spray dryer
Ryuya ITANO, Tomohisa KAWAGUCHI, Koichi NAKASO, Yasushi MINO, Kuniaki GOTOH
Okayama University, Okayama, Japan

Particle generation process from droplet in a spray dryer is investigated. In the spray dryer, droplets generated from an atomizer are introduced to the dryer with hot air. While droplets are heated in the airflow, the air is cooled by exchanging heat with droplets. The atmosphere of the droplet such as temperature and humidity therefore changes with time in the dryer. Because drying behavior is influenced by the temperature and humidity around the droplet, drying of droplet should be evaluated by considering change in atmosphere of droplet. However, the drying of droplet has been studied under fixed conditions in the past researches. In this study, to observe the drying behavior, a droplet suspended on the tip of a wire is heated by the controlled air flow.
A slurry droplet of silica particles in water is studied. The effect of flow rate on the drying of droplet is investigated because flow around the droplet would affect the local heat transfer rate. Fig. 1 shows examples of the drying results with slurry droplet. At higher flow rate, mushroom-shaped particle are obtained. On the other hand, doughnut-like particle is obtained at lower flow rate. The results could be explained in terms of the particle Reynolds number.
The solution droplet of dextrin in water is also investigated. The effect of temperature on the drying is especially studied. As the drying proceeds, a solute layer is formed on the surface of the droplet. The permeability of water vapor through the solute layer is low especially for the use of dextrin. When the temperature is higher than the boiling point of the solution, boiling happens inside of the droplet then expanded particle is formed. On the other hand, the particle containing water inside of the particle is formed for the lower temperatures.

PB308 Evaluation of gas dispersion in stirred tank with fractal shaped impellers
Fukuoka University, Fukuoka, Japan

The gas dispersion in stirred tank is a widespread operation in the chemical and biochemical industry. In the process of gas dispersion, control of bubble size is important factor for the mass transfer process, and the performance relies heavily on its impeller design. Rushton turbine (RT) has been commonly used for the process because of its strong shear force. Thus, we proposed a novel kind of impellers, what we call fractal shaped impellers based on the RT. A kind of fractal structure, Koch curve was applied on blade tips of RT as shown in Figure. We expected that increase of the length of a side by iterations of fractal structure promoted shear around the wingtip and generated multiscale vortex to break up bubbles in gas dispersion.
Consequently, we investigated the effect of fractal shaped impellers on mass transfer process in gas dispersion. A stirred tank of transparent acrylic with four baffles was used for the experiment. An optical dissolved oxygen sensor was located in the front face of a baffle to evaluate the volumetric mass transfer coefficient (kLa) from variation of oxygen concentration in the tank. The bubbles discharged from a blade were visualized by high speed camera. The bubble size was measured by both photographic method and image analysis.
First, the kLa of each impellers was evaluated under the same power consumption. The kLa increased by using KF-I type impellers and KF-Ⅱtype impellers didn't make a difference. The generate bubble size also became smaller by using KF-I type impellers. Finally, we confirmed that the more small bubble generated from the blade, the more kLa increased in the tank.

PB309 Experimental investigation of gas slug shrinking behaviour inside a microchannel
Yusuke NOGUCHI1, Satoko FUJIOKA2, Koichi TERASAKA2, Simon MATTHES3, Michael SCHLÜTER3
1 School of Science for Open and Environmental Systems, Graduate School of Science and Technology, Keio University, Yokohama, Japan
2 Department of Applied Chemistry, Faculty of Science and Technology, Keio University, Yokohama, Japan
3 Institute of Multiphase Flows, Technische Universität Hamburg Harburg, Hamburg, Germany

Gas-liquid slug flow is a flow pattern in which gas and liquid flow alternately.
There are numbers of prior researches on enhancement of extraction and reaction using the mixing effect of circulating flow inside a liquid slug, however, there are few experimental examples focusing on the shape change of gas slug due to dissolution.
This investigation focuses on the shape changing of gas slug in order to control slug size by changing flow rate and channel geometry to apply it for size-controlled micro bubble production.
Liquid phase was degassed and then pressurized from a reservoir to T-junction microchannel made of PDMS with controlling flow rate. Oxygen gas was injected to the microchannel through the gas-injection nozzle by using syringe pump. Size-controlled gas-liquid slug was produced by injecting both fluid and observed with a close focus lens above the microchannel. The change of slug volume and shape effected by liquid flow rate were investigated from captured images.
Figure shows the time course of oxygen slug shrinking behaviour in condition of no flow of gas and liquid phase after slug production.
The change rate of slug length for flowing condition of liquid phase was larger than that of no flow condition, therefore, liquid phase flow promoted gas slug dissolution.
Without degassing of liquid phase, shrinking of gas slug was not observed. It is thought that dissolved gas concentration is important parameter to control gas slug size.
By measuring slug size, the possibility to control the gas slug size was indicated and precisely controlled microbubble production is expected using this method by injecting size-controlled gas slug into vessels filled with liquid.
This method for microbubble production might be the solution to overcome difficulties of small bubble detaching in conventional bubble formation from a nozzle or a slit.

PB310 Evaluation of Particle-Wall Adhesion Characteristics Based on Separation of Adhered Particle by High Speed Air Jet
Yuna ISHIDA, Maho KAGEYAMA, Yasushi MINO, Koichi NAKASO, Kuniaki GOTOH
Okayama University, Okayama, Japan

In many processes in which particles are operated, adhered particles on the wall of equipment and pipes cause problems such as contamination and blockage in feeding or transportation. Therefore, it is required to reflect the adhesion characteristics in the process design and the determination of operating conditions. However, the designing method and the prediction method of operating conditions with taking into the adhesion characteristics have not been established yet.
Because a particle behavior in these process operation is affected by fluid motion, the evaluation of adhesion characteristics based on the force induced by fluid motion is useful for establishment of the designing or the prediction method. As one of simple operation relating to the adhesion and fluid motion, we focused on the air jet removal of particles. In the air jet removal, adhered particles are separated from a wall by high-speed air flow ejected from a nozzle. The removal efficiency of the air jet removal depends on the dynamic pressure of the impinging air flow on a wall. It suggests that the separation force acting on a particle is determined by the dynamic pressure.
In this study, a slit nozzle having a width of 0.25 mm and a length of 20 mm was used as a reference nozzle, and 7-types of spherical silica particles having different particle diameter ranges were used as a reference particle. The removal efficiency of these particles from the borosilicate flat glass plate was determined experimentally. From the correlation between the diameter of reference particles and the required dynamic pressure for the removal, the separation force acting on reference particles was determined as a function of particle diameter and dynamic pressure. By means of these reference particles known to the separation force, the adhesion between the various wall surfaces and the reference particles was determined.

PB311 Droplet breakage in a pulsed disc and doughnut column
Shaowei LI, Shan JING, Hao ZHOU, Xiong YU
Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 100084, China

Lack of experimental data for droplet breakup is one of the limitations for the application of population balance model (PBM). We present here a new method to directly measure the breakage of droplet swarm in a pulsed disc and doughnut column (PDDC). A high speed camera was used to directly measure the droplet breakup frequency and daughter size distribution for a series of liquid-liquid systems. The multiple breakup was treated as an original breakup and several intermediate breakups in order to characterize the process quantitatively. The effects of pulsation intensity, dispersed phase viscosity and flow rate, interfacial tension were investigated in detail. The data covers the main factors affecting the droplet breakage in the PDDC and are sufficient to support the establishment of useful empirical correlations for breakup frequency and daughter droplet size distribution. The experimental results and correlations all indicate that the breakup frequency increases with the decreasing of the dispersed-phase viscosity or the interfacial tension, or the increasing of the pulsation intensity. The daughter droplet size distribution broadens considerably with decreasing interfacial tension. The correlation equations were then used in a CFD-PBM simulation to calculate the droplet number density, which further proved the feasibility of the correlations.

PB312 Whipping behavior of rice flour dough
Chiaki ICHIKAWA, Takahiro FUKUNAGA, Daitaro ISHIKAWA, Tomoyuki FUJII
Graduate School of Agricultural Science, Tohoku University, Sendai, Japan

The bubbles in rice flour dough were investigated under constant temperature. The change of distribution in bubble size plays an important role in controlling food texture. If the formed bubble size depended mainly on three kinds of force, such as inertial, viscous, and surface tension, then the normalized mean bubble diameter should be a function of Reynolds Number and Weber Number. We obtained our experimental data mainly using a home size whipper, and we compared the data with the results obtained from the dough with nine kinds of rice flours prepared by different milling process in this work. We also added the size effect of rice flour particle as Bond Number. Furthermore, we carried out a dynamic wettability test in order to estimate wettability of rice flour surface. The results of the dynamic wettability test were described well by Washburn equation, and dccosθ was calculated as a parameter of wettability (dc : effective diameter of capillary in powder bed, θ: contact angle). The relationship between Bo and dccosθ/dp, normalized wettability parameter by particle size (dp) of rice flour, was obeyed by a straight line. Thus, it was suggested that the powder properties of rice flour could classify by interface properties. The mean diameter of the bubbles (dbm) generated by whipping was expected to be affected by the thickness (d) of the rod of whipper, its movement speed, physical properties of material and gravitational acceleration. The dimensionless mean diameter (dbm/d) was expressed by a dimensionless equation. It was found that We was high contribution for mean diameter from the result of its power index obtained from the dimensionless equation demonstrated. The empirical equation obtained was generally applicable to the variety of materials selected. Consequently, the bubbles in rice flour dough generated by whipping process could evaluate with the interface properties of rice flour.

PB313 Rheological properties of Nitrile Rubber Latex blended with Titanium Dioxide (TiO2)
Tiam-Ting TEE1, Siew-Wai PHANG2, Tin-Sing LEE1, Soo-Tueen BEE1, Heng-Wai KANF1
1 Universiti Tunku Abdul Rahman, Kuala Lumpur, Malaysia
2 Tayloys University, Kuala Lumpur, Malaysia

Nitrile Rubber (NBR) latex is used for making various gloves. The rheological properties of Nitrile Rubber Latex blended with Titanium Dioxide (TiO2) were investigated using a rheometer. By carry out rotational and oscillatory tests, the relationships of viscoelastic properties such as viscosity, complex viscosity, storage modulus, loss modulus and phase angles were investigated.
Rotational test determine the relationship of viscosity and shear rate. Respond on the viscosity was investigated by increasing the shear rate. The samples under studied were pure NBR, compound NBR and compound NBR with different phr value of filler. In these tests, the viscosity of the NBR decreased with increasing shear rates.
Oscillatory tests were carried out to determine the relationship between complex modulus and angular frequency. The higher the angular frequency applied, the lower the complex viscosity were obtained for the samples. Viscoelastic properties such as storage modulus, loss modulus and phase angles were studied. The storage modulus of the sample decreased when angular frequency increased. Whereas the loss modulus increased with increasing angular frequency. This indicates that the fluids are more favourable on energy loosing rather than energy storing. By referring to the phase angles, the fluid's flow behaviour can be easily known. 0 °phase angle indicates the fluid exhibit perfect elastic behaviour, whereas 90 °phase angle indicates that the fluid is exhibiting Newtonian flow (water behaviour). NBR compounds shows viscoelastic behaviour

PB314 Application of DEM simulation to design of a laboratory-scale high pressure grinding roll
1 Waseda University, Shinjuku, Tokyo, Japan
2 National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba, Ibaraki, Japan
3 Furukawa Industrial Machinery Systems Co., Ltd., Tochigi, Tochigi, Japan
4 Furukawa Co., Ltd., Tsukuba, Ibaraki, Japan
5 Nittetsu Mining Co., Ltd., Nishitama, Tokyo, Japan

It is known that high pressure grinding roll (HPGR) is an effective grinding method to enhance the liberation of minerals with high energy efficiency. HPGR grinding has many kinds of operating parameters which affect the liberation state and the optimum operating parameters strongly depend on a types of ores. From the viewpoint of industrial application of HPGR in mineral processing, it is essential to decide the optimum operating conditions depending on ores. Since a batch of HPGR experiment in pilot scale requires huge amount of ore samples, it is difficult to conduct and repeat experiments in various operating conditions. Therefore, it is highly anticipated to newly develop a laboratory-scale HPGR which only requires small amounts of ores at an early stage of mine development.
The objective of this study was to develop a laboratory-scale HPGR which can reproduce grinding results similar to those obtained from a pilot-scale HPGR. To achieve this objective, the discrete element method (DEM) coupled with T10 breakage model was applied to reproduce a HPGR grinding process. First, grinding processes of ores in a pilot-scale HPGR were simulated by the DEM coupled with T10 breakage model. Comparison between simulation results and experimental results was also conducted for the validation of the simulation model. Good agreement was confirmed for throughput of ore, energy consumption and a working roll gap. After the validation of simulation model for a pilot-scale HPGR, this simulation model was applied to a laboratory-scale HPGR. An appropriate shape of a roll installed in a laboratory-scale HPGR was investigated. Simulation results indicated that the suitable roll shape for a laboratory-scale HPGR was designed by a dimensionless roll gap and dimensionless throughput. A laboratory-scale HPGR designed based on simulation results could experimentally reproduce grinding results similar to those obtained from a pilot-scale HPGR.

PB315 Effects of molecular weight on drag force of polyethyleneglycol in flows measured by a scanning probe microscope
Kobe University, Kobe, Hyogo, Japan

Very dilute high-molecular-weight polymer solutions induce complex flow behaviors. This is due to polymer deformation in a flow, which causes mechanical interaction between a deformed polymer and fluids, and between polymers in flows. We consider such polymer-fluids interaction and polymer-polymer interaction clarify the complex behaviors of polymer solution.
In this study, we measured the drag force of polyethyleneglycol (PEG) in flows by using a scanning probe microscope (SPM). Methoxy polyethyleneglycol thiol (mPEG-SH) was attached to the cantilever probe of the SPM, which was further immersed in flows of glycerol and polyethyleneglycol (PEG) solutions. Here, we have prepared several molecular weight of mPEG-SH from 10k to 40k. The mPEG-SH-bonded cantilever detects the extra force due to polymer-fluids and polymer-polymer interaction in flowing fluids. The extra force was increased with increasing the molecular weight. The conformation of the mPEG-SH polymer bonded to the probe of the cantilever was predicted, and the drag force due to the deformed mPEG-SH was calculated. The forces detected by experiments using the SPM and the forces obtained by model calculations were compared, and found to be reasonably close.

PB316 Mass transfer in alternating flow of two immiscible liquids in microchannel
Mayu NISHIYAMA, Takatomo TSUDA, Hiroyuki HIRANO, Tomohiko KIHARA, Hideaki OBATA, Kenya KUWAGI
Okayama University of Science, Okayama-shi, Okayama 700-0005, Japan

The mass transfer of the liquid-liquid extraction process in the alternating flow of two immiscible liquids in the microchannel was experimentally visualized. In this flow, each segment flows alternatively in the microchannel. In this study, water with congo red as the indicator, and cyclohexane with acetic acid were induced into the microchannel with the rugged wall of the diamond shape. The alternating flow of these two kinds of liquids was observed, and the mass transfer of acetic acid from aqueous phase into organic phase was visualized as the change of the color of aqueous phase. Figure 1 shows the experimental result. The microchannel was made of stainless-steel and placed between two quartz glass plates. The narrowest width of the microchannel is 0.3 mm, and the widest one is 1.45 mm in the diamond shape. Two kinds of liquids were fed into the microchannel with the syringe pumps at 0.07 mL/min (13 mm/s). Orange area is aqueous phase of water with congo red, white area is organic phase of cyclohexane with acetic acid. Blue area is aqueous phase of water, congo red and acetic acid which transfers from organic phase, and the color of aqueous phase changes from orange to blue as the concentration of acetic acid increases. The color of the aqueous phase completely changed from orange to blue after 9.95 mm from the confluent point. As the result, the distance from the confluent point where the color changed completely from orange to blue becomes longer as the inlet velocity increases. This result suggests that the ruggedness of the wall is not effective for this extraction process. This work was supported by the Grant for the Promotion of OUS Research Project (OUS-RP-30-4) of Okayama University of Science.

PB317 Influence of The Injection Point on The Mixing Process with A Large-type Impeller in Laminar Mixing
Keisuke SAKATA, Kazuhiro OJIMA, Kazuhiko NISHI
Chiba Institute of Technology

In laminar mixing with a large-type impeller, the initial injection point of the mixing object is known to influence mixing processes and the mixing completion time. This study investigated the relation between the injection points and the mixing performance of MAXBLEND, a large-type impeller, by CFD of tracer particles.
For this study, a 0.1 m diameter vessel was used. 1331 particles were placed on an injection point as a 53 mm3 cube. Based on the three-dimensional particle coordinates for every time, the distance from each particle to the nearest particle is calculated (Lnp). The average of these distances was calculated for every time (Lnp, ave).
In all, we investigated 48 injection points (Fig. 1). In Fig. 1, the results of the numerical simulation of mixing are shown as a relation between time and Lnp, ave . As shown there Lnp, ave gradually becomes larger with advanced mixing from 1 mm (t = 0). It becomes almost constant in a complete mixing state. For injection point No. 32, the mixing completion time was the shortest. However, the mixing completion time of No. 38 was the longest. Results showed a large difference in the complete mixing time depending on the injection point.
To investigate the scale-up effect, mixing in the 0.15 m diameter vessel was simulated. When the Reynolds number was equal using the same liquid, the relation between Lnp, ave and time in a large vessel differs from that in a small vessel.
However, these data are arranged similarly to the lines, independently of scale, using dimensionless mixing time, which is the product of the time and the impeller rotational speed, and the normalized average nearest particle distance, which is calculated by dividing Lnp, ave by the vessel diameter. Results demonstrated that mixing in the large vessel can be estimated from results of the small vessel using this relation.

PB318 Particle dispersion and aggregation under various shear fields
Katsuki MURANISHI1, Hayato MASUDA2, Takashi HASEGAWA3, Takafumi HORIE1, Naoto OHMURA1
1 Department of Chemical Science and Engineering, Kobe University, 1-1 Rokkodai, Nada, Kobe, Japan
2 School of Food and Nutritional Science, University of Shizuoka, 52-1 Yada, Suruga, Shizuoka, Japan
3 Toagosei Co., Ltd., General center of research and development, 8 Showamachi, Minato, Nagoya, Aichi, Japan

Fine particles make an important role for the production of functional materials in various industries such as foods, pharmaceuticals and paints. Because physical properties of fine particles depend on the particle size and the particle size distribution, it is important to accurately control these properties during the processing. Recent developments in functional materials have been required for more accurate control of the particles size and the particle size distribution.
Generally, fine particles are produced using a stirred tank with the aim of large-scale production. However, in the stirring tank, fine particles easily aggregate due to shear in a flow filed. Therefore, in order to control the particle size and the particle size distribution, the effect of shear on particle aggregation should be understood. However, there is the shear force (shear-rate) distribution in a stirred vessel and it differs with the impeller type. It is necessary to clarify how the difference in the impeller type affects the particle size and the particle size distribution. This study investigated the effect of impeller type on the size distribution of aggregate of fine particles.
Two types of impeller, a Rushton turbine and a 3-retreat impeller were used for particle aggregation. The size distribution of aggregates was measured by a microscope (VHX-100, Keyence Co., Ltd.) and a laser diffraction particle size analyzer (SALD-300V, Shimadzu Corp.).
It has been found that the 3-retreat impeller promotes particle aggregation as compared with the Rushton turbine impeller. Besides, energy dissipation with the 3-retreat impeller was larger than it with the Rushton turbine impeller. These results imply that an impeller with smaller energy dissipation would suppress particle aggregation. In the conference, the results using a Taylor-Couette flow apparatus having the relatively narrow shear-rate distribution will be also reported.

PB319 Delivery of hydrophilic materials into tobacco BY-2 cells using PLGA nanoparticles
Hikari AISU, Yasuhiro KONISHI, Toshiyuki NOMURA
Department of Chemical Engineering, Osaka Prefecture University, Osaka, Japan

During the past decades, nanoparticles (NPs) have been widely studied as carriers of drug delivery system. Unlike the animal cells, plant cells have a rigid cell wall, and it is physical barrier for intracellular NP uptake. However, past our study revealed that the poly lactic-co-glycolic acid (PLGA) NPs were taken into the tobacco BY-2 cells with cell wall by controlling the NP exposure condition. In this study, we attempted to deliver PLGA NPs containing hydrophilic biomaterials into the tobacco BY-2 cells. The fluorescent BSA was used as model biomaterials. BSA adsorbed PLGA NPs were prepared as follows: PLGA NP was prepared by the emulsion solvent diffusion method. In order to adsorb negatively charged BSA on the PLGA NPs, the cationic lipid DOTAP was adsorbed on the PLGA NPs and BSA was then adsorbed on them. BSA encapsulated PLGA NPs were prepared as follows: In order to encapsulate hydrophilic BSA in hydrophobic PLGA NP, BSA was hydrophobized using DOTAP and the BSA/DOTAP complex was then encapsulated in PLGA NPs. BY-2 cells and PLGA NPs were mixed in MS medium for 1 hour. Then, the localization of NP and BSA was observed using CLSM. When exposing BSA adsorbed PLGA NPs, the PLGA NPs were taken up into the cells but BSA was remained on the cell wall. This is presumably because the adsorption of BSA on the NP surface reduced the cell affinity of PLGA. In contrast, when exposing BSA encapsulated PLGA NPs, the BSA was found to be taken up into the cells when the charge of the NP surface changed from negative to positive with the increase of DOTAP. These results indicate that hydrophilic biomaterials can be delivered into plant cells by hydrophobizing BSA with DOTAP and encapsulating in PLGA NPs.

PB320 Flow polarization imaging around a rising bubble in aqueous gelatin solution under gelation process
Hiroya TOKUUMI1, Hiroki NAKANO1, Shuichi IWATA1, Ryo NAGUMO1, Hideki MORI1, Tsutomu TAKAHASHI2
1 Nagoya Institute of Technology, Nagoya, Aichi, Japan
2 Nagaoka University of Technology, Nagaoka, Japan

Flow polarization images around a rising bubble launched periodically in a cooling 3 wt% gelatin aqueous solution were captured by the two-dimensional high-speed polarization camera. The flow polarization imaging involves two dimensional retardation profile and orientation angle profile, respectively. The retardation profile correlates significantly with elasticity of the transparent solution under the validity of the optical-stress rule. The gel point of the aqueous solution of gelatin was evaluated in terms of viscoelastic properties of the gelling solution measured by the rheometer.
When the solution temperature was kept at 33 deg-C, shape of the rising bubble with diameter of 8.4 mm was sphere. Because the solution behaves Newtonian fluid of sol and the bubble Reynolds number was order of 1. There is almost no observable change for both retardation and orientation angle profiles.
After cooling down of the prepared mixture to 23 deg-C at a cooling rate of 0.254 deg-C/min for 39.3 minutes, and then the solution was kept at 23 deg-C. The growth of network structure of gelation causes the transition of the bubble shape from spherical to spherical with a cusp at about 3400 seconds. Slight change in retardation and clear orientation angle profile can be observed around the rising bubble. This suggests that at this event the elasticity of the gelling solution became dominant.
At about 3600 seconds of gelation, the bubble shape transformed to oblate shape with a long tail. The long tail was surrounded by high retardation region (i.e., high elasticity solution) in vertical orientation much higher than the others mentioned before. Therefore, the solution surrounding the long tail, which was supplied by the negative wake, was stretched vertically.

PB321 Experimental study of the dynamics of two-fluid displacement and flow through eccentric annuli
University of Adelaide, Adelaide, South Australia, Australia

We have developed a flow system for systematic study of the dynamics of two-fluid displacement and flow in annuli. This flow is relevant to many industrial applications, especially in the cementing operations in oil/gas well completions, where drilling fluids are displaced from the annulus between the casing and the well bore by a series of spacer fluids and cement slurries. The annular flow apparatus was designed such that it can be operated at various degrees of eccentricity and different angles of inclination to simulate the type of flows in oilfield drilling and cementing operations. A special feature of the flow system is that the inner cylinder can be rotated during displacement, allowing the effects of helical flow on the performance of the annular displacement process to be studied. Flow and displacement tests with various model non-Newtonian fluids representing drilling and cementing fluids have been conducted at different eccentricities, pipe inclinations, and over a range of flow rates and cylinder rotational speeds. Flow visualization results consist of video images capturing the movement and evolution of the fluid-fluid interface that clearly illustrate the effects of annular eccentricity, displacement rate, cylinder rotation and fluid rheology on the displacement process. In addition, the velocity profiles through the annulus at a fixed point downstream were determined by Particle Image Velocimetry (PIV) method to elucidate the dynamics of the displacement fluid-fluid interface. PIV results obtained have revealed interesting phenomena in the two-fluid displacement region that depend on the fluid viscosity ratio and the annular eccentricity. Pressure drop measurements produce data that can be used to develop models for predicting friction losses associated with single-fluid flow and two-fluid displacement in eccentric annuli. The results obtained will be useful for assessing the effects of important variables such as eccentricity, pipe inclination, flow rate, pipe rotation and fluid rheology, that impact on the effectiveness of the annular displacement process.

PB322 Continuous production of monodisperse water-in-oil droplets under pulsatile-free flow
Jia Yun XU, Jen Han CHIU, Jen-Huang HUANG
National Tsing Hua University, Hsinchu, Taiwan

Peristaltic pump is a most commonly used equipment to continuously introduce the fluids. However, the peristaltic pump may produce a pulsatile flow, limiting the applications for multiple purpose. To address this issue, we design a flow stabilizer connected to the outlet of the peristaltic pump. When the pulsatile flow enters the flow stabilizer, the elastic membrane is expanded, providing a buffer area for the pulsatile flow to deliver a steady flow at the outlet. The dampener was fabricated with PET and acrylic embedded with polyurethane as elastic membrane. The results show that the flow stabilizer with larger overall membrane area has better Fluctuation Reduced (FR) value. The elastic membrane arranged in parallel shows better FR than in series. Furthermore, we established a droplet generating system, which can continuously form uniform water-in-oil droplets. The system included a droplet generator, a flow stabilizer, and pumps. To continuously generate the droplets, a peristaltic pump connected with a flow stabilizer were used to feed the continuous phase. We used soybean oil with 5% w/v Polyglycerol polyricinoleate (PGPR) as the continuous phase, while pure water as the discontinuous phase. The results demonstrate that the monodisperse water-in-oil droplets with uniform size could be successfully generated. Moreover, the size of the droplets could be well controlled by altering the flow rate of the water. The droplet diameter increased from 0.311 mm to 0.519 mm (CV < 5.7 %) as the water flow rate increased from 5 μL/min to 80 μL/min. In conclusion, the integration of the flow stabilizer reduced the pulsatile flow of the peristaltic pump up to 99.25 %, allowing to continuously generate monodisperse droplets. We envision our continuous droplet generator system can apply to continuous and scalable production of chemical.

PB323 Photocatalytic degradation of volatile organic compounds (VOCs) using ultrasonically-formed droplets containing TiO2 particles
Miyu KIMURA1, Ryoichi NAKAYAMA1, Norikazu NAMIKI1, Kazuhiko SEKIGUCHI2, Naoki KAGI3
1 Kogakuin University,
2 Saitama University,
3 Tokyo Institute of Technology

It has been well-known that photocatalytic degradation of indoor air pollutants such as volatile organic compounds (VOCs) requires a high degradation efficiency for a long time without lowering the efficiency due to coking on UV-irradiated TiO2 surface.
In our previous work, we fabricated a photocatalytic reactor where photocatalytic degradation of toluene vapor took place on TiO2-containing droplets formed by ultrasonic atomization under UV irradiation, and demonstrated that a stable degradation efficiency was kept continuously under the optimal operation conditions. Therefore, the present study aimed to improve the degradation efficiency by dispensing additive particles, such as carbon black (CB) and silica (SiO2) ones, into TiO2 suspension.
Two sorts of additives were added to the suspension of TiO2 particles in the photocatalytic reactor, and then the toluene generated at a concentration of 5 ppm was fed to the reactor where TiO2-contaninung droplets irradiating with UV-A ray. The test air was sampled at the inlet and outlet of the photocatalytic reactor, and the concentration of toluene was determined by a GC-FID to determine the decomposition efficiency Ed.
As a result, Fig1 shows the change in the toluene degradation efficiency with additive particle concentrations in the TiO2 suspension. It was found that the degradation efficiency was increased by dispensing the additives, and had an optimum value at the additive concentration. The addition of CB might increases the adsorption capacity to toluene while it might be considered that CB coats the surface of TiO2 particles and UV-ray does not reach TiO2 when the amount of addition exceeds a certain level. Although the effective surface area of TiO2 particles contributing to the photocatalysis increased due to the presence of suspended TiO2 agglomerates coated with SiO2 particles, the extreme increase in SiO2 particles could enhance the ultraviolet light shielding effect of the SiO2 particles themselves.

PB324 Numerical Simulations using the MOF method of Individual Bubbles Growing and Detaching due to the Nucleate Boiling Process.
Yuya SHUDO1, Mitsuhiro OHTA1, Mark SUSSMAN2
1 Tokushima University, Tokushima 770-8506, Japan
2 Florida State University, Tallahassee, FL 32306, USA

In this study, the growth of single bubbles, due to nucleate boiling, is computationally examined using the moment-of-fluid (MOF) method. The MOF method represents sharp deforming boundaries between phases by evolving both volume fractions and centroids. The numerical simulations are carried out by solving the conservation law equations for mass, momentum, and energy, taking into account the appropriate jump conditions at the interfaces between substrate, liquid, and vapor. The substrate is modeled as a rigid body and the liquid and vapor are simulated as incompressible fluids. In order to carry out the computations as efficiently as possible, dynamic adaptive mesh refinement (AMR) is used in which the computational domain is an adaptive hierarchy of rectangular grids as opposed to a single, uniform, rectangular grid. In this study, the single bubbles periodically growing from a single nucleation site is two-dimensionally and axisymmetrically computed under the temperature difference of 7 K between the heated wall and water. The continuous generation process of nucleate boiling bubbles is successfully reproduced and thermal and flow fields in nucleate boiling are clearly shown. It is showed that the second and subsequent bubbles after the first bubble is released are stably formed. The growth rate of the second and subsequent bubble is faster than that for the first bubble and the growth rate of the second and subsequent bubble becomes constant. It is verify that our computational results for the growth rate of bubbles, the bubble departure time and the bubble volume for the second and subsequent forming bubbles agree well with the previous study. Our computational method using the MOF method can be effective for computing boiling problem.

PB325 An Experimental Study of the Morphology of a Drop Rising through a Hydrophobically Modified Alkali-Soluble Emulsion Polymer Solution
Takuya MAKITA1, Mitsuhiro OHTA1, Shuichi IWATA2
1 Tokushima University, Tokushima 770-8506, Japan,
2 Nagoya Institute of Technology, Nagoya 466-8555, Japan

The dynamic motion of a drop rising in a highly viscous hydrophobically modified alkali-soluble emulsion polymer (HASE) solution with pH = 9.0 is experimentally examined. In this study, a 1.65 wt% HASE polymer solution, which is adjusted to pH ≈ 7.0 by adding a sodium hydroxide solution, is used as the matrix fluid and salad oil is used as the drop. For sufficiently small drops, a threadlike long trailing edge at the rear of a drop is observed, similarly as for the case of a small bubble. It is newly observed that the threadlike trailing edge for the drop is much longer and thicker than that for the bubble. From experimental observations, it is found that a drop is more susceptible to the effect of viscoelastic properties of the surrounding HASE solution than the for the bubble case. For the case of bubble rise motion, the threadlike long trailing edge turned into threadlike branches for increasing bubble size; no such the tendency can be observed for the drop case. In microscopic observations for the bubble, it was reported that very unique microstructures emerged from gas-liquid interfaces in the motion of large bubbles, but on the other hand, microstructures at the liquid-liquid interface cannot be observed for drops. It is revealed that there is a pronounced difference between how the viscoelastic properties of a HASE solution effects bubble morphology versus drop morphology.

PB326 Numerical simulation of droplet breakup in droplet swarm by level set method with multi-levels
Tsinghua University, Beijing, China

In the present work, a level set method with multi-levels was developed to simulate the breakup behaviors of multi-droplets in a macro extraction device, the pulsed disc and doughnut column (PDDC). The deformation and breakage behaviors of droplets in droplet swarm were accurately captured. It was found that the shearing effect of the continuous phase flow, the collision between droplets and internals, and the Plateau–Rayleigh instability of the interface of liquid column would lead to the breakup of droplets. These breakup patterns were in good agreements with the experimental results. Moreover, the influences of pulsation intensity and droplet size in droplet breakup behaviors were investigated. It was concluded that the higher the pulsation intensity, the easier the droplets to break up. In addition, large droplets were found to be more likely to break up into multiple daughter droplets. Generally, the droplet breakup frequencies predicted by numerical simulation presented acceptable agreements with experimental results.

PB327 Determination of dynamic interfacial tension in a pulsed disc and doughnut column
Bo WANG, Shan JING, Shaowei LI*
Institute of Nuclear and New Energy Technology, Tsinghua University

Interfacial tension is an essential physical property in liquid-liquid extraction. Under mass transfer conditions, the interfacial tension changes due to mass transfer and concentration variation. The measurement of dynamic interfacial tension in such condition is of vital importance to direct the design of extraction equipment. In previous study (Zhou at al., Chemical Engineering Science, 197, 172–183), we presented the quantitative relation between the droplet breakup frequency function and interfacial tension. In this work, the droplet breakup frequency function in mass transfer process is measured at four different heights of the pulsed column using the method developed in our previous work (Zhou at al., AIChE Journal, 63(9), 4188-4200). The dynamic interfacial tension at different height of the column is then calculated by regression method. With acetic acid – water as the dispersed phase and 5%TBP – kerosene as the continuous phase, the results show that the dynamic interfacial tension increases with height decreasing. Comparing the dynamic interfacial tension with the static interfacial tension of equilibrium liquid-liquid system, we have found that the former is smaller than the latter when the concentration of acetic acid in the continuous or dispersed phase is the same. This result indicates that interphase mass transfer leads to decreasing of the interfacial tension. The decreasing extent of the dynamic interfacial tension has a positive correlation with the mass transfer flux. Furthermore, under mass transfer conditions, binary breakage occupy the dominant position at different height and up to quintuple breakage can be observed.

PB328 Volume penalization method for gas-liquid-solid flows with immersed free surface
Giang NGUYEN1, Kimiaki WASHINO1, Takuya TSUJI1, Toshitsugu TANAKA1
1 Osaka University, Suita, Osaka, Japan

Particulate flows in a mixture of gas and liquid, i.e. gas-liquid-solid three-phase flows are encountered in many powder handling processes, and it is of paramount importance to understand the complex interactions among phases. This work presents a simulation model for the study of gas-liquid-solid flows. In the given model, the solid-fluid interaction force is introduced by the Volume penalization (VP) method inherited by the study of Engles et al. (2015). Considering solid phase as a porous media, fluid is allowed to flow through the solid body with a certain value of permeability. The solution for determining the local permeability at solid surface is described in this study. The interface between gas and liquid is captured by the Volume of fluid (VOF) method coupled with the Level Set (LS) method. The interfacial interactions, such as the wetting of solid surface and surface tension force, are taken into account by using the Immersed free surface (IFS) model proposed by Fujita et al. (2015). The IFS model is originally designed for LS method, and it is adapted to the VOF framework in this work. Several simulations are performed to validate the proposed model. The resultant drag force acting on the particle as well as the computed surface tension force and contact angle are in good agreement with the theoretical values.

PB329 Molecular simulation of Amphotericin B-Ergosterol channel for the novel water channel
Hao Chen WU1, Tomohisa YOSHIOKA1, Keizo NAKAGAWA1, Takuji SHINTANI1, Toshinori TSURU2, Hideto MATSUYAMA1
1 Kobe University, Kobe, Japan
2 Hiroshima University, Hiroshima, Japan

Global water scarcity and pollution became a serious problem around the world. In order to relieve this issue, membranes processes have been widely applied to water treatment. With the increasing requirement for water, it is indispensable to continue search for membranes that can perform more efficiency on water flux and ion rejection. Although novel Aquaporin channel synchronously transports water rapidly while completely rejecting ions [1], Aquaporin is very costly and has a complex fragile molecular structure. These drawbacks make it formidable to apply or produce on an industrial scale. Some materials were searched for replacing Aquaporin channel, an Amphotericin B-Ergosterol channel (AmBEr) is a type of self-assembly organic channel [2], AmBEr is considered to be potential candidates for the biomimetic artificial channels. In this study, AmBEr was constructed and explored via molecular simulations to understand the structural characteristics and transport mechanism on a molecular scale. The chemical structures of Amphotericin B and Ergosterol monomer were shown in Fig. 1. AmBEr molecular models were constructed and investigated via molecular dynamics (MD) simulation procedures, Monte Carlo (MC) simulations and Quasi-non equilibrium MD were adopted to simulate the properties of calculation models. Structural characteristics and water sorption behaviors were introduced. All these molecular models were constructed using BIOVIA Materials Studio® commercial software.

PB330 Effects of Filling on the Segregation Patterns in a High Fill Level Rotating Drum
Chi-Yun LIN1, An-Ni HUANG1,2, Hsiu-Po KUO1,2
1 Department of Chemical and Materials Engineering, Chang Gung University, Taoyuan City 33302, Taiwan
2 Department of Otolaryngology-Head & Neck Surgery, Linkou Chang Gung Memorial Hospital, Taoyuan City 33305, Taiwan

When we mix particles of different sizes in a rotating drum, segregation may be observed. In this study, the segregation of a granular mixture consisting of 50% v/v 0.55 mm glass particles and 0.77 mm glass particles in a high fill level rotating drum is investigated. The segregation patterns appear after few revolutions, and the surface segregation band size and number become stable within 30 min. For the spatio-temporal diagram, the two smaller-particle-rich segregation bands take longer time to move toward the drum center when the fill level increases from 60%, 70% to 80%. The segregation patterns inside the bed are observed by the cross-sectional slices. Peculiar segregation patterns composed by strikes and core-in-core regions are observed for the first time.

PB331 Validation of CPFD models in for simulating hydrodynamics, heat transfer and reactions in CFB downer reactor for coal pyrolysis with binary particles
Yingya WU, Xiaogang SHI, Xingying LAN*, Jinsen GAO
State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing

It is well known that the low-rank coals such as lignite and sub-bituminous with higher volatile and moisture accounts for a large proportion of coal, which is the most abundant fossil energy resource in the world.Compared to the conventional fixed and Circulating Fluidized Bed (CFB) riser, the downer reactor, in which gas and solids move downwards concurrently, provides prominent advantages such as more uniform gas-solids flow structures, shorter particles residence time, less gas-solids back-mixing.These unique characteristics is particularly beneficial and suitable for coal fast pyrolysis, which need short but uniform contact time to achieve high reaction selectivity and yields of desirable products.
The CPFD approach based on the MP-PIC method was used to study the hydrodynamics, heat transfer and reactions in CFB downer reactor for coal pyrolysis with binary particles. Firstly, the comparison of solids distribution profiles of binary particles showed the CPFD approach with the cluster-based drag model is capable of accurately predicting the gas-solids flow and particle mixing characteristics. On the basis of the suitable gas-solids flow model, we further simulate the heat characteristic by coupling the heat transfer model. The simulation results show the temperature mixing index predicted by the coupled heat transfer model is in good agreement with the experimental value. By analyzing the heat transfer characteristics of particles, it can be found that the heat transfer process mainly occurs near the entrance, the interaction between gas and particles near the nozzle plays a key role. Therefore, more attention needs to be paid on the inlet of particles design of the downer. Finally, the CPFD model was further extended to reveal the coupled flow-reaction behaviors on coal pyrolysis reactor with binary particles. The results demonstrate that the CPFD model can accurately predict the hydrodynamics, heat transfer and reactions behavior of binary particles.

PB332 CFD simulations and optimization for transfer lines
Research Institute of Petroleum Processing, SINOPEC, Beijing 100083, China

Transfer lines are used for petroleum transportation in petrochemical industry, which refers to a pipeline connection between the furnace and the vacuum column in the crude oil distillation unit. A well designed transfer line can increase the evaporation rate of the feed in the vacuum distillation tower, improve oil product quality and save energy for vacuum distillation unit. To better design new pipelines or optimize the existing ones, it is necessary to describe the hydrodynamic behaviors of the multi component fluids flow in the pipelines. However, due to the complexity of the system, the model for analysis of the flow inside the transfer line has been paid less attention.
In this study, a commercial computational fluid dynamics package was used to develop a three-dimensional, fully turbulent flow model for the simulations of the multi component mixture across a pipeline. The simulated results of the pressure, velocity and Ma number distributions provided an insight into the phenomena occurring within the flow field in the transfer line. The analysis showed that the pressure drop of a transfer line is strongly affected by the structure of transition section and junction. On the basis of this, a new structure is presented to optimize the flow, and the pressure drop is lower than that of the original one. The modeling methodology and the results presented will be useful for evolving better designs of transfer line or other similar pipelines.

PB333 Influence of Hansen Solubility Parameter on Resin Flowability
Yuki KATO1, Shinichi TSUTSUMI2, Nobuyuki FUJIWARA1, Hideki YAMAMOTO1
1 Kansai University, Osaka, Japan
2 Panasonic Corporation, Osaka, Japan

The bonded magnet is a composite material formed by mixing a resin and magnetic powder and is used as a magnet for a motor or a sensor. In the case of a bonded magnet by injection molding, it can be molded into various shapes, the degree of freedom in motor design is increased. Furthermore, if the magnetic properties of the injection molded bonded magnet can be enhanced, a more sophisticated motor can be manufactured. To enhance the magnetic properties, it is necessary to increase the concentration of the magnetic powder. However, as the addition amount of the magnetic powder is increased, aggregation of the magnetic powder occurs, the flowability decreases, and there is a problem that molding becomes difficult. To address this problem, measures have been taken to treat the surface of the magnetic powder with a silane coupling agent or the like to improve the affinity to the resin and to disperse the resin highly. However, at present the selection of surface treatment agents is conducted empirically.
Therefore, I focused on Hansen Solubility Parameter (HSP). HSP is a physical property value quantitatively evaluated the affinity between substances, and it is applied in various fields.
In this study, we examined the influence of HSP of magnetic powder on the flowability after mixing. First, the magnetic powder was surface-treated with various silane coupling agents, and HSP was measured to evaluate its affinity to PA6. Thereafter, the magnetic powder was added to PA6 at the same concentration, and the viscosity was measured to measure the fluidity. As a result, as the combination of the magnetic powder and the resin with better affinity in HSP theory, the flowability was improved, and it was possible to confirm a high correlation between the HSP and the flowability.

PB334 Characterization of the Particle Cohesion by the Pressure Drop Monitoring in a Fluidized Bed
Wan-Yi HSU1, An-Ni HUANG1,2, Xuan WANG1, Hsiu-Po KUO1,2
1 Department of Chemical and Materials Engineering, Chang Gung University, Taoyuan City 33302, Taiwan
2 Department of Otolaryngology-Head & Neck Surgery, Linkou Chang Gung Memorial Hospital, Taoyuan City 33305, Taiwan

Evaluation of the flow properties of powders is essential for the designing and operations in powder-related industrial processes. In this study, the powder cohesion is evaluated by the measurement of the pressure drop across the bed during the fluidization and defluidization procedure in a FT4 Powder Rheometer (Freeman Technology). Glass beads with the diameter between 88 μm to 105 μm are fluidized in a cylindrical glass column with inner diameter of 50 mm by dried nitrogen. The pressure drop overshooting at incipient fluidization is used to characterize the powder cohesion and the bed cohesion is altered by Polyethylene glycol (PEG) addition and powder bed normal stress. When no normal stress is applied to the powder bed, the pressure drop shows a linear increasing during the overshooting period. However, when a 20 kPa normal stress is applied to the powder bed, the pressure drop shows a two-stage increasing during the overshooting period. A new cohesive powder fixed bed fluidized bed transition state is initially reported. The measured bed cohesion is ca. 45 Pa, which is comparable to the theoretical prediction of Molerus (1975) and Rumpf (1975).

PB335 Numerical study on fine particles behavior in an incinerator by coarse-graining DEM
Putri Mustika WIDARTININGSIH1, Yuki MORI1, Mikio SAKAI2
1 Department of Nuclear Engineering and Management, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan
2 Resilience Engineering Research Center, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan

In industrial incinerators, hazardous substances from the combustion waste are concentrated in fine particles. Collecting and reducing fine particles is particularly challenging, and thus it becomes one of the major problems in industrial incinerators. A control plate was introduced into an industrial incinerator to reduce the emissions of hazardous fine particles. However, the efficiency of the control plate against smaller sized particles is necessary to be investigated. The coupled discrete element method and computation fluid dynamic (DEM-CFD) are employed in a solid-fluid coupling problem even where the solid particle size is fine. One of the concerns in the DEM-CFD is the requirement of excessive computer capacity when the numerous particles are applied. Therefore, a coarse grain model is adopted here to perform the calculations using a single computer. For the sake of approaching the actual condition of industrial incinerators, poly-dispersed particle system is employed in this study, where expressed by a combination of two coarse ratio. The simulation results show that the control plate works well to capture the fine particles. In addition, the velocity of particle flow is significantly decreasing when a control plate is employed.

PB336 Establishment of a novel universal index to predict particle packing ability for various slurries
Nana KITAI1, Naoya IWATA1, Takamasa MORI2,3, Hiroshi SATONE3,4
1 Graduate School of Science and Engineering, Hosei University, Koganei, Tokyo, Japan
2 Department of Chemical Science and Technology, Faculty of Bioscience and Applied Chemistry, Hosei University, Koganei, Tokyo, Japan
3 Hosei University Research Institute for Slurry Engineering, Koganei, Tokyo, Japan
4 Department of Mechanical and System Engineering, Graduate School of Engineering, University of Hyogo, Himeji, Hyogo, Japan

In wet-shaping process, it is well known that the particle dispersion state greatly affects the product qualities. Thus, it is important to evaluate and control the slurry characteristics properly. However, quantitative evaluation index that can compare the particles dispersion state under different slurry conditions such as particle concentration, primary particle size, particle density, shape, and solvent viscosity, etc. has not been established, yet. In this study, we measured the hydrostatic pressure of slurry prepared in various conditions under gravitational settling. Additionally, the time change of hydrostatic pressure for the slurry whose particles are assumed to perfectly disperse as primary particle was calculated for the slurries used in this study. In order to calculate the hydrostatic pressure curve more precisely, the particle size distribution measured by sedimentation was considered. The novel index, the ratio of measured hydrostatic pressure to calculated one, was introduced to discuss the particles dispersion state. It was shown that the index (hydrostatic pressure ratio) had a good connection to the final packing fraction of the sediment, indicating that the index should be useful to quantitatively represent the particle dispersion state regardless of the slurry conditions.

PB337 Alteration of lipid bilayer permeability and structure of liposomes using gas-liquid flow
Makoto YOSHIMOTO, Tetsuya FUJIE, Yusuke NAKANO
Department of Applied Chemistry, Yamaguchi University

Phospholipid vesicles (liposomes) are soft colloidal particles which are applicable to fabricating carriers of biopharmaceuticals, protocell models, and immobilized enzymes. The permeability of lipid bilayer membranes towards small molecular mass compounds is of significance for the above applications of liposomes. In the present work, 5(6)-carboxyfluorescein-containing large unilamellar liposomes were prepared and suspended in gas-liquid flow generated in external loop airlift bubble columns. The release rate of the dye molecules from the liposomes was examined at 40 °C under various operation conditions of the bubble columns with different configurations. The permeability coefficient of the dye molecules through the bilayers of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine lipids was clearly dependent on the superficial gas velocity of the bubble column (1-3 cm/s). The mean diameter and size distribution of liposomes were practically unaffected by being suspended in the bubble column, as evaluated with the dynamic light scattering measurements. These results indicate that the permeability of liposomes increased in the gas-liquid flow. On the other hand, the release rate of the dye molecules through the lipid bilayers incorporated with small fractions (1-5 mol%) of poly(ethylene glycol)-conjugated lipids exhibited significantly higher than that through unmodified lipid bilayers. The size distribution of the modified liposomes was altered by being suspended in the bubble column, indicating that the membrane integrity of liposomes was significantly altered. The effect of liquid shear stress on the structural stability of liposomes was separately examined by shearing the liposomes in a cone-and-plate geometry to assess the bubbles-liposomes interaction in the bubble column. All of the above results demonstrate that the structural stability of liposomes was controllable using the gas-liquid flow.

PB338 Effects of relaxation time of solutions on vortex deformation and turbulence statistics in two-dimensional turbulent flow
Kobe University, Kobe, Hyogo, Japan

A small amount of polymer in turbulent flow reduces turbulent drag, which is called drag reduction. It is said that extensional rheological properties, such as long relaxation time and extensional viscosity of the fluid are keys for the phenomena. The characteristic extensional rheological properties of the solution deform vortices in turbulent flow, thus, the turbulent flow is also affected.
In this study, in order to focus on the effects of extensional rheological properties of fluids on vortex deformation in a turbulent flow, a flowing soap film known as a two-dimensional (2D) flow with a small influence of shear stress is used. The vortex shedding in the flow were visualized using interference patterns, and the local velocity fields were measured by particle image velocimetry (PIV). The vortices shed at the grid in the 2D flow was affected by polyethylene oxide (PEO, Mw = 3,500,000) concentration. The original shape of the vortices was deformed by increasing the PEO concentration, and the vortices were disappeared close to the grid at a certain concentration. However, the vortices again appeared at even higher concentration. In this study, we categorized these vortices into three types. Indeed, the generation of these vortices were affected by the extensional relaxation time of the PEO solution. The difference of these vortices were also analyzed by the fluctuation intensity of the flow field and by the turbulent statistics. Turbulent kinetic energy transfer, production and dissipation term of the turbulent kinetic energy were calculated the local velocity. The turbulent statistics implies variation of energy transfer in 2D flows, which was caused by the viscoelasticity of PEO solution.

PB339 Study on the fixed salt removal effect by fine bubble
Yuji MIKASA1, Naoya YAMAWAKI1, Hiroaki SHIDA2, Hayato OKUMURA3, Shigenori AKAMATSU3, Yusuke NISHIUCHI3, Takashi HATA3
1 Advanced Course of Material Engineering, National Institute of Technology (Kosen), Kochi College, Nankoku, Kochi, Japan
2 Ligaric Co., Ltd, Suita, Osaka, Japan
3 Department of Social Design Engineering, National Institute of Technology (Kosen), Kochi College, Nankoku, Kochi, Japan

In recent years, it has become clear that fine bubble (micro/ultrafine bubble) have properties different from those of ordinary bubble. For example, the surface area of fine bubbles per the same volume is larger than that of normal bubbles, including chemical reactions and physical adsorption at the gas-liquid interface, a dramatic improvement in mass transport, and having a positive/negative charge (zeta potential) on the surface of fine bubble. Cleaning using the features of fine bubble in particular has been noticed, and there is also a high industrial need. For example, the use of plastic cleaning in recycling industries and anti-corrosion cleaning of structures with flying sea salt particles in coastal areas has begun.
Therefore, in this study, the effect of fixed salt removal by fine bubble was investigated. As a result, it was confirmed that the cleaning effect of fine bubble water was higher than that of control water, and the effect was dependent on the concentration of fine bubble. It was also confirmed that the cleaning effect was higher in the cleaning of ultrafine bubble water than in the control water. The removal mechanism of the fixed salt seems to be that gas in the fine bubble dissolves by the pressure change around the fixed salt, resulting in supersaturation, and the bubble nucleus is generated, and a part of the salt is lifted by the micro bubble, which promotes the fixed salt exfoliation. And, it was confirmed that the cleaning effect was higher by the constant introduction of fine bubble than the system in which fine bubble existed only in the cleaning initial stage (Fig). From these results, the usefulness of fine bubble in cleaning can be expected.

PB340 Synthesis of ε-Fe2O3 particles using Sr2+ doped magnetite-silica core-shell particles
Magnetic Powder Metallurgy Research Center, The National Institute of Advanced Industrial Science and Technology (AIST), 2266-98 Anagahora, Shimoshidami, Moriyama, Nagoya, Aichi, 463-8560, Japan

The magnetite nanoparticles including strontium were synthesized by hydrothermal method. After these particles were dispersed in the ethanol aqueous solution, and coated with the several nano meter silica shell by adding TEOS solution. The ε Fe2O3 particles were prepared by heat-treating these core-shell particles by the fixed temperature. Silica was removed from these core-shell particles by use of the NaOH solution, and the particles only of ε Fe2O3 were made. The magnetic property and the special quality of the form of particle and the particle diameter were argued to the dope amount of the strontium, the silica covering amount and the synthesis condition of the heat treatment temperature to this particle. As a result, the crystal system by heat-treatment time and the change in form of particle were checked by XRD and TEM.
Samples with 5% added Sr2+ were examined for several holding times set at 900 °C. Figure was XRD at 900 °C. The sample held for 1 hour has an aspect ratio of 1, and mostly contains ε phase and a little γ phase. Furthermore, in the sample which passed for 6 hours, although it was mainly ε phase, a little α phase was generated. The aspect ratio increased to 2 or more, and the rod width also increased to 60 nm. The crystal of silica developed with the increase of the amount of Sr2+. It is considered that this is because Sr2+ infiltrates into the silica by the doping of Sr2+, and influences the crystallization. It was found that the addition of Sr2+ causes the formation of an ε phase at a low temperature, the extension of the particles in a rod shape, and the change of the magnetic properties.

PB341 Improvement of mixing performance for highly viscous fluid using asymmetrical anchor blades
Marina YAHATA1, Takafumi HORIE1, Yoshiyuki KOMODA1, Naoto OHMURA1
1 Kobe University, Kobe, Hyogo, Japan

In chemical process industries, research and development on liquid mixing is important to save energy and resources, improve productivity and develop new materials. An appropriate impeller shape is selected to optimize mixing state in a chemical process. Very high viscosity of a fluid is an obstacle for performance of mixing processes. An anchor blade impeller is frequently used for mixing of highly viscous fluid is effective for heat transfer by scraping the tank wall but poor for the mixing. This is because the axial flow is not enough to be developed. It has been reported that mixing of highly viscous fluid can be improved by imposing unsteadiness on the flow field. This study, therefore, proposed two types of asymmetric anchor blade to improve agitation performance. Power consumption and flow patterns were experimentally and numerically observed. The asymmetric anchor blades proposed in this study were half anchor and G-shaped anchor. It is shown in Figure 1. As the results obtained by numerical simulation using a commercial CFD code (R-Flow), the power consumption using the asymmetrical anchor blades becomes smaller than that of the regular anchor blade. However, no significant difference between the half anchor and G-shaped anchor could be found. As the results of the flow pattern observation, it has been found that the mixing performance is improved in asymmetric anchor blades as compared with the regular anchor blade. It can be considered that asymmetric anchor blades make the flow field unsteady. Furthermore, it has been found that using the G-shaped anchor shows better mixing performance than the half anchor. The axial flow can be generated by the protruding portion of the G-shaped anchor. Mixing time was measured by decolorization experiments using iodine and sodium thiosulfate. The G-shaped anchor progressed the decoloring reaction most quickly and the mixing time the shortest.

PB342 Synthesis of red light emitting Si nano-particles in liquid phase
Keiichiro ISHIHARA1, Yoshiko TSUJI1,2
1 Department of Chemical System Engineering, the University of Tokyo, Tokyo, 113-0033, Japan
2 Environmental Science Center, the University of Tokyo, Tokyo, 113-0033, Japan

Semiconductor nanoparticles, known as quantum dots, are biocompatible semiconductor fluorophores and highly stable against exposure of light, which cannot be expected for organic fluorescent materials.1 Controllability of luminescence energy is also advantageous for bio-imaging since bio-permeability is good in near infrared to visible red region. However, toxic metals frequently used in quantum dots are problematic for practical use. In this context, non-toxic silicon-based nanoparticles meet the demand of bio-imaging although its stability cause the difficulty in the liquid phase synthesis, which realize large scale fabrication.
In this paper we fabricated silicon nanoparticles with two different liquid-based approaches, “Top-down” and “Bottom-up” methods. In “Top-down” method, Si powders are etched by hydrofluoric-nitric acid and decreased in its particle size to nm scale in suspension to obtain silicon nanoparticles, which show red light emitting (about 620 nm) in its PL spectra. In “Bottom-up” method, 3-Aminopropyltrimethoxysilane was used as precursors and reduced by reducing agent to obtain Si nanoparticles. The PL spectra of the nanoparticles show blue light emitting (about 420 nm), indicating that the obtained nanoparticles have smaller diameter than the nanoparticles prepared by “Top-down” method.

PB343 Optimal conditions of paddle shape and rotational speed for flow homogenization inside honeycomb
Hiroki UCHIYAMA, Takehiro ESAKI, Yousuke MATSUKUMA
Fukuoka University, Fukuoka, Japan

The dependence of the paddle rotating speed and its optimal paddle length for flow homogenization inside honeycomb has been investigated experimentally. Three types of honeycomb having various square hole size and the number of holes was used. The paddle length was varied within the range of 62, 81.6 and 120 mm and its width was 22 mm. The paddle was made of polylactic acid, which was fabricated using a 3D printer. The inlet volumetric flow rate was constant, 200 L/min. The air flowed into the header section and then into the honeycomb. The paddle attached to the motor was set to the windward side of the honeycomb. The flow rate was measured with a hot-film anemometer, which was positioned using a traverse device. The uniformity of the velocity at the honeycomb outlet was evaluated using the standard deviation of the velocity. The standard deviation is the arithmetic mean value calculated with the 169-point velocity data.
Table1 shows the experimental results. It was found that the optimum condition was almost 500 rpm of rotational speed with 120 mm paddle diameter.

PB344 Vibro-fluidized bed separation of particulate construction waste residue based on density-segregation
Tetsuaki MATSUOKA1, Takamasa YOKOUCHI1, Jun OSHITANI1, Yoshihide MAWATARI2
1 Okayama University of Science, Okayama, Japan
2 Kyushu Institute of Technology, Kitakyushu, Japan

Construction waste residue (CWR) consists of particulate organic and inorganic materials like woodchips and gravels. In Japan, the CWR should be discarded at a controlled landfill site to avoid decay of the organic materials. However, illegal dumping of the CWR is a serious trouble, because the discard at a controlled landfill site is “expensive”. If the organic materials are separated to reduce the amount to be < 5 wt%, the CWR can be discarded at an “inexpensive” least-controlled landfill site (≈ 1/5 $ of controlled landfill site). The organic materials can be easily removed from the CWR using a wet separation. Woodchips float and gravels sink in water. However, the wet separation has disadvantages; waste water treatment is necessary to avoid water pollution, a drying process is required after separation, and leakage of water may occur from the separator. Therefore, the development of dry separation is in great demand as a substitute for the wet separation. In this study, we focused on “density-segregation” in a vibro-fluidized bed. If a particulate mixture having different density is fluidized by an airflow through the bottom, lighter particles move up and heavier particles go down; this phenomenon is called “density-segregation”. If vibration is added to the fluidized bed, the density-segregation becomes clearer. We applied the vibro-fluidization to reduce the amount of organic materials in the CWR. We found that the upper layers of the fluidized bed consist of the organic materials, and the amount of organic materials in the lower layers is reduced to be < 5 wt%.

PB345 Coating of ibuprofen crystal with products from hydrothermal hydrolysis of polysaccharides
Chuo University, 1-13-27 Kasuga, Bunkyo-ku, Tokyo 112-8551, Japan

In the pharmaceutical industry, many of drugs are poorly soluble in water [1]. Ibuprofen, a nonsteroidal anti-inflammatory drug [2], is widely used to reduce fever and to treat pain or inflammation but it is poorly soluble in water. Coating with sugar is commonly used to enhance water solubility of drugs and expected to improve solubility, mask bitter taste of drugs and preserve medical effects. Due to relatively high values of the ionic product of H+ and OH- [3], mono- and oligosaccharides can be produced from the hydrothermal hydrolysis of polysaccharides [4]. The objective of this study is to demonstrate coating of less soluble drug crystal with products derived from hydrothermal hydrolysis of polysaccharides: ibuprofen was employed as a drug species, and polygalacturonic acid as a polysaccharide component. Mono- and oligo-galacturonic acids were hydrolytically obtained in a semi-batch flow reactor. The hydrolysis product solution played as a role of an anti-solvent for ibuprofen crystallization. The morphology and surface of ibuprofen crystal was observed with a scanning electron microscopy (SEM). Figure 1 (a) and (b) shows the SEM images of the neat ibuprofen crystal and coated ibuprofen crystal, respectively. The crystal structure was analyzed with the X-ray diffraction, and melting temperature of the ibuprofen crystals by differential scanning calorimetry. The effects of operating conditions on the amount of coating layer on the ibuprofen crystal surface were investigated.
[1] E. Merisko-Liversidge et al., Eur. J. Pharm. Sci., 2003, 18, 113-120
[2] A. Mauricio et al., Fluid Phase Equilib., 2013, 354, 185-190
[3] T. Funazukuri et al., J. Chem. Technol. Biotechnol., 2004, 79, 229-233
[4] T. Miyazawa et al., Ind. Eng. Chem. Res., 2004, 43, 2310-2314

PB346 Generation, identification and characterization of ultrafine bubbles in water
Takashi GOSHIMA, Susumu NII
Kagoshima University, Kagoshima City, Kagoshima, Japan

Fine bubble (FB) attracts keen attention and the appilcation is spreading in various fields. FB is classified into microbubbles (MB) and ultrafine bubbles (UFB) depending on the size. Although benefits of UFB have been recognized in many applications, there are many obstacles for deeper understanding of the effect due to the lack of methods to characterize UFB. This study aims to introduce series of UFB generators invented by the author and propose methods to identify and characterize UFB.
For identification, a method to differentiate bubbles and impurities was proposed. The dominant matter in water, either bubbles or impurities was successfully differentiated by analyzing signals obtained from a laser-based instrument, Nanosight LM-10. Comparison of the distribution patterns obtained from mixtures of UFB and various impurities (Fig. 1) suggested that UFBs are stabilized by adsorbing impurities in water. For characterization, the effect of salt addition on the number density and size distribution of UFBs was examined. Addition of NaCl solution into UFB water gave rise to UFBs' expansion and agglomeration depending on the condition. The dissolved gas concentration in NaCl solution and UFB determines the dominant change to occur. When the gas concentration in NaCl solution concentration is higher than that in UFB water, majority of the UFBs expand while the rest of UFBs agglomerate, vice versa. Furthermore, the net surface tension of single UFB in water was experimentally determined by using the invented system to estimate the volume of gas dissolved and/or dispersed in liquid. The net surface tension was lower than the surface tension of pure water.
These results provide supporting information for a suggested mechanism for stability of UFB in water by Yasui (2016) and the report of decreased surface tension of UFB water by Terasaka (2018).

PB347 Experimental study on jet asymmetry of two-component layer impinging stream mixer
Jianwei ZHANG, Yuhang YAN, Fanrong MA, Yifan ZHANG, Xinli SHA
School of Energy and Power Engineering, Shenyang University of Chemical Technology, Shenyang 110142, China

The flow field energy and mixing characteristics of the two-component layer jet asymmetric impingement mixer were studied by two-dimensional high-speed particle image testing technology (TR-PIV) and laser induced fluorescence (PLIF). In this study, the POD analysis method is used to extract the large-scale structure of the flow field and decompose the instantaneous flow field to obtain the main modal energy. The flow field energy is mainly concentrated in the first-order mode, which is easy to describe the flow characteristics of the whole flow field. Flow field reconstruction can accurately reduce the distribution of the initial flow field vortex structure. The asymmetric flow field energy formed by the up and down and left and right offsets of the stagnation point is always larger than the symmetrical flow field, and the mixing rate is lower than the symmetrical flow field. Under the same working condition, the stagnation cross flow field energy is higher than the stagnation point on the same side. The mixing efficiency is opposite; the lower tracer (stagnation point) is left (fully developed) to facilitate flow field mixing (Figure 1). Therefore, this asymmetry of the jet is beneficial to increase the flow field energy, and the initial development of the tracer promotes flow field mixing.

PB348 Modeling and Numerical Study of Ceramic Paste Extrusion
Boris GOLMAN1, Piotr Skrzypacz1, Wittaya Julklang2
1 Nazarbayev University, Nur-Sultan, Kazakhstan,
2 Suranaree University of Technology, Nakhon-Ratchasima, Thailand

The extrusion process of ceramic pastes is commonly used for the production of high-value products such as catalyst pellets for the chemical reactor, honeycomb catalyst for purifying gas exhausted from an automobile, ceramic packings for adsorption and direct heat transfer, etc. Recently, extrusion-based 3D printing was successfully applied for manufacturing of ceramic superconductors, zeolite monoliths, and porous scaffolds.
Ceramic paste extrusion is a complex process which depends on the paste rheological properties, die and extruder geometries, and operational parameters. The paste rheological properties are controlled by several factors including volume fraction of particles and their size distribution, shape, packing density and surface characteristics, as well as amount and properties of binder and other additives. Modeling and quantitative analysis of paste molding are important to design the extrusion process for the production of high-value extrudates of desired strength, shape and morphology.
The objective of this paper is to construct the mathematical model of ram extrusion of ceramic materials and use it for the optimization of the extrusion process. The paste extrusion was modeled as a flow of non-Newtonian fluid. The paste continuity and momentum equations were solved numerically for fluid based on the modified Herschel-Bulkley viscous model. Fig. 1 illustrates the velocity distribution in the extruder. The effects of materials properties, extruder and die geometries, temperature and inlet paste velocity on the distributions of paste velocity and pressure in the extruder and die were investigated numerically.
1. M. Li, L.Tang, R.G. Landers, M.C.Leu, Extrusion process modeling for aqueous-based ceramic pastes, J Manuf Sci E-T ASME, 135, 051008, 2013.
2. N.Labsi, Y.K.Benkahla, A. Boutra, Hydrodynamic and thermal characterization of the flow of a Herschel-Bulkley fluid in a pipe, ESCAPE20, 1-6, 2010.

PB349 Numerical simulation of gas-solids flow in bubbling beds with different internal structures
Jiang YUAN, SHI Xiaogang, LAN Xingying, GAO Jinsen
China University of Petroleum, Beijing, China

Bubbling beds are widely used in process industry, e.g. stripper of Fluid Catalytic Cracking (FCC) in petrochemical industry. It is important to enhance gas-solids contacting by improving the gas-solid flow, bubble distribution, bubble diameter and gas-solid backmixing in the stripper by adding internal structures. Different types of internal structures have been reported including disk and donut baffles and grid baffles. In this study, an Eulerian–Eulerian approach was used to compare the gas–solids flow behaviors in strippers with disk and donut and grid packing and in the empty stripper. Simulation results with respect to the solid volume fraction agrees well with experiments, indicating that the model is accurate in predicting gas-solids flow behaviors in bubbling beds. The CFD model also clearly predicts the local dead zones underneath the disc and donut baffles. The gas-solids flow behaviors are more uniform in the grid stripper than in other types of strippers. A machine-learning based method of capturing and characterizing the bubble was proposed. It was found that any strippers with internal structures can obtain smaller bubbles than the empty bubbling bed. The number of bubbles in the grid stripper is about 10 times more, and the bubble size is much smaller than those in the empty-type stripper. The present work indicates that the internal structures can enhance bubble breakup. The performance of the bubbling bed can further be improved by optimizing the internal structures.

PB350 Development of new synthesis method for hollow polymer particles
Yusuke KAWAI, Tetsuya YAMAMOTO
Graduate School of Materials Design Innovation Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, Aichi, Japan

Polymer hollow particles have many advantages: great light diffusivity, high heat blocking rate, low density, low cost, and good dispersion in resin. However, the conventional synthesis methods have problems with their uniformity and productivity, which prevent application for products. In this research, we developed a new method to synthesize a large amount of uniform hollow polymer particles. Polymer solid particles were synthesized by soap-free emulsion polymerization using styrene as a monomer and 2,2'-Azobis [2- (2-imidazolin-2yl) propane] dihydrochloride (VA-044) as a polymerization initiator. In the colloid of the polymer solid particles prepared above, methyl methacrylate (hydrophilic monomer) divinylbenzene (crosslinker), and ethyl acetate (good solvent for polystyrene) were added and the polymer solid particles were swollen with the monomers and the solvent. Then, VA-044 was added and the polymerization was started. Through drying the fine particles, polymer hollow particles were obtained. A TEM image of the polymer hollow particles synthesized by this method is shown in following. Monodispersed hollow particles were synthesized (Cv: 9.2%, Cv = particle diameter dispersion / particle diameter distribution × 100). In addition, it was shown that the hollow polymer particles have different optical characteristics and heat blocking properties.

PB351 Effect of geometrical configuration of baffles on mixing performance in a stirred vessel
Eri SATO1, Hiroo HORIFUCHI2, Takafumi HORIE1, Yoshiyuki KOMODA1, Naoto OHMURA1
1 Kobe University, Kobe, Hyogo, Japan
2 Sumitomo Heavy Industries Process Equipment Co., Ltd., Saijyo, Ehime, Japan

Mixing is a general process operation and plays an important role in many chemical process industries. It is used for various purposes such as gas-liquid, liquid-liquid, and dispersion of solid-liquid. In agitation in a stirred tank, a vortex is formed in a turbulent flow. When the vortex is formed, the circumferential rotational flow becomes dominant and makes the vertical mixing weaken. Consequently, performance of mixing decreases. Installing baffles can break the vortex and the flow is complicated, so that the performance of mixing is improved. Thus, the baffles play a very important role in fluid mixing. However, there are very few researches on the effect of geometrical configuration of baffles on mixing performance. Therefore, in this study, baffle length, width, clearance and the number of sheets were varied to investigate the agitating power consumption and mixing characteristics. A transparent acrylic tank with a semi-elliptical bottom was used as a stirring tank, and MAXBLEND© was used as an impeller. Five geometrical configurations of baffles with different length and width were used. Rotational torque was measured using tap water as the liquid to determine the power number, and the power diagram was obtained by plotting the power number as a function of the impeller Reynolds number. Decolorization experiments of iodine and sodium thiosulfate were conducted to determine mixing time. It is generally known that the power number in the stirred tank with baffles is independent of Reynolds number in fully developed turbulent flows. This study, therefore, tried to correlate the power number with the geometrical parameters, and a relatively good non-dimensional correlation equation with accuracy within ± 10% was successfully obtained in fully turbulent flow regions.

PB352 Formation Mechanism of Dead Water Region and Its Influence on Solute Transport in Irregular-Shaped Micro Channels
Kizuki TOYAMA, Fumina TOGI, Tetsumi KUBOTA, Shusaku HARADA
Hokkaido University, Sapporo, Japan

It is important to understand solute transport in micro-channels in various fields of engineering. For example, solute transport in natural flow channels, such as rock cracks or gaps in soils, is closely related to resource extraction or pollutant dispersion in underground. In a micro-channel, a laminar dispersion, which is known as Taylor dispersion, plays a significant role on the solute transport. However, most of the natural channels have an irregular shape and the solute dispersion is greatly influenced by the irregularity of the channel such as variance of the cross-sectional shape and the roughness of the channel wall. This is because dead water region (stagnant region) is formed in irregular-shaped channels.
The purpose of our study is to understand the formation mechanism of dead water region and its influence on solute transport and to make clear the dispersion process in various-shaped micro-channels. We examined the effect of the irregularity of wall surface on solute transport experimentally. We quantified the solute concentration field in micro-channels by image analysis based on absorption photometry and also measured the flow velocity distribution in the channels by particle image velocimetry technique. From the measurement results, we quantified the dead water region formed near the channel sidewall.
From the experimental results using rough-walled channels with various heights and wavelengths, it is found that dead water region decreases the effective aperture length and the solute transport is enhanced in flow direction. We developed a model on the formation of dead water region as a function of the height of wall roughness in micro-channels. The model describes well the formation mechanism of dead water region and the relationship between dead water region and solute dispersion in various-shaped channels.

PB353 Measurement of microbial adhesive forces using parallel plate flow chamber and atomic force microscopy
Takumi MATSUMOTO, Akinori YOSHIHARA, Yasuhiro KONISHI, Toshiyuki NOMURA
Osaka Prefecture University, Sakai, Japan

The vast majority of environmental microorganisms adhere to every interface and form highly structured microbial aggregates called biofilms. Biofilms are structured communities of microbial cells enclosed in a self-produced extracellular polymeric substance (EPS). The presence of the EPS provides up to 1,000-fold greater resistant to antimicrobial agents when compared with their planktonic counterparts. The adhered cells usually cause piping corrosion in various types of facilities. Removal of adhered cells on various surfaces is an important issue that improves productivity and ensures safety in industrial processes. In this study, the effects of the physicochemical properties of microbial cell surfaces on cell detachment from solid surfaces were investigated using a parallel plate flow chamber (PPFC) and an atomic force microscopy (AFM). Gram-positive Lactococcus lactis was used as model microbial cell, and negatively charged glass slide was used as model substrate. The cumulative number of detached cells from the model substrate as a function of flow rate in PPFC was fit with the Weibull distribution function, and the drag force distribution was calculated from the hydrodynamic force required to remove attached cells. Based on the DLVO theory, because the microbial cells and the glass substrate are negatively charged, it can be predicted that the interaction force between the microbial cells and the glass increases with an increase of the ionic strength. However, interestingly, the drag force to remove the attached cells on the surface shifted toward smaller values with increasing ionic strength. AFM imaging of microbial cells attached on the glass surface was carried out with a stepwise increase of the contact pressure. The required removal forces estimated form the lateral forces in AFM deceased with an increase of ionic strength. This was found to be agreed well with the result in PPFC.

PB354 Experiment and CFD simulation of flow characteristics in stairs model
Fukuoka University, Fukuoka City, Fukuoka, Japan

Wind flows through stairs cause various problems, such as subway trains wind, and chimney effects in stairs of high-rise buildings, but the flow structure in stairs has not been fully understood yet. In the present study, scale model of a 4-storey stairs and a 4-storey slope model having same inclination were fabricated using by a 3D printer. This model experiment was performed on the assumption that windows of the landing stairs were closed. Each model inlet was connected with a wind tunnel outlet in order to obtain uniform velocity distribution condition. The flow structures of the stairs model and the slope model were compared. Velocity was measured with the hot wire anemometer. The flow velocity was calculated with the OpenFOAM. The observed velocity was agreed with the CFD values. Therefore, the k-e model is applicable for flows of the stairs and slope model. Flow structures of the stairs were found to be similar to that of the slope.

PB355 CFD-PBM simulation of drop size distributions in a pump-mixer: Influence of the local turbulent dissipation
Han ZHOU, Shan JING, Shaowei LI
Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 100084, China

Coupling the computational fluid dynamics (CFD) and population balance model (PBM) is a promising approach to simulate the liquid-liquid two-phase flow. In this study, the influence of the local turbulent dissipation on drop size distribution (DSD) in a pump-mixer is studied using the CFD-PBM approach. The breakup kernels obtained in our previous study (Zhou et al., 2019. Measurement of droplet breakage in a pump-mixer. Chem. Eng. Sci. 195, 23–38.) were adopted and the class method is selected to solve the population balance equation (PBE). The drop size distributions (DSDs) at five different rotating speeds were simulated to investigate the influence of the local turbulent dissipation. The prediction of the DSDs was compared with the experimental results and show a good agreement, which verified the correctness of the breakup kernels.

PB356 Cluster characteristics in the jet mixing zone of fast fluidized bed
Zihan YAN, Yiping FAN, Chunxi LU, Chunming XU
China University of Petroleum-Beijing

As an efficient equipment for gas-solid reaction, mass and heat transfer, fast fluidized bed is widely used in modern chemical industry. For example, catalytic cracking, fluidized coking, coal gasification and combustion, and the gas phase polymerization. In these processes, high-speed nozzle jets are usually employed to realize a full mixing and reaction between gas and solids. The dynamic contact of feed jets with fluidized particles will directly affect the reaction results. Thus, it is important to know the cluster behaviors in this mixing process. By combining the wavelet decomposition theory with particle concentration signals, method for identifying clusters in the jet mixing zone of fast fluidized bed was proposed. Characteristics of clusters during the dynamic mixing process were obtained. Comparisons between upward and downward jets were made by analyzing the cluster time fraction. Results show that the characteristics of clusters in the upward and downward jet mixing zones are quite different. Overall, the time fractions of clusters are much higher for the upward jets, especially in the initial contact region of jets with particles. For the whole jet mixing zone, when the jets are upward, the average cluster time fraction is about 8.91%, while for the downward jets, the average cluster time fraction is only 6.19%. Besides, it is shown that the cluster time fraction is quite high near the wall of fluidized bed in the upward jets mixing zone, which results in the low efficiency of mass and heat transfer between gas and solids. In the industrial production, some undesirable phenomenon occurs. For example, the coking problem in FCC riser. On the contrary, if the jets mixing with the fluidized particles countercurrently, the time fraction of clusters decreases significantly. The gas-solid mass and heat transfer efficiency is expected to be improved.

PB357 Lagrangian analysis of solid particle concentration distribution in solid-liquid stirred tank with various particle concentration and impeller height
Masato KURODA, Shunnosuke IMAI, Ryuta MISUMI, Meguru KAMINOYAMA
Yokohama National University, Yokohama, Kanagawa, Japan

Solid-liquid mixing is widely used in crystallizer and chemical reactor with catalysis. In these processes, there is a problem that solid particles do not disperse uniformly and deposit on the bottom of the tank. So it is necessary to quantify the solid particle concentration distribution in the tank and investigate the conditions for improving particle suspension in order to solve these problems. However, it is difficult to measure the detailed particle concentration in the tank under many conditions. So, in this study, Euler-Lagrangian simulations were performed with various particle diameter, particle density, particle number, impeller speed, and impeller height to quantify the vertical distribution of solid particle concentration in the vessel and identified the factor that determines the dispersion state.
The Euler-Lagrangian approach, which tracks all particle motion, was adopted. Turbulent flow in the vessel was represented by large eddy simulation. The interactions of particle–particle and particle–solid surfaces were modeled using the distinct element method. The fluid was presumed to be water. The standard deviation of particle concentration in the vertical direction, σc, was calculated and time averaged σc, σc,av, was used as the evaluation index of dispersion state in the vessel.
Results show that particles suspension was promoted and σc,av decreased as the particle number increased because particles collisions increased around vessel bottom. And σc,av was correlated with terminal settling velocity (determined by particle size and particle density) and impeller tip velocity (determined by impeller speed and impeller diameter). Finally, when the flow pattern changed greatly by changing the impeller height in the liquid depth, H, the particle dispersion state with impeller height of H/3 and H/9 were promoted comparing to that with impeller height of H/5.

PB358 Evaluation of mixing performance in Porous Hollow Fiber Membrane device
Department of Chemical Engineering, Osaka Prefecture University

Nanoparticles are used in biomedical, optical, and electronic fields. In general, it is important for the synthesis of nanoparticles to bring about highly supersaturated reaction solution conditions. However, batch type reactions often result in wide size distributions of resultant particles and low reproducibility, because the non-uniform supersaturation condition inside the reactor cannot be avoided due to its poor mixing performance. In this study, therefore, we proposed usage of porous hollow fiber membrane (PHFM) device as a new approach of mixing process for the improvement of mixing property. PHFM devices are mainly used in the waste water treatment process. On the other hand, PHFM device have possibility to provide a more efficient mixing condition than the conventional mixing equipment, because they have large number of small pores in the wall surface of the hollow fiber. However, the mixing performance in PHFM devices have not been evaluated quantitatively. The objective of this study is characterization of mixing performance in PHFM devices by the Villermaux-Dushman method and understanding mixing mechanism in PHFM devices using the computational fluid dynamics (CFD) simulations.
Fig. 1 illustrates the champion data of the mixing time using different four mixing devices (PHFM device, batch-type mixer, T-shaped mixer, and microreactor). The PHFM devise shows much fast mixing time of approximately 0.3 ms as well as the microreactor. Moreover, PHFM devices achieved the high mixing performance despite a low Re number. This would be because the large number of small pores provide infinite water jet streams. Furthermore, the CFD simulations of the mixing process were conducted to investigate the mixing performance and the effect of pore size and feed flow rate on the mixing performance.

PB359 Experimental measurement of particle sedimentation in modified raceway ponds
Ryunosuke OSAKA1, Yoshiaki UEDA2, Yusuke SAKAI3
1 Graduate Student, Setsunan University, Neyagawa, Osaka, Japan
2 Setsunan University, Neyagawa, Osaka, Japan
3 Kumagai Gumi Co.Ltd., Shinjyuku, Tokyo, Japan

Microalgae have been paid attention for biofuels production in the bioenergy sector. Recently, an open-channel raceway pond system is commonly used from the viewpoint of the production rate and construction/operation cost. In the open-channel raceway ponds, a dead zone around the corner of a central baffle inhibits the mixing and, therefore, the dead zone volume is required to decrease in volume to increase the growth rate of microalgae. In this study, we experimentally seek to optimal geometry of a raceway pond for efficient production rate of biofuel energy. In practice, the tracer particles having the specific density of 1.02 are included in a newly proposed raceway ponds, and the sedimentation of particles are recorded every one minute with the use of a digital camera. In addition, the flow patterns in the raceway ponds are measured with the particle image velocimetry (PIV) and computational fluid dynamics (CFD) simulation. Based on the results obtained in the experiments, the physical model to design an optimal layout of the baffle in a raceway pond are proposed successfully.

PB360 Formation and Evaluation of Au/ZnO Particles by Spray Pyrolysis Method
Young-Jun LEE1, Toshiyuki FUJIMOTO2, Shinya YAMANAKA2, Yoshikazu KUGA3
1 Division of Engineering, Muroran Institute of Technology, Muroran japan
2 College of Environmental Technology, Muroran Institute of Technology, Muroran japan
3 Muroran Institute of Technology, Muroran japan

In order to expand the absorption wavelength range of zinc oxide utilized as a photocatalytic catalyst, studies of Au nanoparticles depositing on zinc oxide (Au/ZnO) have been actively carried out. Since the Au nanoparticle can absorb visible light, Au/ZnO is expected to have catalytic properties for absorbing UV-ray and visible light. The purpose of this study is to generate Au/ZnO particles by an ultrasonic spray pyrolysis method (USP).
A dilute aqueous solution of Zn(NO3)2 and HAuCl4 was used as a raw material solution. Small droplets of raw material solution generated by ultrasonic nebulizer were thermally decomposed in the reaction tube. The generated Au/ZnO particles were characterized by SEM, XRD, TEM and UV-Vis equipment. In order to prevent particle aggregation, Trion X-100, a non-ionic surfactant, was added, and its effects were also examined.
The particle size was found to be several micrometer by SEM observation. ZnO and metallic Au crystalline were found by the XRD analysis. As shown in lower part of Figure, the color of obtained Au/ZnO particles was from thick purple to pale purple. As shown in the upper part of the Figure, the TEM images of the particles showed that the Au crystals were well dispersed inside the ZnO particles. Crystallite size estimated by Scherrer's equation was agreed with that measured from TEM images: the cristallite size decreased as decreasing the additive rate of HAuCl4. The obtained particles were measured by UV-Vis equipment. The smaller the size of the Au particles, the higher the visible absorption peak near 400 nm. This is considered to be the result of resonance with light having higher energy as the atomic vibration caused by surface plasmons increases as the Au particle size is smaller. In the case of adding Trion X-100, the absorption peak shifted toward the longer wavelength side: aggregation of Au particles was enhanced by the addition of Triton X-100.

PB361 Langevin Dynamics Calculation of Brownian Coagulation Coefficient for Spherical Equal-size Aerosol Particles in Transient Regime
Toshiyuki FUJIMOTO1, Shinya YAMANAKA1, Yoshikazu KUGA2
1 College of Environmental Technology, Muroran Institute of Technology, Muroran, Japan
2 Muroran Institute of Technology, Muroran, Japan

Coagulation coefficient of aerosol particles due to Brownian motion is an important issue in aerosol science and technology. Motion of aerosol particles is diffusive in continuous region (small diffusive Knudsen number, KnD), or like free molecular motion of gaseous molecular in free molecular region (large KnD). Fuchs (1964) presented an expression of coagulation coefficient in transition regime by so-called "Flux Matching" method: physical model of this method was very clear and have been well accepted. In his method, the particles transport inside of the "limiting sphere" was assumed to be like free molecular, or diffusive outside of the sphere.
These days, some researchers presented coagulation coefficient of aerosol particles by direct calculation of motion of aerosol particles. They employed Langevin dynamics equation to represent the stochastic motion of aerosol particles. In this study, we developed new model to calculate the coagulation coefficient. As shown in Figure, our model employed spherical space in which one scavenging particles are in the center of it: the spherical space moves together with the motion of the scavenging particle. Other colliding particles move in the spherical space until the particles collide to the scavenging particle (1). The collided particle is re-generated at the surface of the spherical space (2). The particle escaped from the spherical space (3) is re-entered (4). The coagulation coefficient can be calculated from the mean time interval of collision and the concentration of colliding particle.
By using the above numerical model, we have calculated the coagulation coefficient of spherical particles of from 4 nm to 400 nm in diameter. Our results were slightly greater than that of Fuchs. The difference was significant considering the uncertainty caused by Monte Carlo Method. The results were organized by using KnD, then we presented an expression of non-dimensional diffusion coefficient.

PB362 Optimum mixing ratio of sewage sludge and food waste in cylingrical agitated vessel for composting
Young Sei LEE, Kiyoung LEE
Kyungpook National University, Sangju City, Gyeongbuk, Koera

During the past decade, the proportion of food waste in municipal waste stream is gradually increasing and hence a proper food waste management strategy needs to be devised to ensure its eco-friendly and sustainable disposal in the world. The most well-kwon approach to treat food waste has been considered compositing, which is breaking down biodegradable waste by naturally occurring micro-organisms with oxygen, in an enclosed vessel or tunnel or pit. In order to achieve optimal compositing, the mixing ratio of food waste and micro-organisms in sewage sludge and the reaction behaviors are quite important.
In this work, we studied about reaction rate, salinity, carbon/nitrogen ratio, reaction temperature, and organic substance during compositing process in the mixture of food waste and sewage sludge to find optimal composition. For our study, the sewage sludge and food wastes were collected from a rural area and garbage trucks operated by Sangju City.
Compositing experimental was carried out with various mixing ratio of the food wastes and sewage sludge such as 10:30, 30:70, 50:50, 60:40, 70:30 and 90:10 wt.%, respectively.
Finally, we reveal that the optimum ratio for compositing was 60 : 40 wt.%. Moreover, the detailed results show that the temperature was 18 ~ 22 oC at the initial stage, then it was sharply increased to 44 ~ 46 oC up to 1day, which was maintained over the fermentation period. In the case of a pH change depending on fermentation process, it was decreased to 4.5 ~ 6.2 due to production of organic acid at the initial stage of reaction. Later on, ammonia was produced that leads to increasing pH value of 7. 3~ 8.0.

PB363 Constant drying rate of wet material containing solvent with low-boiling point
Shizuoka University, Hamamatsu, Shizuoka, Japan

A constant drying rate is important to evaluate the performance of dryer. The constant drying rate is difficult to measure when a surface evaporation rate is extremely high like the material containing solvent with a low-boiling point. To measure the constant drying rate, the material surface must be wet during measuring. In this study, to keep the material surface wet, liquid (solvent) was supplied to the material (a sintered-glass ball filter was used as the material). The validity of the method was confirmed for water as the supply liquid. Ethanol and acetone were used as the solvents with the low-boiling point. The constant drying rate and the temperature of material were measured at steady state. The temperature of material obtained from the experiment was compared with the results calculated from the conventional method (Chilton-Colburn analogy).
Table 1 shows the results of constant drying rate, temperature of material and heat transfer coefficient on material surface. In the case of water, calculated temperature of material (wet-bulb temperature) is 297.8 K which is almost equal to that in experiment (297.2 K). The difference of the material temperature between the calculation results (Chilton-Colburn analogy) and experimental data was large when the material surface was assumed to be covered with the pure solvent (ethanol). It implies that the water vapor in air affects the evaporation of solvent (ethanol) on the material surface. The gas-liquid equilibrium (water-ethanol system) on the material surface is considered to predict the temperature of material, and the results are in good agreement with the experimental data (in Table 1). A heat transfer coefficient can be calculated from the experimental data (drying rate and temperature of material). The heat transfer coefficients obtained from the experiment are in orderly agreement with the values predicted (Ranz-Marshall equation).

PB364 Flow pattern analysis of self-induced sloshing due to bubble flow in a rectangular vessel
Ryohei AOKI1, Satoko FUJIOKA2, Koichi TERASAKA2
1 School of Science for Open and Environmental Systems, Graduate School of Science and Technology, Keio University
2 Department of Applied Chemistry, Faculty of Science and Technology, Keio University

Self-induced sloshing is oscillatory phenomenon of a liquid free surface caused by a flow of a fluid. This phenomenon is reported in some gas-liquid reactors, and it is important to predict and prevent its occurrence from the viewpoint of safe operation of the reactors. However, the mechanism of this phenomenon has not been clarified.
Therefore, in this study, self-induced sloshing caused by bubble flow in a rectangular vessel was experimentally examined in order to elucidate its generation mechanism. In our experiment, air bubbles were dispersed into tap water from the bottom of the rectangular vessel.
First, the effects of gas flow rate and liquid height on the oscillation of liquid surface were investigated by image photographing. Oscillation frequency and amplitude of liquid surface were analyzed. It was confirmed that self-induced sloshing occurred by increasing the gas flow rate at specific initial liquid height. The gas flow rate threshold varied depending on the initial liquid height. Pendulous oscillation of bubble flow was observed simultaneously with free surface oscillation. The frequency decreased with the increase in liquid height.
Second, PIV was carried out. Figure shows unique circulating flow observed only when self-induced sloshing occurred. Liquid circulating flow occurring on both sides of the bubble flow transitioned within one cycle of self-induced sloshing. It is suggested that the circulating flow contributes to the oscillation of bubble flow and liquid free surface.
CFD modeling was also considered for scale-up of the vessel. It is difficult to reproduce the self-induced sloshing caused by bubble flow because it is a multiscale phenomenon that includes both a small-scale bubble interface and a large-scale free surface. We tried to reproduce oscillation of bubble flow and liquid free surface simultaneously using Multi-Fluid VOF model of Eulerian multiphase flow model in ANSYS FLUENT.

PB365 Observation of pseudo plume behavior by hydrate sedimentary layer decomposition
Yusuke TAKAHASHI, Ryosuke EZURE, Shun TAKANO, Hiroyuki KOMATSU, Kazuaki YAMAGIWA, Hideo TAJIMA
Niigata University, Niigata, Japan

We are focusing on the practical use of methane hydrate, which is expected in the future as alternative energy. The surficial and shallow methane hydrate presented under the seafloor generates bubble groups (that is “plume”) by decomposition. For recovery and use as energy resource, it is necessary to consider the possibility of clogging in the recovery pipe due to rehydration of bubbles. The purpose of this research is to observe experimentally and evaluate theoretically the decomposition behavior of hydrate sedimentary layer and the rising behavior of bubbles generated by hydrate decomposition. Chlorodifluoromethane was used as a low pressure model gas of methane. Hydrate sedimentary layer was produced by cooling and pressurizing water in countercurrent contact with gas using a hydrate formation recovery device. The recovered hydrate was decomposed by the heating or depressurization method, without flowing water. Since the water was sufficiently saturated with the gas component during decomposition, the bubble radius reduction by gas dissolution was negligible. Two theoretical rising velocities were derived from the theoretical value with using the Navier-Stokes equation or the values in consideration of the bubble shape and hydrate film existence. The experimental rising velocities of small spherical bubbles radius agreed well with the theoretical value by Navier-Stokes equation. The relatively large elliptical bubbles showed a behavior close to the theoretical value of bubble with hydrate film. The rising velocity may decrease for any reason. Further investigation is needed for the influence of the bubble shape term in the theoretical formula. Under the pressure and temperature conditions closer to the hydrate equilibrium line, almost no generated bubbles could be identified. This may be because of fine bubble generation

PB366 Effect of homogenizer dispersion on particle size and size distribution in continuous production of silica microcapsules
Naoki KURODA, Takafumi HORIE, Ruri HIDEMA, Keita TANIYA, Kosuke SUZUKI, Yoshiyuki KOMODA, Yuichi ICHIHASHI, Satoru NISHIYAMA, Naoto OHMURA, Hiroshi SUZUKI
Kobe University, Kobe, Hyogo, Japan

Low temperature heat less than 423 K exhausted from factories and power plants has been wasted due to the low usability. If it is properly transported and distributed to each homes, it can be utilized for the air heating and hot water supply. Latent heat transport by using phase change slurry is expected to be used for filling this space gap. However, the latent heat transport slurry still has problems such as plugging in the pipes and increase flow resistance. The problems can be solved by encapsulating the phase change material in silica microcapsules. In this study, we developed a continuous process enabling large production of silica microcapsules for application to a latent heat transport slurry. In the first stage of this process, W/O emulsion was produced with a homogenizer, and in the second stage, W/O/W emulsion was formed with hydrolysis reaction occurring at the oil-water interface. The correlation between the water droplet diameter of the W/O emulsion and the diameter of the silica microcapsules indicated that the W/O emulsion process using the homogenizer determined the capsule diameter. It was also observed that silica microcapsules formed when the water droplets escaped from the oil droplets. Furthermore, by considering Shinner's equation, it was found that the average capsule diameter can be controlled by the rotation speed of the homogenizer. Finally, the stirred tank of the liquid-liquid dispersion process with the homogenizer was changed to the small one in order to make the residence time became uniform. Monodispersed silica microcapsules could be obtained with this continuous process.
Acknowledgements: This study was supported by JST-Mirai-project: #JPMJMI17EK.

PB367 Drag coefficients of a rising ellipsoidal droplet in a stagnant liquid
Saitama University, Saitama City, Saitama, Japan

In order to design drop dispersion systems, such as flows inside solvent extraction columns, it is necessary to know the shape and motion of the dispersed droplets. In this study, numerical analysis of the motion of ellipsoidal droplets in a stagnant liquid was performed by using a three dimensional Front-Tracking method. Drag coefficients of the ellipsoidal droplets were determined from the numerical results by two different projected areas: one calculated based on spherical droplets and the other based on numerically obtained projected area. The drag coefficients based on the numerically obtained projected area were in good agreement with the ones predicted by the semi-empirical model for spherical droplets proposed by Myint et al (J. Fluid Sci. Technol., 1, 72, 2006). The drag model was derived by correcting the projected area, and successfully predicted drag coefficients for ellipsoidal droplets.

PB368 Particle impact energy variation with the size and number of particles in a planetary ball mill
Fumie HIROSAWA, Tomohiro IWASAKI, Masashi IWATA
Osaka Prefecture University, Osaka, Japan

Dry powder grinding is an important unit operation in many industries such as mining, fine chemical, food and pharmaceutical, ranging from coarse mineral ore to submicrometer-sized fine drug powder. Recently, ultrafine dry grinding processes with high energy milling, which can produce fine particles with enhanced performance and/or improved properties, have attracted much attention. In the ultrafine dry grinding, planetary ball mills have been employed, and the milling conditions can vary the particle breakage induced by the impact energy of particles, altering the particle properties, such as size distribution, specific surface area and microscopic structure. Therefore, the impact energy must be appropriately adjusted to produce the particles with controlled properties. In order to understand the impact energy under given milling conditions such as revolution speed of the mill pot, size and density of the grinding balls and ball-to-particle filling mass ratio (BPR), the behavior of particles and balls is often simulated using the discrete element method (DEM). Many studies on the analysis of planetary mills using the DEM simulation have been published, indicating that the impact energy depends strongly on not only the milling conditions but also the particle properties. In the ultrafine dry grinding processes, both the particle size and the number of particles can drastically change as the milling time elapses, resulting in temporal variation of the impact energy. However, the impact energy in planetary mills has not been sufficiently analyzed taking into account the change in particle size and number of particles. In this paper, in order to study its effect on the impact energy, the DEM simulation of a planetary mill was performed under various conditions of particle size and number of particles. The results showed that the impact energy in the normal and tangential directions was greatly affected by these factors, suggesting that the grinding mechanism changes during milling.

PB369 Power characteristics of closed impellers with different geometries of flat blades for agitation
Masaya NAKATA, Hironori MATSUNAGA, Masanori YOSHIDA
Muroran Institute of Technology

Agitation impellers for liquid-phase mixing in chemical processes were designed based on a conventional disk turbine impeller with six flat blades which sucks liquid across the planes including the upper and lower edges of the blades. The altered impeller has the structure for the inflow entrance to be fully confined. We call this “fully closed impeller” and the prototype “open impeller”. The fully closed impeller was modified for the blade geometries, namely, the number and the axial width of the blade. An impeller with the 12 flat blades of standard width (12-STD) and an impeller with 6 flat blades of small width (6-Small) provided narrower flow paths between the neighboring blades of the rotating impeller. Additionally, an impeller with 6 flat blades of tapered width (6-Tapered) provided the flow path with a constant cross-sectional area. These flow paths were expected to produce nearly uniform liquid flows there. Liquid flows in the impeller rotational region of a baffled vessel with the closed impellers were examined for the flow path between the neighboring blades of the rotating impeller and the internal flows were compared with that with the open impeller. Energy consideration in terms of the dimensionless parameters on the basis of the flow and power measurements demonstrated that the closed impellers were successful in the head characteristic rather than the flow one. The power transmission efficiency were enhanced notably for the 6-Tapered closed impeller because of a reduced viscous loss.

PB370 Simulation analysis of the effects of adhesive force distributions in a particle bed on improving discharge particle flowability
Doshisha University, Kyotanabe, Kyoto, Japan

One techniques for improving flowability is admixing smaller particles than main particles. In this technique, an adhesive force have a different value in all contact points between main particles. This is because a combinations of smaller particles coverage states changes in all contact points. This adhesive force distribution would improve a particle flowability. In this study, we examined effects of the force distribution on improving flowability by DEM simulation.
We used DEM simulation of a two-dimensional system. The particle diameter was 60 μm. Physical properties of the particle were mainly set based on glass material including TiO2 and BaO. Two kinds of Hamaker constants, 1.0×10-20 and 1.0×10-22, were used for changing an adhesive force. Adhesive force distributions were given to particle beds by following 2 types; 1) particle surface distribution by setting different adhesive forces at a contact point on the surface, 2) spatial distribution in a particle bed by arranging positions of different adhesive forces particles. The width of particle bed container was 600 μm and the container have a discharging hole of 400 μm at the bottom. The flowability was evaluated by a particle discharging rate. As a result, when we gave a particle surface adhesive force distribution, the flowability increases with increasing surface ratios of the smaller Hamaker constant. On the other hands, in spatial adhesive force distribution results, the flowability shows the maximum value at particle number ratio 50%, which means mostly the largest adhesive force spatial distribution. This is because a particle flow structure depends on the spatial distribution. From these results, we obtained a useful knowledge, which adhesive force spatial distribution has a large effect than the surface distribution for improving discharging flowability.

PB371 Coagulation of latex particles in the aqueous dispersion of epoxy resin
Takahashi TORU, Komoda YOSHIYUKI, Ohmura NAOTO
Kobe University, Kobe, Hyogo, Japan

The mixture of functional latex particles and epoxy resin matrix is known as one of polymer composites and can improve various functions of epoxy resin. Since the remaining of particle aggregates deteriorates the appearance of epoxy composite, the production process of easily dispersed latex aggregates is now strongly required. If aggregates of weakly attached latex particles containing epoxy resin is obtained, such an aggregate may contribute to realized prompt and uniform dispersion of latex particles in epoxy resin matrix. In the present study, therefore, the dispersion state of epoxy resin in water was controlled by dispersion conditions, and the effect of the dispersed state of epoxy resin on the salt coagulation of latex particles was studied. Aqueous dispersion of epoxy resin was prepared using homogenizer or high shear device, Filmix. The droplet prepared using homogenizer had the diameter of 0.1 - 50 μm and easily settled down. In contrast, Filmix could produce highly stable dispersion of epoxy resin having the size of 0.03 μm. And then, the change of latex aggregates in the salt coagulation process was studied based on mean size and morphology. In the epoxy free salt coagulation process, latex aggregates first grew up and then gradually destroyed as increasing mixing time. Additionally, it was observed that tightly packed latex aggregates were produced. Similar trend was obtained when added unstable epoxy dispersion prepared by homogenizer. On the other hand, latex aggregates produced with stable epoxy dispersion was loosely connected and became larger as increasing mixing time. It was probably caused by the following mechanism: Fine droplets of epoxy resin covered the surface of latex particles and the surface layer was contributed to form loosely connected aggregate and increase bonding strength between particles.

PB372 Electrophoretic classification based on differences in electrophoretic mobility caused by change in the applied electric field
Kosei ONO, Tomonori FUKASAWA, Toru ISHIGAMI, Kunihiro FUKUI
Department of Chemical Engineering, Graduate School Engineering, Hiroshima University, Hiroshima, Japan

We propose a novel electrophoretic wet classification method using the applied electric field strength as an operation parameter. The influence of the applied electric field, electrolyte concentration, and particle size on the electrophoretic mobility was evaluated via direct measurements by microscopic electrophoresis. For high electrolyte concentrations or small particles, the electrophoretic mobilities decreased with decreasing applied electric field, unlike the basic theory of electrokinetic phenomena. Then, we fabricated an electrophoretic classification device and investigated the separation efficiencies for various particle sizes, electrolyte concentrations, and applied electric fields. For low electrolyte concentrations, the change in separation efficiency with respect to the applied electric field depended on the particle size. Finally, we performed a classification experiment using the applied electric field as an operation parameter. For low electrolyte concentrations, the classification performance changed according to the applied electric field. The applied electric field that provided the highest classification performance was the same as that where the difference in the separation efficiency was the highest. These results highlight the possibility of electrophoretic wet classification using the applied electric field strength as an operation parameter.
Keywords: wet classification; electrophoresis; electrophoretic mobility; particle

PB373 Direct Measurement of Fluid Pressure in Gas-Solid Fluidized Bed by Capsule-type Sensor
Yuji HONDA1, Shiori SAITO1, Tetsuya ANZAI1, Shusaku HARADA1, Shunsuke KATO2, Jun OSHITANI2, Yuya SAKAMOTO3, Takuya TSUJI3, Hirokazu KAJIWARA4, Kei MATSUOKA5
1 Hokkaido University, Sapporo, Japan
2 Okayama University of Science, Okayama, Japan
3 Osaka University, Osaka, Japan
4 Ebara Environmental Plant Co., Ltd., Tokyo, Japan
5 Ebara Corporation, Tokyo, Japan

Fundamental understanding of the floating-sinking motion of solid objects in a gas-solid fluidized bed is important for various engineering processes such as a density separation technique. Basically the vertical motion of objects in a fluidized bed is explained by “hydrostatic effect”, i.e., the objects having the density larger than the apparent density of the fluidized bed sink into the bottom of the bed. However, recent studies have suggested that the floating-sinking motion of the object is influenced by various factors such as the object shape or the fluidization state of the bed.
The purpose of this study is to examine the fluid force (pressure force), which is the most significant force in the fluidized bed, acting on various-shaped objects and to investigate the shape dependency on the floating-sinking motion. We developed capsule-type pressure sensors and put them into the fluidized beds with various fluidization states. We measured the pressure difference between the upper and the lower surface of various-shaped objects. From the measurement results, it is found that the pressure around the object greatly varies with the object shape. The pressure field around the object in the fixed bed at low air velocity almost agree with the theoretical prediction from Brinkman equation which describes the permeation flow in porous media. On the other hand, the pressure in the fluidized bed at high air velocity largely fluctuates due to the interaction with rising bubbles, however, the average pressure difference between the upper and the lower part of the object reaches almost constant and does not depend on air velocity so much.
The results of this study suggest that the fluid force acting on an object in a gas-solid fluidized bed greatly depends on its shape and the floating-sinking motion is influenced by the fluidization state of fluidized bed.

PB374 Preparation of TiO2-x/C nanocomposite by milling of titania and polypropylene
Daisuke ORITA1, Nobutaka TAKEZAWA2, Kazuhiko SAEKI2, Taiji MATSUMOTO2, Mamoru SENNA3, Yasuyoshi SEKINE4, Kyoko OKUYAMA4, Masahide SATO1, Noboru SUZUKI1
1 Utsunomiya University, Utsunomiya, Japan
2 Industrial Technology Center of Tochigi Prefecture, Utsunomiya, Japan
3 Keio University, Yokohama, Japan
4 Nippon Coke & Engineering Co., Ltd., Tochigi, Japan

Lithium-ion batteries (LIB) are used in various fields, but there is a demand for higher performance to meet the needs for further safety, cost reduction, and long life. Although titanium dioxide is characterized by its chemical stability and high theoretical anode capacity, oxygen deficiency is known to enhance performance via increased conductivity and ion diffusion rate. Thus, the titania-based materials have attracted much attention as an alternative of graphite for the anode material. Although the electrode performance is improved by introducing oxygen deficiency into titanium dioxide, there is a drawback of higher cost such as heating up to 1500 °C under pressurized hydrogen atmosphere. In this study, we propose a new simple method obtaining such a modified titania via a mechanochemical route. Mixture of anatase nanoparticles and polypropylene were milled by a high performance media agitating mill (Nippon Coke & Engineering, AL01). The mechanochemical effects were recognized as a phase transformation from anatase to rutile and color change from white to gray, attributable to the introduction of oxygen deficiencies. These effects were more intensive with smaller amount of polypropylene. Subsequent heat treatment at temperatures as low as 500 °C in the atmosphere of 5 % hydrogen/argon brought about carbon-coated and oxygen deficient titania. Their electrical properties were examined mainly by the impedance spectra measurement.

PB375 Characterization of a technique to remove particles adhered on a surface using pulse air-jet blowings
Ami ISHII1, Ryoichi NAKAYAMA1, Norikazu NAMIKI1, Koya BABA2, Tomokatsu SATO2
1 Kogakuin University,
2 Techno Ryowa Ltd.

Demands for dry precise cleaning of various product surfaces contaminated with particles has been extended at various sorts of production processes such an assembly process of lithium ion batteries.Consecutive pulse-air jet (PAJ) blowings using a nozzle with a silt-shaped opening (rectangular nozzle) are effective for removal of micrometer-sized particles from various surfaces. In the present work, we aimed to make this dry surface-cleaning technique a more practical one for removing particles on separator film surfaces.
1.5 μm-sized PSL particles generated by a Colison atomizer were deposited to a silicon wafer used as a test surface placed in an inertial impactor. The test surface was exposed to PAJ blowings formed from the rectangular nozzle with the jet interval of 20 s and its duration of 1 s. Counting of the remaining particles was performed in the unit measurement area (0.25 × 0.33 mm2) using a microscope on the test surface at each pulse of blowing to determine the removal efficiency, fr_N. The planar distribution of the removal efficiency, fr_N on the test surface was obtained using the fr_N values of 143 points of the unit area in the staggered array of the measurement area (9.50 × 9.90 mm2).
Fig. 1 compares the planar distribution of particle removal efficiency between the rectangular nozzle and the circular nozzle with the same opening area. It was found that the rectangular nozzle successfully removed particles on a wider area at a higher efficiency compared to the circular one. The area mean removal efficiencies were over 90% for the rectangular nozzle, and 47% for the circular one.

PB376 Development of non-contact evaluation method to evaluate aggregation degree of nano particles using fluorescence spectrum analysis
Yusuke ANDO, Noriaki SANO
Kyoto University, Kyotodaigaku-Katsura, Nishikyo-Ku, Kyoto 615-8510 Japan

Nanoparticles are used in various industrial fields such as electronic devices, pharmaceuticals, and catalysts. The aggregation and dispersion of particles have a great influence on product quality in their manufacturing process. For example, production of multilayer ceramic capacitors includes a process of forming a thin film of the slurry and drying it. If there is a portion with a non-uniform degree of aggregation, it will cause product failure. So, understanding and control of the degree of aggregation of nanoparticles is important. In this study, we propose a new method to inspect the degree of particle aggregation using fluorescence spectrum analysis. Because this method is rapid, non-contact, and non-destructive, it can be a promising method of evaluating the degree of agglomeration of the nanoparticles on production lines.
We examined the influence of the aggregation degree of γ-alumina nanoparticle on fluorescence. We prepared two types of dry alumina particle aggregates with different aggregation states by different drying methods from a slurry of γ-alumina particles dispersed in water. By one, the slurry was dried at room temperature and, by another, the slurry was freeze-dried. From the difference in these drying processes, the particles dried at room temperature are more firmly agglomerated than freeze dried. The results of fluorescence spectrum measurement for these particle aggregates are shown in Figure 1. It can be seen that the fluorescence spectrum of the particles dried at room temperature is shifted to the longer wavelength side than freeze dried. The shift of fluorescence indicates the difference in the degree of aggregation from drying process. Namely, as the particles are aggregated, the wavelength of the fluorescence spectrum shifts to the longer wavelength side. This phenomenon would be considered to be similar to quantum size effect.

PB377 (canceled) <101531-1>
PB378 Investigation of the necessity of bottom punch movement in a rotary die-filling system
1 Department of Nuclear Engineering and Management, School of Engineering, The University of Tokyo, Tokyo, Japan
2 Resilience Research Engineering Center, School of Engineering, The University of Tokyo, Tokyo, Japan

A rotary die-filling system is widely employed to produce pharmaceutical tablets. In order to manufacture the tablet, the powder should be fed into a cavity uniformly. For the efficient feeding of powder, the punches are equipped under the die. As the punch starts moving downward, the powder inside the shoe is fed into the cavity. The exact depth of the punches is controlled to measure the filling amount of the powder inside the cavity. Although this system is widely used, its effectiveness has not been examined so far. In the current study, the powder feeding process is conducted using the Discrete Element Method coupled with Computational Fluid Dynamics (DEM-CFD) method. For the representation of the arbitrary shaped moving wall boundaries, the Signed Distance Functions (SDF) are employed, where the scalar field of minimal distance from the nearest wall is computed at the beginning of the calculation. Besides, for the evaluation of the interaction between gas and moving wall boundaries, the Immersed Boundary Method (IBM) is coupled with the SDF, in which the tracking of the interface between gas and wall boundaries can be precisely calculated in the staggered grids. Through comparing the results between with and without the moving punches, the mechanism is revealed for the first time. Consequently, the yield rate can be drastically improved using the numerical simulation techniques.
This study was financially supported by JSPS KAKENHI (17H02825), JSPS KAKENHI (17KK0110) and by Grant-in-Aid for JSPS Research Fellow from the Japan Society for the Promotion of Science (18J12267).

PB379 Starting Torque of Two Disk Turbines
Yukiya KUDO, Takanori KANEKO, Kazuhiko NISHI
Chiba Institute of Technology

When rotation of an impeller starts, strong torque (starting torque) is generated compared to the steady state in which the flow is fully developed. The starting torque is important for the strength design of the device. This study investigated the starting torque of two disk turbines within a mixing vessel, the relation between the starting torque and the distance of the two impellers, and the impeller rotational speed. Furthermore, CFD analysis was conducted to elucidate the starting torque generation mechanism.
Three starting torques, Ts1, Ts2, and Ts3, were observed as presented in Fig. 1. Ts1 is the torque generated during acceleration of the impeller. In this study we investigated Ts2 and Ts3. In Fig. 1, the relation between Ts2, Ts3 and the distance of two impellers (c) is shown. When c is small, Ts2 is small. Results show that Ts2 increases rapidly at c = 0.02 m and becomes almost constant from 0.035 m. Actually, Ts3 shows the same tendency, but Ts3 was not detected after 0.07 m. The following were found from the results of CFD analysis. Ts2 and Ts3 were generated when a flow is strong only around impellers and the flow of the whole mixing vessel is underdeveloped. When Ts2 was generated, two impellers produce the independent flow. When Ts3 is generated, two independent flows seen in Ts2 merge to one flow. Based on these results, Ts3 is not observed when c is large in Fig. 1 because the two flows generated by two impellers in each do not merge.
The relation between impeller rotational speed (n) and each of Ts2 and Ts3 was investigated. Ts2 and Ts3 were proportional to the square of n. Results show that Ts2 and Ts3 are torques based on pressure drag attributable to the relative velocity of impellers and a fluid.

PB380 Direct measurement of interaction forces between a yeast cell and a microbubble using atomic force microscopy
Satoshi KATO, Shohei YUMIYAMA, Yasuhiro KONISHI, Toshiyuki NOMURA
Osaka Prefecture University, Sakai, Japan

The removal of adhered microorganisms on surfaces is an important issue in every industrial process. The interfacial area of the gas-liquid interface increases and the residence time of bubbles in the liquid phase becomes longer with a decrease of an air bubble size. In addition, the production cost of air bubbles is low and their environmental load is also low. These positive features make air bubbles potentially suitable for use in physical cleaning technologies, such as removal of organic materials that have adhered to surfaces and cleaning of membrane fouling. However, cleaning effects using air bubbles and their mechanisms related to interaction forces are poorly understood. Thus, it is necessary to understand the interaction forces between air bubbles and target materials in detail for the further development of industrial usage of air bubbles. Atomic force microscopy (AFM) is a powerful tool for direct measurement of the interaction forces between surfaces. However, few studies have reported on quantitative measurement of interaction forces between a single microbial cell and a natural hydrophobic bubble surface. In this study, we attempted to conduct a direct measurement of the interaction forces between a yeast cell and a microbubble (MB) using AFM. We emphasize that the adhesive force between a cell and a MB measured in this study was one order of magnitude larger than those between microorganisms and hydrophobic substrates. This means that microorganisms that have only recently adhered on surfaces can be removed by adding a hydrodynamic drag force to the adhered MBs on the microbial cells. These findings provide useful information for various applications using MBs, including cleaning technology for any industrial process.

PB381 Numerical Simulation of Binary Particles in Vibrated Fluidized bed Using DEM-CFD Model Based on Particle-Scale Similarities
Jiang ZHAOHUA, Kenta RAI, Takuya TSUJI, Kimiaki WASHINO, Toshitsugu TANAKA
Osaka University, Osaka Prefecture, Japan

Segregation and mixing of binary particles with different densities are concerned in engineering. To improve its efficiency, the usage of vibrated fluidized bed which is a combination of fluidized bed and vibrated bed has been proposed. Due to the coexistence of both aeration and vibration, the phenomena of segregation and mixing of particles in vibrated fluidized bed is complex, whose detail is more important to understand for new designs. However, it is not easy to observe internal flows experimentally, considering the opaque nature of granular systems. Coupled DEM (Discrete Element Method) - CFD (Computational Fluid Dynamics) method is an attractive numerical tool to investigate particle motions in vibrated fluidized beds in detail, while large computational time is required to consider the dynamics of large amount of particles in real engineering systems. It is necessary to find out a proper approach to enable DEM-CFD calculations with reduced computational cost. In this study, enlarged particles are used while keeping the original bed size to reduce particle number. To obtain the similar segregation and mixing behavior in bed, governing equations are non-dimensionalized by characteristic variables in particle scale. Overall flow behavior is expected to be similar when the non-dimensional variables are kept same but changing particle size. In the present study, a numerical model based on particle-scale similarities is introduced and applicability of the proposed model is verified against density segregation problem in a vibrated fluidized bed by varying model particle size.

PB382 (canceled) <101532-1>
PB383 (canceled) <100207-1>

Session 3. Heat transfer and thermal engineering

E401 [Invited] Buoyancy effect on the secondary flow and heat transfer in a marginally turbulent square duct
Atsushi SEKIMOTO, Mizuki NAKAMORI, Yasunori OKANO
Osaka University, Toyonaka, Osaka, Japan

In an isothermal straight duct flow, the 'eight-vortex' secondary flow of Prandtl's second kind as in Fig. 1(a) is generated as a footprint of turbulent coherent structures [1]. When the bottom wall of the horizontal square duct is heated from below, the buoyancy affects these turbulent structures and drastically changes the skin friction and heat transfer rate over the walls and the behavior of coherent vortices under a various strength of buoyancy force the corner has been revealed at low Reynolds numbers [2]. However, at a transitional Reynolds number, the buoyancy effect has not been investigated.
At very low Reynolds numbers, the mean diameter of turbulent vortices is the same order of the duct width, therefore, the duct geometry strongly affects the generation mechanism of the secondary flow. As the bulk Reynolds number decreases, the secondary flow pattern drastically changes and becomes 'four-vortex' patterns [3]. And, at lower Reynolds number, the streamwise-localized turbulent puffs appear as in circular pipe flow.
In this study, the buoyancy effect on the four-vortex secondary flow pattern and localized puffs are investigated using direct numerical simulations. It is revealed that one of the four-vortex secondary flow patterns as in Fig. 1(b) is selectively stabilized by a weak buoyancy effect, and the generation of puffs is suppressed. Furthermore, it is revealed that the secondary flow also depends on the thermal physical property, i.e. the Prandtl number.
[1] Pinelli, A. et al., Reynolds number dependence of mean flow structure in square duct turbulence, J. Fluid Mech. 644, 107-122, (2009)
[2] Sekimoto, A. et al., Turbulence- and buoyancy-driven secondary flow in a horizontal square duct heated from below, Phys. Fluids 23, 075103 (2011)
[3] Uhlmann, M. et al., Marginally turbulent flow in a square duct, J. Fluid Mech. 588, 153-162 (2007)

E402 Heat transfer from a semi-circular cylinder to a Newtonian fluid under rectangular confinement
Avinash CHANDRA1, Arvind Kumar Gautam2, Raj Kumar Arya3
1 Department of Chemical Engineering, Thapar Institute of Engineering & Technology, Patiala, Punjab, India -147004
2 Department of Chemical Engineering, National Institute of Technology, Hamirpur, Himachal Pradesh, India -177005
3 Department of Chemical Engineering, Dr. B. R. Ambedkar National Institute of Technology, Jalandhar, Punjab, India - 144 011

Heat transfer from a heated semi-circular cylinder placed in rectangular confinement has been investigated over wide ranges of the governing parameters as Reynolds number (1≤Re≤50), Prandtl number (0.7≤Pr≤50) and blockage ratio (0.2≤β≤0.8). The numerical solutions of the obtained governing equations for flow and heat transfer have been solved by considering, steady laminar flow in a channel. The combined influence of all governing parameters (Reynolds number, Prandtl number, and blockage ratio) on the flow and heat transfer characteristics have been delineated for the above ranges of the governing parameters. The streamline and isotherm profiles are obtained and used to represent the detailed flow and heat transfer characteristics. The gross engineering design parameters like recirculation length, drag coefficient, and Nusselt number are presented for scientific calculations and record. The distribution of pressure coefficient and local Nusselt number along the surface of the semi-circular cylinder are also presented to show the local variation in the quantities. The drag coefficient has shown an inverse relationship with the Reynolds number and positive dependencies on the blockage ratio, whereas the recirculation length has shown a reverse trend. Similar to drag coefficients, the Nusselt number shown positive dependencies on Reynolds number, Prandtl number and blockage ratio. Additionally, The functional dependence of recirculation length and average Nusselt number on Reynolds number, Prandtl number, and blockage ratio have been explored and the appropriate correlations to predict the intermediate values.
Keywords: Confined flow; Semi-circular cylinder; Nusselt number; Reynolds number; Blockage ratio; Prandtl number; Newtonian fluid

E403 Flow and Sedimentation Characteristics of Hard-Shell Microcapsule Slurries Including Phase Change Materials Treated with Additives
Sohei USA1, Ruri HIDEMA1,2, Keita TANIYA1,2, Takafumi HORIE1,2, Yoshiyuki KOMODA1,2, Yuichi ICHIHASHI1,2, Satoru NISHIYAMA1,2, Naoto OHMURA1,2, Hiroshi SUZUKI1,2
1 Department of Chemical Science and Engineering, Kobe University
2 Complex Fluid and Thermal Engineering Research Center, Kobe University

The flow and sedimentation characteristics of the microcapsules including phase change materials were investigated. As a phase change material, trimethylolethane (TME) clathrate hydrate which has the latent heat of 218kJ/kg was used at the concentration of 25 wt%. The mean diameter of microcapsules was 17 μm and the density of them with TME was 1.32kg/m-3 The concentration of silica hard shell microcapsules with TME was set at 10wt%. As drag reducing surfactants, oleylbishydroxyethylmethylammonium chloride was used with counter-ions of sodium salicylate whose molar ratio to the surfactant was fixed at 1.5. The concentration of surfactans was changed from 2.000 to 6,000 ppm. Polyvinyl alcohol (PVA) was also used as a stabilizer. The concentration of PVA was changed in two steps; 0 and 2000 ppm. Sedimentation experiments were performed in a test tube and the time variation of the apparent volume fraction of micorcapsule dispersion to the slurry was measured at 10 °C of temperature. The friction coefficients of the slurries treated with those additives were measured with a once-through flow system. The Reynolds number defined with water viscosity was changed from 200 to 25,000.
From the results, it was found that the microcapsules in the cases without additives and only with PVA settled to the bottom of the test tube immediately. On the other hand, the sedimentation delays in the cases with the combination additives of surfactants and PVA. The sedimentation was also found to occur slower with increase of surfactant concentration. From the measurements of the friction coefficients, it was found the friction coefficients show lower values in the larger region of 15,000 of Reynolds number. However, the friction coefficients increase with the surfactant concentration. Thus, the optimum condition was concluded to exist for the sedimentation and fluidity.
Acknowledgements: This study was supported by JST-Mirai-project:#JPMJMI17EK.

E404 Investigation of correlation between phase separation structures and melt convection in Cu-Co molten alloys using neutron CT and DNS
Shosei ISOGAI1, Eita SHOJI1, Masaki KUBO1, Takao TSUKADA1, Tetsuya KAI2, Takenao SHINOHARA2, Yoshihiro MATSUMOTO3, Hiroyuki FUKUYAMA1
1 Tohoku University, Sendai, Japan
2 Japan Atomic Energy Agency, Tokai-mura, Japan
3 Comprehensive Research Organization for Science and Society, Tokai-mura, Japan

Since some Cu-based alloys, such as Cu–Co or Cu-Fe alloy, exhibit a metastable miscibility gap in the undercooled state, phase separation occurs when undercooling the alloys below their liquidus-line temperature. Such alloys are expected as new materials with novel properties depending on the phase separation structures. Although the phase separation structure is obviously affected by melt convection during undercooling, the correlation between the phase separation structure and the melt convection is not still clear.
The objective of this study is to elucidate the correlation between them in the Cu-Co alloy system. We utilized an electromagnetic levitator superimposed with a static magnetic field, which can control the strength of melt convection in an electromagnetically levitated molten alloy sample by the static magnetic field, to investigate the effect of melt convection on the phase separation structures of Cu-Co alloys. The sample diameter was 5 mm and the composition of alloys were Cu80CO20 and Cu58Co42. The strength of static magnetic field ranged from 0 to 5 T. Neutron computed tomography (CT) was used to visualize the three-dimensional phase separation structures. In addition, a series of direct numerical simulation (DNS) was also performed to calculate the three-dimensional velocity fields of melt convection in an electromagnetically levitated molten Cu-Co droplet under static magnetic fields, particularly magnetohydrodynamic (MHD) convection was focused on.
The neutron CT results showed that the phase separation structures depend on the static magnetic field strength. In particular, the marked difference in structure between 0.5 T and 3 T was observed, i.e., the size of Co-rich phases at 3.0 T is much larger than that at 0.5 T. The DNS results showed laminar-turbulent transition around 1 T. These results indicate that the marked change of phase separation structures has a strong relation with the laminar-turbulent transition.

E405 [Keynote] Functional material fabrication and thermophysical property measurement using Containerless processing
Jianding YU
State Key Lab of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Dingxi Road, Shanghai 200050, China

Containerless processing is an attractive synthesis technique as it permits deep undercooling in molten materials and the catalytic sites for heterogeneous nucleation are minimized. Thus, it provides a possibility to solidify the undercooled liquid into a selected phase to synthesize metastable materials with higher density and novel properties. It also offers a new approach to grow single crystal and forming new optical glasses using the containerless processing.
For oxide material, the containless processing is usually perfomed by aerodynamic levitation and electrostatic levitation methods. Electrostatic levitation furnace (ELF) is been operated in international space station (ISS) by Japan Aerospace Exploration Agency (JAXA) for thermophysical properties measuring of oxide melts in microgravity environment. Chinese academy of science (CAS) also is developing a new electrostatic levitation furnace for using in China space station (CNN).
In the recent years, we have successfully fabricated some fuctional oxide materails: the hexagonal BaTiO3 single crystal exhibited a dielectric constant value higher than 100,000 at room temperature; the new LaTi2O5 glass with a distorted five-coordinated TiO5 polyhedra glassy structure and a refractive index value higher than about 2.2. The thermophysical properties of density, viscosity and surface tension for high temperature melts up to 3,000 K have been measured using containerless levitation technology.

E413 Large eddy simulation of piloted methane/air jet flame using flamelet based tabulated chemistry
Shota AKAOTSU1, Ryoma OZAWA1, Yohsuke MATSUSHITA1, Hideyuki AOKI1, Weeratunge Malalasekera2
1 Department of Chemical Engineering, Graduate School of Engineering, Tohoku University, 6-6-07 Aoba, Aramaki, Aoba-ku, Sendai, Miyagi 980-8579, Japan
2 School of Mechanical, Electrical and Manufacturing Engineering, Loughborough University, Loughborough LE11 3TU, UK

There is still a large demand for advanced combustion technologies for the stable production of power and electricity in our societies. Recently, numerical simulations have made outstanding achievements, and the number of research projects with Computational Fluid Dynamics remarkably increases with developing a computer performance. Under such situations, flamelet based tabulated chemistry has received much attention due to its high accuracy and relatively a low computational cost. In this work, using this approach based on a non-premixed flame, piloted methane/air jet flame was simulated by large eddy simulation. The numerical solutions showed good agreements to experimental data of temperature and major chemical species. Although the numerical solutions of temperature slightly overestimated the experimental data in the downstream, this difference was also reasonable because the effect of radiation was not included in the present simulation. Flame index, which is the indicator of local combustion mode, suggested the coexistence of premixed and non-premixed regions in the computational domain. Specifically, a premixed region was located in the inner side of the piloted jet while the combustion mode in the outer side of the piloted jet was non-premixed mode. To evaluate the influence of the flame type which is calculated prior to the main simulation, the look-up table based on premixed flame was constructed and used in an additional simulation. The detailed data obtained from the above simulations provided reliable insights for understanding the transport phenomena and chemical reactions of the chemical species in turbulent jet flames.

E414 Combustion of hydrogen-methane/air diffusion flame on a micro-jet array burner
Jun LI1, Noriyuki KOBAYASHI1, Takeshirou ITOU2, Kouichirou TANAHASHI2, Hiroyuki MATSUDA2, Kenji ITOU3, Syouji YOSHIMOTO4, Kazuhiko SAKAGIBARA4, Mitsuhiko MIYACHI5, Hongyu HUANG6
1 Graduate School of Engineering, Nagoya University, Nagoya, Aichi, Japan
2 Ito Racing Service Co., Ltd., Okazaki, Aichi, Japan
3 Seto Ceramic Technology Center, Aichi Center for Industry and Science Technology, Seto, Aichi, Japan
4 Tokoname Ceramic Technology Center, Aichi Center for Industry and Science Technology, Tokoname, Aichi, Japan
5 Alpha System Co., Ltd., Nagoya, Aichi, Japan
6 Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou, China

The combustion and heat release characteristics of hydrogen-methane/air (H2-CH4) diffusion flames on micro-jet array burner are focused in this research. The effects of H2-CH4 co-combustion and equivalence ratio on the flame structures, temperature, free radicals, heat release rate, and NO emission distributions of the H2-CH4/air diffusion flames are numerically investigated. The results show that the simulation results of OH distribution and flame length based on GRI 3.0 and Bilger mechanism are agreed well with the experimental results, showing an acceptable and repeatable results of H2-CH4 combustion based on those mechanisms. Furthermore, uniform and small flames can be formed at various H2-CH4 ratios. The intensity and distributions of heat release rate can be adjusted by H2-CH4 ratios and equivalence ratios. Finally, the dramatically enhancement of NO emissions at CH4 addition conditions are considered from the promotion of prompt NOx when CH4 added to the H2 flame.

E415 [Invited] Investigation of temperature fluctuation of diode-rectified multiphase AC arc by high-speed visualization
Kyushu University, Fukuoka, Japan

An innovative multiphase AC arc (MPA) was drastically improved by diode rectification technique with bipolar electrodes. Temperature fields of the diode-rectified MPA (DRMPA) were successfully visualized on the basis of a high-speed camera with appropriate band-pass filters. The DRMPA had been developed to solve the electrode erosion issue, which was critical issue for MPA to be utilized in industrial fields. Diode-separation of AC electrode into a pair of cathode and anode led to drastic improvement of the electrode erosion characteristics. However, fundamental phenomena in the DRMPA are still poorly understood because of its novelty, although spatiotemporal characteristics of the arc and/or electrode temperature are necessary to develop the DRMPA for industrial applications. The purpose of the present study is to investigate temperature fluctuation characteristics of the DRMPA. Six phase AC arcs with and without diode-rectification were generated and their temperatures were measured by the high-speed camera system with appropriate band-pass filters on the basis of Boltzmann plot method. Figure shows electrode configurations and the two-dimensional temperature field of the DRMPA (a) and the conventional MPA (b)during one AC period of 60Hz. Results indicated that the arc temperatures of both DRMPA and MPA were fluctuated in the range from 7,000 to 13,000 K. The arc temperature near the electrode was higher than 10,000 K, while the temperature in the center region in the furnace was about 7,000 K. These obtained results suggest that the DRMPA is a promising heat source to fabricate attractive nanomaterials at a high productivity.

E417 Development of composite pellet of calcium carbonate for thermochemical energy storage
Rui GUO1, Hiroki TAKASU2, Shigehiko FUNAYAMA1, Seon Tae KIM2, Yukitaka KATO2
1 Graduate major of Nuclear Engineering, Department of Chemical Science and Engineering, School of Materials and Chemical Technology, Tokyo Institute of Technology. 2-12-1-N1-22, Ookayama, Meguroku, Tokyo 152-8550, Japan
2 Laboratory for Advanced Nuclear Energy, Institute of Innovative Research, Tokyo Institute of Technology. 2-12-1-N1-22, Ookayama, Meguroku, Tokyo 152-8550, Japan

Thermochemical energy storage (TCES) has grown more attention in energy storage and conversion field, for its benefits in better reversibility, lower cost and safer chemical compounds, and higher energy releasing and storage density than conventional sensible and latent heat storage system among thermal energy storage systems. Calcium oxide/water/calcium hydroxide (CaO/H2O/Ca(OH)2) TCES system adapts for heat storage and releasing potential at 400 °C to 600 °C. Calcium carbonate (CaCO3) is used as a precursor for the TCES. However, the raw CaCO3 material from nature shows insufficient performance during heat storage capability and durability experiments. A composite material impregnated with silicon-related material of 0.6 wt% was developed and demonstrated superior reactivity and durability on repetitive operations than a conventional material studied previously. Instead of powder figure TCES materials, real reactors favor materials in pellet figure, then, the composite material in the pellet figure was developed and discussed kinetically TCES material performance in this study. The developed composite pellet material was evaluated by thermogravimetric analysis. The composite pellet was compared with a pure CaCO3 reference pellet on both hydration and dehydration processes. The heat output and storage density and their reaction rates of both materials were compared and discussed under the same operating condition. According to 6 cycles experiment, the composite pellet maintained stable reaction conversion and showed an increase of the hydration reaction rate. It was demonstrated that the additives for the composite had the positive effect and heat output density, Qh,m [kJ kg-material-1], of the composite pellet increased 32.7% in comparison with the pure pellet as shown in Fig. 1. Morphology change of samples before and after experiments indicated that the vapor diffusion and heat transfer were guaranteed by the additives which performed well as effective agglomeration prevention.

E418 Thermal performance of heat exchanger using zeolite/vapor adsorption
Soichiro OHNO, Shuji HIRONAKA, Jun FUKAI
Kyushu University

About 60% of the energy input in the chemical industry is discarded from the plant. Energy saving can be achieved in the entire plant by recovering these waste heats and reusing them as power and heat sources in the power plant. An adsorption heat pump has been developed for the purpose of regeneration of such unused energy.
In this study, saturated humid air was supplied to a device packed with 13X zeolite particles of 4 mm in diameter. The time variation of temperature in the apparatus was measured experimentally. Then, the maximum temperature was estimated from the relationship between heat balance and adsorption equilibrium. The trend of the maximum temperature calculated from the heat balance is consistent with experiment. Further, it was found from the result of the heat balance equation that the sensible heat of the moist air supplied and the heat of adsorption of the zeolite are mainly distributed to the sensible heat of the zeolite. In the future, it is important to make effective use of the sensible heat of this zeolite. In order to extract more thermal energy from the device, it is necessary to improve the heat transfer between the packed bed and medium.
A double pipe heat exchanger having a zeolite packed bed on the annular side was proposed as an apparatus. Flow direction of the humid air supplied to device was changed in two different ways. The one of them is supplying humid air vertically to the device and another is supplying the air in parallel. The influence of flow direction on heat transfer between packed bed and medium is studied with numerical simulation.

E421 [Keynote] On the performance enhancement of spray cooling with the inverse Marangoni effect: chasing the heat
Sung TSANG, Chia-Hsuan LIN, Chen-li SUN
National Taiwan University, Taipei 10617 Taiwan

By inducing the inverse Marangoni convection, we successfully utilize a self-rewetting fluid to enhance the evaporative cooling of a spray system. The self-rewetting fluid is able to produce a surface-tension-driven fluid flow, which continuously replenishes the heated region to prevent dryout. As a result, cooling rate can be drastically increased. We find that the formation of a liquid film after the spray discharge is vital to this cooling enhancement, which requires a superhydrophilic surface and a proper spray height. Once the inverse Marangoni convection commences, the total heat transfer can be augmented three to seven times for a single pulse of spray. On the other hand, using the self-rewetting fluid in an intermittent spray system can be beneficial because comparable heat transfer rate can be delivered by spraying the self-rewetting fluid at much lower frequency. Although a longer spray pulse increases the heat transfer rate per cycle, the spray frequency also decreases for a given duty cycle which is unfavorable when a given time span is considered. Despite the moderate cooling rate per cycle for a shorter spray pulse, the time-averaged heat transfer rate is improved by the increase in spray frequency. For a fixed pulse duration, lower duty cycle leads to more sparse spray, higher surface temperature, and stronger inverse Marangoni convection. However, the resultant cooling rate is poorer and dry-out may occur if the duty cycle becomes too small. For large cooling-area application, we add more spray heads and find that deploying more nozzles helps to reduce the fluctuation in surface temperature but has little effect on the cooling rate. Increasing the spray frequency not only improve the cooling rate but also reduce temperature fluctuation. This enhancement becomes more apparent as the number of nozzles increases.

E423 Effect of Marangoni convection in a droplet containing surfactant on thin film shape
Kyushu University

In recent years, printed electronics, in which wiring of electronic devices are formed by an inkjet method, has been focused. However, when a droplet is deposited on substrate by the inkjet method, there is a problem that it is difficult to control the width and the shape of the thin film. In our laboratory, it has been reported that the addition of surfactant to the coating solution causes Marangoni convection towards the center of the droplet at the surface due to the difference of surface tension, and the film becomes finer. However, the relationship between the flow in droplet and the shape of the film after drying droplet has not been clarified. Therefore, the purpose of this study is to clarify the effect of Marangoni convection on thin film shape by visualizing the flow inside droplet. Samples of the anisole-polystyrene solution with a surfactant are prepared. Each of them includes surfactant in various concentration and a small amount of fluorescent polymer as tracer. Surfactant in each solution is one of the four. Then a small amount of powder fluorescent polymer was added to each solution as tracer. Two experiments for prepared solutions were conducted, which are the dropping them on substrate and measurement of surface tension. Each solution was deposited on a hydrophilic substrate as a droplet with diameter of 80 micrometers using an inkjet method. Finally, the internal flow of droplet during evaporation and the shape of the thin film after drying were observed. Surface tension was measured for solutions including surfactant in various concentrations. As a result, it was revealed that the thin film after drying of a droplet became fine and ring shape tends to be suppressed by Marangoni convection. Additionally, the measurement of surface tension showed that the visualized flow is Marangoni convection.

E424 Formation mechanism of amorphous silicon nanoparticles synthesized by induction thermal plasma
Xiaoyu ZHANG, Kentaro YAMANO, Ririko HAYASHIDA, Hirotaka SONE, Manabu TANAKA, Takayuki WATANABE
Kyushu University, Fukuoka, Japan

This study focus on the synthesis of amorphous silicon nanoparticles by induction thermal plasma and understanding the formation mechanism. Crystalline Si powder with 5 μm of average diameter was injected into the induction thermal plasma at 20 kW-4MHz under atmospheric pressure. The powder feed rate ranges from 64 mg/min to 400 mg/min. Counter-flow quenching gas up to 70 L/min was axially injected from downstream of the torch to enhance the quenching effect for silicon nanoparticles. In the high temperature plasma region, the raw materials immediately evaporate. In the tail region of the plasma flame, supersaturated Si vapor starts to nucleate and then condenses onto its nucleus forming Si nanoparticles. The effect of the operating parameters such as quenching gas flow rate and powder feed rate have been investigated. The collected particles were characterized by using X-ray diffraction (XRD) and transmission electron microscopy. The amorphization degree was defined as the mass fraction of amorphous silicon in the silicon nanoparticles including both crystal and amorphous, and was calculated by internal standard method with XRD results. The obtained results show that higher quenching gas flow rate and lower feed rate lead to smaller diameter with higher amorphization degree. Figure 1 shows the diffraction patterns of nanoparticles with diameter which is equal to 140 nm and 8 nm, respectively. Smaller nanoparticles in Fig. 1 (b) are amorphous because of the appearance of the diffuse rings, while most small nanoparticles agglomerated together. For huge nanoparticle in Fig. 1 (a), some clear and regular diffraction spots are observed in the patterns, and means that the sample is crystal. This research indicates that induction thermal plasma can be used to synthesize pure amorphous material at a single step.

E425 Screening and Performance Evaluation of Hydrogen Bond Donors (HBDs) and Acceptors (HBAs) as CH4 hydrate inhibitors
Woojin GO1, Dongyoung LEE1, Ki-Sub KIM2, Yongwon SEO1
1 School of Urban and Environmental Engineering, Ulsan National Institute of Science and Technology, Ulsan 44919, Republic of Korea
2 School of Chemical and Materials Engineering, Korea National University of Transportation, Chungbuk 27469, Republic of Korea

Oil and gas pipeline blockage due to gas hydrate formation in the deep ocean should be well managed because it would lead to environmental disasters and economic losses. To avoid this issue, researchers have been searching for effective hydrate inhibitors. Kinetic hydrate inhibitors (KHIs) are well-known substances to suppress gas hydrate formation with a small dosage (typically less than 1 wt%) whereas thermodynamic hydrate inhibitors (THIs) require a dosage up to 60 wt%. In this study, we examined inhibition performances of specific HBDs and HBAs using a high-pressure autoclave reactor and a high-pressure micro-differential scanning calorimeter (HP μ-DSC). We used a ramping method with a gradual decrease of temperature (0.2K/min) to measure onset points of hydrate formation which was detected by an abrupt pressure drop. The onset temperatures obtained by this method enabled us to estimate the performance of each inhibitor molecule as a KHI. Furthermore, we used COSMO-RS (COnductor like Screening MOdel for Real Solvents) program to see how the molecular structure and electron distributions of these HBDs and HBAs can affect CH4 hydrate inhibition. We obtained an electron density histogram named σ-profile and a characteristic function named σ-potential to visualize relationships between experimental results and screening results of each molecule. These results will demonstrate how HBD and HBA molecules affect CH4 hydrate inhibition with molecular interaction between inhibitor molecules and host water molecules and contribute to guiding us in the search of effective and environmentally benign inhibitors.

E426 Stable operation of rotary stoker furnace for industrial waste
Koichi SHINOHARA1,2, Daisuke KONO1, Masayoshi MINAKAMI1, Tatsuya KAWAJIRI1, Shuji HIRONAKA2, Jun FUKAI2
2 Kyushu University

Incineration is one of the most general methods to treat industrial waste. Much amount of bottom ash is landfilled without being reused. Reduction of components such as harmful metals contained in bottom ash under appropriate incineration conditions makes it possible to reduce the amount of landfill waste and to increase the amount of reuse bottom ash. Management of conditions to control of bottom ash content has to be done for various kinds of industrial waste whose contents changes every day.
As the first step to improve incineration conditions, the effect of the primary air supplied to the bottom of a rotary stoker furnace is mainly investigated in this study.
Combustion characteristics of industry waste with typical component are numerically investigated using a combustion simulation program. It is confirmed that auxiliary fuel is necessary to burn the waste when preheated primary air is not supplied. On the other hand, preheated primary air enhances dry rate of input materials and enables to burn the waste without auxiliary fuel.
On practical process (commercial facility), components and calorific values of input material are commonly controlled by mixing some kinds of wastes. The preheated primary air effects on reduction of bottom ash amount, decrease of auxiliary fuel consumption and stabilization of furnace operation. The fluctuation ranges of the measured values such as temperatures in the facility are narrowed by preheated primary air, being independent of components of the input materials. This is mainly because the air enhances dry rate in the furnace. Consequently, preheated primary air is found to result in stable operation.

PA301 Effects of nano-hole size and porosity on equilibrium characteristics of calcium chloride in the microcapsules with nano-holes
Iori KANZAKI1, Hiroshi SUZUKI1, Ruri HIDEMA1, Keiko FUJIOKA2
1 Department of Chemical Science and Engineering, Kobe University
2 Functional Fluids Ltd.

In order to develop a novel material for chemical heat pumps using hydration/dehydration of calcium chloride, the hydration equilibrium characteristics of calcium chloride encapsulated in silica hard-shell microcapsules has been investigated. The microcapsule with the mean diameter of about 20 micron has nano-size holes on their surfaces for hydration and dehydration reaction. In this study, the effect of the nano-hole size was focused on. The effects of the shell thickness on the equilibrium characteristics of calcium chloride were also discussed. The nano-hole size was changed from 147 to 1110 nm. The open ratio of hole area to the microcapsule surface increases with nano-hole size from 0.80 to 3.9 % in the present condition. The shell thickness was changed in two steps of 1.9 and 2.3 micron. The calcium chloride six hydration was inserted into the microcapsules. The equilibrium temperature of the dehydration was measured by a thermogravimetry at atmospheric pressure. The heating rate was set at 5 K/min.
From the results, it was found that the dehydration temperature of calcium chloride included in a microcapsule is slightly low. It was also found that the equilibrium temperature decreases with the nano-hole size decrease, in spite of the pressures loss increase for finer nano-hole cases. This indicates the equilibrium condition changes due to a capillary force by interface tension or osmosis effects in the nano-holes. In the case of thin shell, the dehydration temperature was found drastically to decrease. This might occur due to the above reasons under the condition of decrease of pressure loss effects. From the present results, it was concluded that the calcium chloride encapsulated in the microcapsules with fine nano-holes and with thin shell is a promising candidate for the high-performance chemical heat pump composites.

PA302 On Al synthesis, Morphology Control and Heat Transfer Application of Carbon Nanotubes
Mayu ASAKA1, Hisashi SUGIME1, Aun OTA2, Hisayoshi OSHIMA2, Suguru NODA1
1 Waseda University, Tokyo, Japan

Al is widely used as a material for various heat exchangers because of its high thermal conductivity, small mass density, and high plasticity. The device performance has been improved by making the fins finer, however, it is difficult to make finer structure (< 1 mm). Carbon nanotubes (CNTs) also have high thermal conductivity and small mass density. In addition, simple fabrication of fine structure is possible via their self-organization process. Here we propose CNT-Al hybrid heat exchangers by growing micro-fins of CNTs directly on the conventional Al fins.
CNT arrays can be grown directly on Al sheets by chemical vapor deposition (CVD), however, their height remained 0.1 mm or less due to the low melting point of Al (660 °C). We realized 1.1 mm-tall CNT arrays by CVD at 600 °C [1]. To prevent the deactivation of catalyst pre-sputtered on Al, the C2H2 source was fed at low concentration with CO2 additive at high concentration. This method enabled tall CNT arrays but in a long CVD time (1.1 mm in 12 h). Then we elevated the C2H2 concentration and fed ferrocene (Fc) simultaneously, to grow CNTs fast and deposit Fe catalyst continuously. This method enabled >0.5 mm-tall CNT array in 2 h. Al sheet was prepatterned by using a pen-ink for selective catalyst deactivation (Fig. 1a) and the resulting CNT array was densified by wetting with ethanol and successive drying (Fig. 1b,c). Finally, we examined the heat dissipation performance using plate heater and N2 gas flow. Compared with the Al sheet, the performance improved about 1.5 times with the CNT fin arrays set parallel to the flow and about over twice set perpendicular to the flow (Fig. 1d). It is surprising to obtain such significant improvement. CNT fin structure induces vortex and make boundary layer thinner. Detailed analysis is underway.

PA303 Theoretical study on heat transfer mechanism of confined nanofluid containing graphene flakes
Eun Min GO, Eunhye SHIN, Sang Kyu Kwak
Department of Energy Engineering, School of Energy and Chemical Engineering, Ulsan National Institute of Science and Technology (UNIST), Ulsan 44919, Republic of Korea

Nanoparticles in heated pipe flow are known to enhance the heat transfer ability of fluids. Although positive effects on the improvement of heat transfer ability of nanoparticles have been experimentally confirmed, it is difficult to identify the reason and mechanism of heat transfer with solely empirical way. Thus, we theoretically investigated the heat transfer mechanism of nanofluid containing graphene flakes (GFs), which exhibits good thermal conductivity, using coarse-grained molecular dynamics (CGMD). The size of 2.2 nm GF was used for nanofluids and four carbon atoms were replaced by one CG bead to maintain the hexagonal structure of GF. Heat transfer coefficient (HTC) of coolant, a mixture (50:50 wt%) of water and ethylene glycol (EG), containing GFs (1 wt%) was estimated in nanopipe flow system, of which the pipe is made of iron. Heat transfer trend was studied according to the functional groups (-H, -OH, -COOH) of GF. GF with hydrophilic functional groups (-OH, -COOH) showed higher dispersibility in the fluids than H-terminated GF. Also, nanofluid with COOH-terminated GF showed 25% higher thermal conductivity than that of without GF. In the nanopipe flow system with 0.1 â/ps of flow rate, we presented temperature, velocity, HTC profiles of nanofluids to elucidate the heat transfer mechanism. In the entrance region, GFs were located near the pipe wall and worked to transfer the heat of pipe to fluid. In the thermally fully developed region, GFs gradually moved to the center of pipe. Interestingly, the thermal boundary layer was maintained in the thermally fully developed region in the fluid. Additionally, GFs with hydrophilic functional groups showed larger HTC with higher rotation rate in the fluid.

PA304 Hydrothermal synthesis of functionalized copper nanowire and its application for hydrofluorocarbon-base nanofluid with enhanced thermal conductivity
Sarii YAMAGUCHI, Shohei KANAZAWA, Masahide SATO, Takeshi FURUSAWA, Noboru SUZUKI
Department of Material and Environmental Chemistry, Utsunomiya University

Copper nanowire (Cu NW) with high aspect ratio was obtained by D-glucose reduction under mild hydrothermal conditions. Use of oleylamine/oleic acid as Cu NW surface stabilizer led to obtain high aspect ratio over 1,000 of Cu NWs. Addition of small amount of sodium chloride for improvement of yields of Cu NWs up to over 90 % at optimum experimental condition. After centrifugal washing and recovery, direct surface modification of Cu NWs by immersing into hexane solution of fluoroalkylthiol self-assembled monolayer (SAM) were performed for achieving long lifetime well-dispersibility of Cu NWs into hydrofluorocarbon (HFE) -base heat transfer fluids. Applying the vacuum drying process of fluoroalkylthiol SAM functionalized Cu NWs in order to remove resume solvent such as deionized water and hexane surface led to obtaining highly dispersion stability over six months of fluoroalkylthiol SAM functionalized Cu NWs into HFE fluids.
The thermal conductivities of fluoroalkylthiol SAM functionalized Cu NWs dispersed HFC base nanofluid were measured by using transit thin hot wire (THW) method. A platinum thin wire coated with 3-mercaptopropyltrimethoxysilane (MPS) / tetraethoxysilane (TEOS) / 1H, H, 2H, 2H-perfluorodecyltriethoxysilane (PFDTS) hybrid film was used as a heating element and a resistance thermometer. High quality thermal conductivity measurement could be achieved by using thicker MPS/TEOS/PEDTS hybrid insulator coated platinum thin wire because of minimizing electrical leakage of fluoroalkylthiol SAM functionalized Cu NWs nanofluid in measurement cell. The effective thermal conductivities of obtained SAM functionalized Cu NWs dispersed nanofluids were increased as Cu NW concentration increases and maximum increase ratio was up to 80% comparing with the base HFC fluid.

PA305 Numerical simulation of the transport phenomena occurring in the Bottom Seeded Solution Growth (BSSG) process of SiC
Jiangao ZHANG1, Taichi YOSHIMURA1, Atsushi SEKIMOTO1, Takahiko BAN1, Yasunori OKANO1, Hossein Khodamoradi2, Toru UJIHARA3, Sadik Dost4
1 Department of Materials Engineering Science, Osaka Univerisity, Osaka, Japan
2 Physics Department, Bu-Ali Sina University, Hamedan, Iran
3 Department of Crystalline Materials Science, Nagoya Univerisity, Nagoya, Aichi, Japan
4 Crystal Growth Laboratory, Univerisity of Victoria, Victoria, Canada

Silicon carbide (SiC) is a promising wide-band gap semiconductor material for power devices due to its high electrical breakdown field and high thermal conductivity. But the performance of SiC devices is limited by the quality of the crystal growth because of the high dislocation density and high residual stress. In order to remedy these shortfalls, solution growth processes have been developed to grow high quality crystals. One of such solution growth processes is the Top Seeded Solution Growth (TSSG) method. However, it was found that in this growth process the Marangoni convection developing in the melt is strong and has an adverse effect on crystal homogeneity [1]. Therefore, we focus on the bottom seeded solution growth (BSSG) method shown in Fig. 1, since this technique had shown reduction in dislocation density in growth of GaAs [2]. In addition, the adverse effect of Marangoni convection is not significant because the seed is at the bottom of the crucible.
To the best of our knowledge, most numerical simulations in the literature were conducted in 2D. In this study, we carried out a 3D numerical simulation to investigate the transport phenomena occurring during the BSSG process of SiC. The simulation model includes the induced electromagnetic field, the radiative and conductive heat transfer in the furnace, and the mass transfer and fluid flow in the melt. The results showed that the Lorentz force in the 3D flow structures of melt is dominant while the contributions of buoyancy and Marangoni flows are small and the corresponding flow patterns remain axisymmetric. It was also found that the crucible rotation has a significant effect on growth rate. While the crucible rotation improves crystal uniformity, it decreases the average growth rate.
[1] T. Yamamoto et al., J. Cryst. Growth., 470 (2017), 75-88.
[2] K. Hoshikawa et al., J. Cryst. Growth., 94 (1989), 643-650.

PA306 Direct numerical simulation of turbulent heat transfer in a plane channel flow with stable density stratification
Liya WANG, Atsushi SEKIMOTO, Yasunori OKANO
Dept. of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, Osaka, Japan

The direct numerical simulations of fully-developed turbulent plane channel flow with a spanwise narrow computational box to understand the turbulent heat transfer over the wall. We would like to demonstrate the effects of near-wall turbulent vortices on the heat transfer rate. The configuration is stably stratified channel flow with an imposed temperature difference between the top and bottom walls as shown in Fig. 1(a). The equations of continuity, Navier-Stokes and energy are discretized by using a high-fidelity spectral method and third-order Runge-Kutta semi-implicit scheme in the time integration [1].
In the present configuration, the spanwise narrow computational domain significantly reduces the computational cost and enables a parametric study of buoyancy effect on the instantaneous turbulent structures. In this study, the effect of the Richardson number which is the ratio of buoyancy force and inertial force are investigated at relatively high Reynolds number at the Prandtl number, Pr = 1. The obtained turbulent statistics are used to validate by comparing with the existing databases and the agreements and discrepancies due to the spanwise narrow computational domain are also discussed.
The vortical structures in the lower half of the channel flow are visualized as in Fig .1b using so-called Q criterion, i.e. the second invariant of the velocity gradient tensor. These turbulent vortices contribute strong turbulent intensity near the wall and turbulent heat transfer over the wall is enhanced. The effect of buoyancy on the turbulent statistics and the relationship between coherent vortices and the mean heat transfer rate will be discussed.
[1] J. Kim, P. Moin, and R. D. Moser. Turbulent statistics in fully developed channel flow at low Reynolds number. J. Fluid Mech., 177:133-166, 1987.

PA307 Simulation of a thin film evaporator for polymer solution
Kaneka Corporation, Takasago, Hyogo, Japan

In a thin film evaporator (TFE), the axial distribution of liquid concentration is not clear, so it is difficult to predict the final concentration under various equipment design patterns and operating conditions. The focus of this research is on the evaporation of an acrylic polymer solution in TFE, a simulation model of which is proposed in this research.
In this model, the axial distribution of the concentration from top(inlet) to bottom(outlet) in TFE is simulated by sequentially calculating the shell balance of energy and mass. As outputs of this simulation, final concentration of the acrylic polymer is obtained. Parameters for correlating heat transfer coefficients and some factors are determined by least squares method using bench scale and plant scale equipment.
This simulation model is useful for predicting final concentration of polymer solution under unknown design patterns. For example, in case of changing blades number, there are several patterns (ex. position, number), and each of them have a different final concentration. By using this simulation, the several patterns of the final concentration can be calculated. As a result of changing blades number in plant scale, the measurements of the final concentration are within 2σ (95% confidence limit) of the predicted value, and it can be seen that both of them is in good agreement.

PA308 Thermo-irreversible supramolecular hydrogel using an imine bond that visualizes thermal hysteresis
Kobe University, Kobe, Hyogo, Japan

In general, a supramolecular gel is known to show reversible gel-sol transition responsive to various external stimuli such as heat and pH changes because of its weak non-covalent crosslinking. In this study, however, we designed a thermo-irreversible supramolecular gelator. The gelator was prepared by mixing a peptide lipid, NH2-C12-Gly-Gly-Gly-His (amino-C12G3H), and 4-ethylbenzaldehyde (EBAL) in an aqueous solution (pH 10.0). Mixing amino-C12G3H and EBAL forms an imine bond, which is a reversible reaction (Figure 1). We anticipated that the formation of an imine bond produced a supramolecular gelator to gelate an aqueous solution. Heating the resultant gel caused the gel-sol transition and evaporated the volatile aldehyde (EBAL). The removal of EBAL did not allow gelation upon cooling, which would achieve thermo-irreversible gel-sol transition in the supramolecular gel. In fact, the formation of a supramolecular gelator gave a supramolecular hydrogel and a microfibrous structure (self-assembly of the gelator molecules) was observed by TEM. After the supramolecular gel was heated at 80 °C for 40 min with keeping a cap of a sample vial open, the solution never turned to gel again (thermo-irreversible gel-sol transition). 1H-NMR measurements confirmed the removal of EBAL after heating. Finally, we tried to visibly record thermal hysteresis on a supramolecular gel. Tuning the EBAL concentration and heating time at 80 °C controlled the thermo-irreversible gel-sol transition, indicating that the present system can visualize and record the thermal hysteresis as gel or sol. The use of benzaldehyde as an aldehyde, which is more volatile than EBAL, allowed the thermo-irreversible gel-sol transition at 50 °C, meaning that the temperature for the thermo-irreversibility can be controlled by the selection of an aldehyde.

PA309 Simulation of energy balances for installation of thermal energy storage at paper mills in Japan
Ayumi YAMAKI, Yuichiro KANEMATSU, Yasunori KIKUCHI
the University of Tokyo, Tokyo, Japan

Power generation by variable renewable energy (VRE) is increased for decarbonization, which need suppress output to control the quality of electricity. As a power reserve, wind powered thermal energy system was proposed, which stores heat generated from rotating energy and produces steam to drive turbine or direct use. In this study, we examine Thermal Energy Storage system in Paper mill (TESP) and simulate to estimate capacity of thermal energy storage (TES) at paper mills all over Japan. Paper mills converts large amounts of energy by in-house boilers and turbines , the capacity utilization ratios (CUR) of which are fluctuated depending on the paper demand and fuel prices .
A concept of TESP is that heat from boilers and VRE is stored in TES and converted into steam or electricity like the system of concentrated solar power. Excess heat stored in TES generates constant electricity to sell to power grid. Constant generation of steam and electricity can reduce cost by raising CUR of energy plants, and decarbonize by accepting VRE .
We simulated energy balances with and without TES in a paper mills. Without TES, CUR of energy plants were low due to the fluctuation of energy demand. With TES, CUR were basically increased by storing excess heat. The necessitated capacity of TES varies by operation patterns. When production lines stop all together, large capacity of TES is required since large amounts of excess heat is generated. Through this simulation, we can estimate capacity of TES depending on paper demand all over Japan.
We conducted a simulation to design appropriate specification of TES depending on paper milling process and operation. This simulation will facilitate the design of appropriate scale of TESP depending on paper demand, cost and environmental impacts. Paper mills may be a supplier of heat and electricity from distributed energy sources.

PA310 Interfacial tension between decane-water with Triton X-100 and different concentration of NaCl by microwave irradiation
Yosuke SHIBATA1, Satoshi SONOBE1, Yusuke ASAKUMA1, Anita Hyde2, Chi Phan2
1 University of Hyogo
2 Curtin University

Some processes such as flotation with nano or micro bubbles, mechanical operation like centrifuge separations and electro conglutination have been used for the demulsification of the wastewater produced from the well. Recently, demulsification by mean of usage of quick thermal response of microwave heating has been proposed as an efficient method. Our previous study found special microwave behaviors for interfacial tension between two liquids [1]. For example, there is hysteresis of interfacial tension between heating and cooling process and the tension after the irradiation does not return to the original value. Moreover, difference between thermal effect and non-thermal effect like non-equilibrium local heating, which is caused by the vibration of water molecule around the interface, is not clear. In this study, interfacial tension between decane-water was measured during and after microwave irradiation when concentration of NaCl in water was changed to investigate effect of saline solution on the microwave special behavior. First, hysteresis was observed between the heating and cooling interfacial tension as well. The above special behavior such interfacial tension reduction was confirmed and the effect was prompted by addition of salt in water phase. This is because microwave absorbs in water phase with salt more strongly. As a result, more emulsions are produced around the interface, and they interrupt tension along the interface. Recently, the efficient separation process of emulsion water produced at mining crude oil has been required. Finally, this technique has a potential as higher performance of the separation process by interface modification.

PA311 Homogenization method for thermal radiation of a packed bed of binary particles
Yusuke ASAKUMA2, Itsuro HONDA2, Tsuyoshi YAMAMOTO1
1 Kyushu University
2 University of Hyogo

Thermal analysis of packed bed with two particles, which show different emissivities and thermal conductivities, was conducted by homogenization method. Sigmoidal curve as a function of Nusselt number with a thermal radiation coefficient was obtained. The emissivities are enclosed in the Nusselt number, and parameters representing shape of sigmoidal curve are mainly decided by ratio of the particle number and the thermal conductivities of two particles. Finally, it was found that thermal radiation analysis in more complex structures like packed bed and porous medium became simpler by homogenization method, and this multi-scale simulation is expected to contribute reduction of computational cost.

PA312 Effect of external magnetic field on long DC arc characteristics with ring-shaped anode
Akio HASHIZAWA1, Manabu TANAKA1, Takayuki WATANABE1, Tomohiro KOGA2
1 Department of chemical engineering, Kyushu University
2 Clean Technology Co. Ltd.

Fluctuation phenomena of plasma jet flow in an innovative long DC arc system with ring-shaped anode were successfully clarified on the basis of the high-speed camera visualization. The long DC arc with long electrode gap distance more than 350 mm has been applied to gas decomposition due to its advantages of long plasma length, resulting in long residence time of treated gas. However, large heat loss at a conventional hemispherical-shaped anode was critical issue in the long DC arc system. Therefore, a ring-shaped anode was utilized to convert large energy loss at the anode into the plasma jet flow. Calorimetric measurements were carried out to evaluate energy balance in the long DC arc system with the ring-shaped anode. Results indicated that the 60% of heat loss at the conventional hemispherical-shaped anode was converted into the plasma jet flow when the ring-shaped anode was utilized. High-speed camera observation revealed the effect of external magnetic field on the fluctuation phenomena in the long DC arc. Figure 1 shows the high-speed snapshots of arc and plasma jet (a) with and (b) without external magnetic field. Upper images correspond to the arc images while bottom images show the plasma jets. External magnetic field leads to arc swirl motion. Plasma jet fluctuates with the frequency of several tenth Hz when the magnetic field was applied. These understanding of arc and plasma jet fluctuation enables to improve the capability of long DC arc system.

PA313 Analysis of thermal and light properties of greenhouse considering greenhouse sheets characteristics in hot and h humid area in Asia
Seiji MATSUO1, Yuki HONZAWA1, Toyohisa FUJITA, Yasunaga IWASAKI2
1 The University of Tokyo, Tokyo, Japan
2 National Agriculture and Food Research Organization, Tsukuba, Japan

Food market in Asia is expanding at dramatic rate. In the near future, there will be about 400 million rich people who will eat raw vegetables as well as Japanese people, which is a great business opportunity for the farmer in Japan who has the know-how to produce high-quality vegetables. However, the weather conditions in Asia, especially in south-east Asia, can induce poor growth of plants because of its distinctive high temperature and humidity. In this case, it is effective to put a light shielding material on the outside of the house film, but the yield loss may be caused by shy bearing of fruits due to the lack of solar radiation.
In this study, the authors investigated the effects of some greenhouse heat-shielding sheets on the yield of tomato production in hot and humid regions of Asia. In particular, the spectral and optical properties of the heat-shielding sheets were compared with those of conventional greenhouse sheets, and the thermal properties such as the temperature and the amount of solar radiation in the greenhouse covered with these were analyzed. Modern greenhouse sheets must be sufficiently strong to withstand different climatic conditions. It should allow good transmission of solar photosynthetically active radiation (PAR) and maintain the good heat insulation properties over a long time period.
Consequently, it became possible to analyze the degree of suppression of the temperature rise of the greenhouse due to absorption of heat rays and the distribution of visible light necessary for photosynthesis when using heat-shielding materials for the greenhouse at high temperature. It was suggested that focusing on the absorption rate and considering characteristic of film by wavelength are also important by this simulation.

PA314 Establishment of microwave thawing calculation method for heterogeneous food
Yasuaki TAGUCHI1, Mika FUKUOKA1, Naoki YOSHIOKA2, Tomonori HOSODA2, Takashi KIMURA2, Kayoko ONIZAWA2, Noboru SAKAI1
1 Tokyo University of Marine Science and Technology, Tokyo, Japan

There are many reports on calculation method for homogeneous food, but few method for heterogeneous foods such as cooked rice. In this study, using some containers for storing frozen cooked rice, which are commercially available, microwave thawing calculation method for heterogeneous food was proposed. Furthermore, change of temperature distribution with time for calculation result was compared to that of experiment result to verify accuracy.
As experiment method, cooked rice of 177g was filled into a container and was frozen with domestic refrigerator for 24 hours. When filled rice, 0.2 mm thick polypropylene film was set in the center of container to bisect the rice and get temperature distribution easily. After that, that sample was heated by microwave with 600W and temperature distribution of vertical section was captured by infrared thermal camera. Heating time was 180 s, time interval for camera shooting was 30 s.
Using FEMAP which is a commercial software, 3D model was made based on the size of microwave oven, cooked rice and container. Created model of cooked rice had 29% pore elements which were assigned randomly in the rice model. Calculation conditions were determined for electromagnetic field analysis and heat transfer analysis. When frozen cooked rice is heated, heat convection of vapor will be occurred because cooked rice has pore in the system. But heat transfer model used in this study can't calculate convection heat transfer. Therefore, we tried to estimate apparent thermal conductivity to represent heat convection. After setting condition, calculation was carried out by coupling two models.
As a experiment result, the temperature was risen from bottom side of container, then cold spot was confirmed above dent structure after microwave heating. Calculation results also showed the same tendency and change of temperature distribution with time was agreed with the experiment result. Thus, the calculation method for heterogeneous food was established.

PA315 Measurement of internal temperature distribution of double film robber heat exchanger
Tomoya KANAI1, Nobuhiro MARUOKA2, Hiroshi NOGAMI2
1 Graduate School of Engineering, Tohoku University,
2 Institute of Multidisciplinary Research for Advanced Materials, Tohoku University

Double film robber (DFR) heat exchanger that mechanically scrapes the temperature boundary layer by the combination of the rotating heat transfer tube and the fixed blades can achieve quite high performance, namely the heat transfer coefficient higher than 10000 Wm-2K-1. It, however, is known that its performance largely depends on the operating condition, and it is necessary to grasp the improving mechanism of heat transfer rate for designing the equipment and the operating conditions. This study discussed the heat transfer mechanism from thermal fluid flow in the DFR heat exchanger. The temperature distribution in the heat exchanger was measured by inserting the multiple thermocouples. Fig. 1 shows the temperature distributions of outer fluid with and without the tube rotation. Without tube rotation, the temperature of the fluid only in the vicinity of the heat transfer tube rises. Contrarily, the temperature of fluid rises uniformly over the whole radius. This means that, not only scraping the temperature boundary layer but also the fluid mixing that lets the fluid away from the heat transfer tube to participate in the heat exchange improves the heat transfer performance.

PA316 Modeling of atmospheric freeze-drying of food product operated above glass transition temperature
Nakabayashi, M.1, KOBAYASHI, T.1, NAKAGAWA, K.2
1 Graduate School of Agriculture, Kyoto University, Kyoto, Japan
2 Graduate School of Engineering, Kyoto University, Kyotodaigaku-Katsura, Nishikyo-Ku, Kyoto 615-8510 Japan

A mathematical model that simulates atmospheric freeze-drying for minced salmon was developed and validated with experimental drying runs. This study was targeted for an atmospheric freeze-drying that operated far over the glass transition temperature of the products, where we must admit the product deformation such as shrinkage and micro-collapse due to glass-rubber transition. The developed mathematical model was based on the mass and heat balance equations, and the solution could be obtained by assuming the quasi-steady-state energy balance at the sublimation interface. Air temperature could be programmed to increase as the progress of drying in order to accelerate drying rate. A simulation was carried out based on the mathematical model by applying the experimentally obtained parameters such as mass and heat transfer coefficients, air flow temperature etc. The apparent water vapor pressure of products was assumed to be dependent on the temperature and moisture content, and it was experimentally measured by carrying out the pressure rise test for samples with different temperature and moisture content. It was confirmed that the simulation well predicts the experimental drying kinetics. The present simulation is based on a mechanistic mathematical model, so it simultaneously gives the other important values such as product temperature, mass and heat flow rates, etc. The simulated product temperature suggested that the drying progressed far above the glass transition temperature of salmon, so some phenomena that may occur in a rubbery system (e.g. shrinkage, micro-collapse) are not avoidable in this drying system. This simulation approach would be useful to design favorable drying protocol, where freeze-drying progresses under atmospheric condition.

Session 4. Separation processes

J201 Quick refolding of high concentration protein via microchannel flow dialysis
Hidenori OHASHI, Aoi KATO
Tokyo University of Agriculture and Technology, Koganei, Japan

This paper offers how to realize quick refolding of high concentration protein via microchannel flow membrane dialysis. E. coli. are suitable host cells for mass production of proteins due to their fast proliferation and translation rate. On the other hand, proteins produced by E. coli. are often expressed as insoluble inclusion body, which have no activity. In that case, the “refolding” process to recover the original protein structure and activity is required. A quick refolding of high-concentration protein is important issue for industrial process but generally quite difficult. Dilution method can quickly refold protein but the concentration becomes low, while dialysis method can refold high concentration protein but requires long time. Considering the rate determining step of the dialysis is the slow permeation of denaturant through dialysis membrane, here, we propose the design to realize both of quick and high-concentration protein refolding by using microchannel flow dialysis.
Dialysis membrane was sandwiched with two microchannels; feed channel and permeation channel. Carbonic Anhydrase (CA) (as model enzyme) denatured by denaturant (guanidinium chloride (GdmCl)) was fed into feed channel. On the other hand, refolding buffer was fed into permeation channel. The denaturant was quickly removed from feed channel to permeation channel through dialysis membrane due to high specific membrane surface area in microchannel flow. As a result, CA can be refolded in only twenty minutes, which are much shorter than the time for conventional dialysis method, and just a bit longer than the time required for refolding of CA. Furthermore, the microchannel flow process realizes almost 100% protein recovery and active recovery for CA with concentration as high as conventional dialysis method within the quick process. The demerit of the microchannel flow is low flow rate but it can be easily solved by numbering up and increasing flow rate with longer channel flow.

J202 Bio-inspired chemical engineering by using liposome membrane platform
Hiroshi UMAKOSHI, Keishi SUGA, Yukihiro OKAMOTO
Osaka University, 1-3 Machikaneyama-cho, Toyonaka, Osaka, Japan

A “Biomembrane” is a highly-organized self-assembly of biomolecules (i.e. lipid, protein etc.) and a key interface for the survival of biological cell. The “Membranome” can be defined as the properties of vesicle (or liposome), which arise from the bilayer molecular assembly of amphiphiles, focusing on “emergent properties” which are not present in the individual components, and is gradually recognized as an important research methodology to investigate the potential functions of vesicles (or liposome) and to apply them for the bioprocess design. “Self-Organizing System”, such as liposome or vesicle, possesses several benefits in the recognition of (bio)molecules, where it can recognize them with (i) electrostatic, (ii) hydrophobic interaction, and (iii) stabilization effect of hydrogen bonds at its surface. A key of next chemical engineering is the use of “Self-Organizing System”, where “enthalpy-driven” nature of chemical process would be converted to “entropy-driven” one. We call this strategy as “Bio-Inspired Chemical Engineering”. In this study, the basic and applied aspect of the self-organizing system were reviewed, especially focusing on chiral separation and chiral conversion process.
P. Walde et al., Chem. Commun., 50, 10177-10197 (2014). T. Ishigami et al., ACS Appl. Mater. Interf., 7, 21065-21072 (2015). T. Ishigami et al., Langmuir, 32, 6011-6019 (2016). M. Hirose et al., Langmuir, 31, 12968-12974 (2015). F. Iwasaki et al., ACS Omega, 2, 91-97 (2017). F. Iwasaki et al., ACS Omega, 2, 1447-1453 (2017).

J203 Molecular dynamics simulation of FO/RO water permeation in amphotericin B water channel
Tomohisa YOSHIOKA1, Keisuke KOTAKA1, Keizo NAKAGAWA1, Takuji SHINTANI1, Takahiro KAWAKATSU2, Yu FUJIMURA2, Hao-Chen WU3, Hideto MATSUYAMA3
1 Center for Membrane and Film Technology / Graduate School of Science, Technology and Innovation, Kobe University
2 Kurita Water Industries Ltd.
3 Center for Membrane and Film Technology / Graduate School of Science, Technology and Innovation, Kobe University

Polyamide and cellulose triacetate are known to be materials for reverse osmosis (RO) membranes, which are used in desalination of seawater. In order to deal with increasing water demands all over the world, a development of higher performance RO membrane and membrane processes are required. A drastic change in RO membrane materials would lead to one of the solutions to improve RO membrane performance. Amphotericin B-Ergosterol (AmBEr) is a biomimetic channel, and water and specific ions can be selectively transported through the channel [1]. RO membranes in which AmBEr channels can be embedded suitably are expected to be utilized high performance RO membranes. In order to design high water permeable channels, it is indispensable to understand microscopic channel structures and water transport mechanisms in a molecular scale.
In this study, a quasi-non-equilibrium MD simulation technique with applied (RO mode) or osmotic (forward osmosis, FO mode) pressure difference of several MPa was conducted to estimate water permeability through an AmBEr channel (Fig.). We had successfully carried out direct simulation of forward osmosis (FO) water permeation in artificial water channels [2]. In RO simulation, the virtual pressure was applied by increasing density of seawater side in RO simulations. Simulated FO and RO water permeability for an AmBEr channel were equal to or greater than the water permeability in Aquaporin [3] and carbon nanotube [4] water channels. No permeation of Na+ and Cl- ions were observed during the simulation time of several nanoseconds. The results suggested the excellent performance of AmBEr channel as an artificial biomimetic membrane material.
[1] H. Wu et al., J. Memb. Sci., 545, 229 (2018), [2] H. Wu et al., Desalination, 424, 85 (2017), [3] M. Kumar et al., Proc. Natl. Acad. Sci., 104, 20719 (2007), [4] B. Corry, J. Phys. Chem. B, 112, 1427 (2008)

J204 Development of novel molecular dynamics technique for nanofiltration with multi-component feed solution
Kogakuin University, Hachioji, Tokyo, Japan

Nanofiltration has been applied to various separation systems, in particular, for the separation of aqueous or organic solvents. For a development of more efficient membrane process, better understanding of separation mechanism of solvent including multicomponent species is of fundamental. Molecular modeling becomes a powerful tool for prediction of membrane performance and design of membrane materials for particular separation systems. Our group has reported a novel simulation scheme of molecular dynamics for the permeation of feed solution through nano porous membranes. Molecular dynamics of multi component species in the feed, however, is still difficult to be simulated because a feed concentration of multicomponent such as ions cannot keep at a constant in our simulation techniques as well as other conventional non-equilibrium molecular dynamics scheme. In this paper, to model multicomponent solutions through nanofiltration or reverse osmosis membranes, we will present a novel molecular dynamics technique that can control the feed concentration including multicomponent species at constant. This simulation technique is completely new and first methodology that could model multicomponent solution systems in membrane separation from atomistic level, as long as our knowledge. We will report that this simulation technique works well and can produce the permeation of multicomponent feed solution. The flux and ions selectivity were calculated and compared to the theoretical values to examine the validity of our proposed scheme.

J205 Scale-up of high performance mordenite membranes for dehydration of water-acetic acid mixtures
Yuqin LIA1, Tian GUIA1, Xiaowei WUA1, Meihua ZHUA1, Xiangshu CHEN1, Hidetoshi KITA2
1 Jiangxi Normal University, Nanchang, 330022, P.R. China
2 Yamaguchi University, Ube, 755-8661, Japan

We have synthesized 80-cm-long mordenite membranes on mullite supports by secondary growth method. Mordenite has a moderate Si/Al ratio of 3–10 and regular pore size of 0.65 × 0.7 nm. These advantages allow mordenite membranes to be a potential candidate for separating water from acetic acid solutions with excellent acidic-resistant property and hydrophilicity. The enhancement of flux as well as high reproducibility is critical for industrial application of mordenite membranes. To improve the flux of membrane, we rapidly prepare mordenite membranes on macroporous mullite supports in a fluoride-containing precursor gel. The molar composition of synthesis solution is 1SiO2: 0.08Al2O3: 0.25Na2O: 0.2NaF: 40H2O. The hydrothermal treatment is carried out at 170 °C for 5 h. After synthesis, the as-synthesized membranes are characterized by XRD, SEM and pervaporation (PV) test. The surface SEM image of the membrane prepared under optimal conditions shows compact and highly intergrown zeolite layers composed with ellipsoidal polycrystalline grains. The membrane thickness is approximately 8 μm. High-flux mordenite membranes exhibit a long-term acid stability for a 90 wt% HAc/H2O mixture at 75 °C, the flux and separation factor ultimately keep stable at approximately 1.03 kg m-2 h-1 and 4500 for 10 d. Furthermore, mordenite membranes are successfully scaled-up from 10 cm to an industrial scale of 80 cm with transverse crystallization. These high performance 80-cm-long mordenite membranes with good roeprducibility show a promising industrial application for dehydration of water-acetic acid mixtures.

J213 Fabrication of niobium oxide based nanosheet membranes and their nanofiltration performance in water and alcohol
Keizo NAKAGAWA1, Misato KUNIMATSU2, Tomohisa YOSHIOKA1, Takuji SHINTANI1, Eiji KAMIO2, Hideto MATSUYAMA1,2
1 Center for Membrane and Film Technology / Graduate School of Science, Technology and Innovation, Kobe University, Kobe, Japan
2 Center for Membrane and Film Technology / Department of Chemical Science and Engineering, Kobe University, Kobe, Japan

Two-dimensional (2D) nanosheet membranes are expected to function as size-selective molecular separation membranes, based on their unique atomic thickness with micrometer lateral dimensions. Stacked nanosheet membranes are formed by assembling single molecular sheets into thin membranes, and contain 2D nanochannels between the stacked sheets that allow water or solvents to pass through whilst rejecting unwanted solutes [1]. Therefore, they represent promising materials for potentially high-functional membranes for liquid separation such as water treatment and organic solvent filtration. The structural stability of nanosheet membranes during filtration is also a critical issue for their application.
In this study, we fabricated nanosheet membranes using single 2D nanosheets of niobium oxide (NbO) on a porous cellulose nitrate or anodic alumina support by a simple vacuum filtration. The thickness of NbO membranes were controlled by adjusting the volume of nanosheet colloidal solution used during the vacuum filtration. The stacked NbO nanosheet membranes had a dense structure and were highly stable during separation tests, because of the chemical cross-linking between nanosheets. The method allowed the formation of nanochannels in the NbO membranes. The NbO membranes showed high rejection performances against anionic dyes and salts in water [2,3]. Furthermore, membrane structure and separation performances in alcohols were also investigated. There was little difference in the interlayer spacing of the stacked structure between water and alcohols, suggesting the stable layered structure in alcohol solvents. The NbO membranes demonstrated relatively high rejection performances such as 85% rejection for Evans blue (EB, Mw: 960.8) in methanol. The channel structure and separation mechanism for NbO membranes in water and alcohols will be discussed.
[1] G. Liu, et al., Angew. Chem. Int. Ed.55, 2–16 (2016), [2] K. Nakagawa et al., Chem. Commun. 53, 7929-7932 (2017), [3] K. Nakagawa et al., Sep. Purif. Technol, 219, 222-229 (2019)

J214 Improved propylene separation from propane using ZIF-8 membrane prepared using sodium formate from secondary growth synthesis
Nguyen Tien TRAN, Jinsoo KIM
Kyung Hee University, Young-In, Korea

High purity propylene is an octane-enhancing chemical and also feedstock to industrially important chemicals. Purification of propylene from propane mixture is technologically and financially challenging because of their close boiling points. ZIF-8 membrane has the potential to separate propylene from propane effectively due to the gate opening effects, although the theoretical ZIF-8 aperture size (0.34 nm) is smaller than the kinetic diameters of propylene (0.4 nm) and propane (0.43 nm). In this work, defect free ZIF-8 membranes were successfully developed from the secondary growth seeding technique with sodium formate as deprotonating agent that facilitated continuous, well-intergrown ZIF-8 membrane on α-Al2O3 support. The defects formed by the crack formation in the membrane was steadily and effectively removed by the uniquely discovered self-healing property that the sodium formate extended. The ZIF-8 membranes demonstrated their excellent molecular sieve separation capability for equal molar propylene/propane mixture with the highest separation factor of 115 and average propylene permeance of 50.40×10-10 mol/m2 s Pa.

J215 [Keynote] Omniphobic inorganic membranes fabricated through nanoarchitectured design of ZnO depositions
Kuo-Lun TUNG, Allen HUANG, Yi-Ray CHEN, Chien-Hua CHEN, Chia-Chi KAN
National Taiwan University, Taipei 10617, Taiwan (R.O.C.)

In this talk, I will report the development of novel omniphobic membranes and operation modes for various process applications with membrane contactors (MCs). An omniphobic membrane was fabricated for membrane distillation (MD) by effectively depositing ZnO nanoparticles on a hydrophilic glass fiber (GF) membrane to create hierarchical re-entrant structures, followed by surface fluorination and the addition of a polymer coating to lower the surface energy of the membrane. The omniphobic membranes possessed a particulate membrane morphology and an extremely high fluorine concentration on the surface. The omniphobicity of the fabricated membrane was indicated by the contact angles for water and ethanol, which were as high as 152.8±1.1 ° and 110.3±1.9 °, respectively. In particular, it will focus on the development of tuned hydrophobic, hydrophilic and asymmetric wettability membranes. Membrane contactors are membrane systems that can find application in different fields of industrial interest, covering, for example, gas-liquid operations, liquid-liquid extractions and vapor-liquid distillation. In past decade, the use of membrane absorption to capture carbon (membrane absorption, MA), to prepare emulsions (membrane emulsification, ME), to recover resources from sea (membrane crystallization, MCr) to carry out distillation processes for water scarcity issue (membrane distillation, MD) has been subject of many research activities worldwide. Focus of this talk will be placed on the applications of the developed novel aerogel membranes for MA and MD processes to resolve the carbon abundance and water scarcity issues, respectively, for achieving an ultimate goal toward a sustainable planet.

J217 Development of hydrothermal stable silica membranes by using counter diffusion CVD method
Shibaura Institute of Technology

Silica membranes have been developing as hydrogen permselective membranes. A counter diffusion chemical vapor deposition (CVD) method is the preparation method for the silica membranes. One of the problems for the application of hydrogen permselective membranes is hydrothermal stability. In this study, effects of organic groups in the silica structure on hydrothermal stability was investigated.
γ-alumina (φ10 mm, L30 mm, Noritake Co..) was used for a porous substrate. γ-alumina layer or silica sol-gel layer was coated on the porous substrate. Aluminum sol 5S (Kawaken Fine Chem. Co) with polyvinylalcohol (PVA) was used for the coating of the γ-alumina layer. The parent sol of Tetraethoxysilane (TEOS):EtOH: H2O:HNO3=1:0.1:4:5 was employed for the silica coating. The coated substrates were calcined at 600 °C. CVD was carried out by using HTMOS (Hexyltrimethoxysilane) or TMOS (Tetramethoxysilane) as a silica source at 450 or 600 °C for 15 min. Single gas permeation tests were carried out by using H2 and SF6 at 270 °C.
The hydrothermal stability under steam was examined for the TMOS derived membrane deposited at 550 °C and for the HTMOS derived membrane deposited at 450 °C. The time courses of H2 permeance through the both membranes were shown the figure. The H2 permeance through the TMOS derived membrane decreased gradually, and the permeance was reduced by 37% under the steam treatment for 12h. On the other hand, the reduction rate of the H2 permeance through the HTMOS derived membrane on the silica coated substrates after 23h of the steam treatment was only 10%. In order to confirm the effects of coating of the substrates, the results through the membrane deposited on the coating of the γ-alumina layer were also shown as open plots in the same figure. The H2 permeance looks the similar indicating that there were little effects on the HTMOS derived membranes.

J218 Influence of steam on permselective performance of dimethoxydiphenylsilane-derived silica membrane
Masahiro SESHIMO, Hiromi URAI, Yuichiro YAMAGUCHI, Shin-ichi NAKAO
Inorganic Membranes Research Center, Research Institute of Innovative Technology for the Earth, Kyoto, Japan

Membrane separation technology has been paid attention for one of the energy saving technologies. A silica membrane is categorized as one of the typical inorganic membranes, and the silica membranes show high hydrogen permselective performance comparing with the other inorganic membranes, such as zeolite and carbon membranes. On the other hand, it is generally known that permselective performance of silica membranes are affected strongly under hydrothermal conditions.
In this study, influence of steam on permeation performance of the DMDPS-derived silica membrane was evaluated to develop the silica membranes having relatively high hydrothermal durability. The silica membrane was prepared by counter-diffusion chemical vapor deposition method on a porous alumina support purchased from Nikkato co., Japan. After membrane preparation, permeation performance was measured using single component H2, N2 and SF6, respectively. Heat-treatment of the membrane was conducted at 573 K for 50 h. During heat-treatment, H2, N2 and SF6 permeances showed approximately constant value. To evaluate effect of heat-treatment, durability test was conducted under 0.1 ~ 1.0 mol% steam co-existed conditions at 573 K by using heat-treated and non-treated silica membranes. Comparing influence of steam on permeation performances of these membranes, permeance decreasing ratio of heat-treated membrane showed lower value than that of non-treated membrane in any steam concentrations. In addition, in-situ diffuse reflectance FT-IR spectra of heat-treated and non-treated silica powder was obtained. The heat-treated silica had less amount of adsorbed water molecules than the non-treated silica because the silanol group was decreased owing to heat treatment. From these results, it is considered that hydrothermal durability of the silica membrane is determined by the silanol group density.

J221 Analysis for diffusion and desorption behavior of hydrocarbon from silicalite-1 membrane by gas permeation measurement
Motomu SAKAI1, G. KOBAYASHI2, Masahiko MATSUKATA1,2,3
1 Research Organization for Nano & Life Innovation, Waseda University, 3-4-1 Okubo, Shinjuku-ku, Tokyo 169-8555, Japan
2 Department of Applied Chemistry, Waseda University, Okubo, Shinjuku-ku, Tokyo 169-8555, Japan
3 Advanced Research Institute for Science and Engineering, Waseda University, Okubo, Shinjuku-ku, Tokyo 169-8555, Japan

In generally, permeation phenomenon in microporous membrane can be divided in three steps, adsorption, diffusion, and desorption. Though investigation of these factors in membrane is quite important to understand permeation mechanism, these factors are hardly evaluated in direct.
We previously reported non-destructive adsorption measurement for zeolite membrane.1 In this study, we estimated diffusion property of hydrocarbon in silicalite-1 membrane from gas permeation measurement.
Silicalite-1, pure silica zeolite with MFI-topology, membrane was synthesized by a seed-assisted crystallization method on an outer surface of porous tubular a-alumina support (Noritake, i.d. = 7 mm, o.d. = 10 mm, average pore size = 150 nm).
Diffusion and desorption behavior was evaluated as follows. At first, permeation flux of helium through silicalite-1 membrane was detected. After that hydrocarbon vapor were fed to a membrane with flowing helium. When micropore of zeolite membrane was saturated by adsorbed hydrocarbon, the helium flux drastically decreased. Finally, hydrocarbon feeding was stopped, and then micropore would open by desorption of hydrocarbon. Thus, we can estimate the diffusion and desorption behavior of hydrocarbon from the rate of helium flux increase by pore opening. In addition, diffusion coefficient of hydrocarbon in mocropore could be calculated by using Fick's second law.
(1) M. Seshimo, K. Matsumoto, M. Mastukata, Evaluation of micropore volume of zeolite membrane under non-destructive condition by nitrogen adsorption method, 16th International Conference of Inorganic Membrane, P2.11, July, 2016.
This work was partially supported by JST CREST (Japan Science and Technology agency, Create REvolutionary technological seeds for Science and Technology innovation program), Grant Number JPMJCR1324, Japan.

J222 Effect of grain boundary region of CHA zeolite membranes on gas selectivity investigated by Non-equilibrium molecular dynamics
Fumiya HIROSAWA, Hiromitsu TAKABA
Kogakuin University, Tokyo, Japan

Zeolite membranes have unique properties such as molecular sieving and thermal stability. Therefore, the practical use of zeolite membranes for a purification process of natural gas has been investigated. Grain boundaries in inorganic membranes are known to degrade membrane performance, however, the detailed information of effect on selectivity still difficult to predict prior to the permeation test. Non-equilibrium molecular dynamics (NEMD) method is one of the theoretical prediction method of separation characteristics in inorganic membranes. The NEMD simulation is an atomistic-scale modeling, thus this can easily apply to the prediction of permeability and selectivity in multicomponent gas systems. The effect of trace components for membrane performance can be also investigated using NEMD.
In this study, we investigate the separation properties of CHA and MFI type zeolite membranes by NEMD for CO2/CH4 systems, and elucidate the mechanism of the effect of grain boundary on selectivity for ternary separation systems. Two different types of zeolite membranes having different pore sizes of MFI and CHA are considered to investigate the effect of pore size on selectivity. Two different models used in NEMD are shown in the figure. In the left side model in figure, grain boundary exists insides the zeolite crystal. In the right side model in figure, grain boundary runs lengthwise of zeolite crystal. In Generation region in the feed side gas molecules appear at every certain period. In Deletion region in the permeate side a permeated gas molecule is removed from the system. Our NEMD results indicates that the presence of grain boundary could increase the selectivity, which means that a control of grain boundary is a key factor to enhance the selectivity. In the conference, we will discuss the details of the effect of grain boundaries as well as pore size on this interesting phenomena regarding the selectivity.

Shigeki HARA, Masakazu MUKAIDA, Hiroyuki SUDA
AIST, Tsukuba, Japan

Palladium membranes made of pure palladium, palladium-silver, palladium-copper, etc. are promising in terms of high selectivity to hydrogen. Because palladium is limited in resources and costly, various attempts have been made to reduce necessary amount of palladium preparing not only membranes supported by porous materials but also foil-shaped thin self-supported membranes. Hoverer, self-supported membranes are difficult to seal with frames of modules because welding is not easy for thin foils. To utilize self-supported membranes in practice to process large amount of hydrogen, technology to compose modules is necessary.
In this study, therefore, membrane modules for self-supported palladium membranes have been developed. A prototype module had eight sheets of palladium-silver foils 0.02 mm thick and 30 mm × 60 mm wide including sealing area. The foil-shaped membranes and spacers were alternatively accumulated and combined by thermal diffusion. The combined structure was set inside a stainless-steel container and welded between one of the spacers and the container. The module had three ports for feed, permeate and retentate gases. The module size was 34 mm × 44 mm × 64 mm excluding three ports.
Hydrogen permeation performance of the module was investigated using 1-MPa pure hydrogen as a feed gas at 623 K. As a result, 6 L(at 293 K, 1 atm)/min hydrogen was obtained from the permeate port. Durability was proved at least for 467 hours. This kind of modules are expected to enlarge the applicability of palladium membranes.

J224 Effect of coexisting components on gas permeation through carbon molecular sieve membranes prepared from a polyimide
Kouhei SAKAI, Takuya ASANO, Kazuhiro TANAKA
Yamaguchi University, Ube, Japan

Membrane gas separation have the potential to reduce energy consumption in chemical industry. Currently polymeric membranes are widely used. However, their applications are limited because of their low selectivity. Carbon molecular sieve (CMS) membranes have higher permselectivity than commercially available polymeric membranes and lower fabrication cost than silica and zeolite membranes. The CMS membrane are expected to expand the range of application of membrane gas separation. One of problems to be considered for application is the effect of impurity. In this study, we have investigated the effect of coexisting component on gas permeation and separation through CMS membranes. Mixed gas permeation experiments have been carried out for binary mixtures of hydrogen (H2)-nitrogen(N2) and tertiary mixtures of H2, N2 and water vapor. Two CMS membranes prepared from a polyimide have been used.
Permeance to H2 at a constant partial pressure did not change with increasing N2 partial pressure for both membranes. Permeance to N2 at a constant N2 partial pressure did not changed with increasing H2 partial pressure for one membrane. However, N2 permeance increased with increasing H2 pressure for another membrane. Consequently selectivity of H2 over N2 decreased with H2 partial pressure for the latter membrane.
Coexisting water vapor decreased both H2 and N2 permeance for both membranes. However, H2/N2 selectivity decreased for one membrane and it increased for another membrane. Water vapor had a complex effect on a H2/N2 mixed gas permeation for CMS membranes.

J225 Inorganic/organic Double-Network Ion Gel Membrane for CO2 Separation
Center for Membrane and Film Technology / Department of Chemical Science and Engineering, Kobe University, 1-1 Rokkodai-cho, Nada, Kobe, Hyogo, Japan

New class of tough gel membranes containing a large amount of ionic liquids (ILs) in an inorganic/organic double-network, termed inorganic/organic double network ion gel (DN ion gel) was fabricated. The inorganic/organic double-network could be easily synthesized in the same IL pot, which allowed the preparation of freely shapeable DN ion gel, including a film shape. The DN gels showed excellent mechanical strength (more than 25 MPa of compressive fracture stress) without any leakage of ILs under compression. From tensile stress loading/unloading test, it was confirmed that the excellent mechanical strength of the DN ion gel was owing to the inorganic network which acted as a sacrificial bond to dissipate the loaded energy and the organic network which played a role of hidden length to sustain large deformation.
The gas permeation under pressurized condition was examined by using the tough ion gel membrane containing more than 80 wt% of an IL. As expected, the ion gel film was not destroyed under high trans-membrane pressure differences up to 700 kPa. Regarding the CO2 separation performance, the CO2/N2 selectivity was almost same as that of the supported ionic liquid membranes. The DN ion gel membrane with optimized network composition and 80 wt% ionic liquid sustained about 1200 barrer of CO2 permeability and 25 of CO2/N2 selectivity for more than 300 h at 50 oC under humid condition. In addition, it was confirmed that the CO2 permeability as well as CO2/N2 selectivity of the ion gel membrane containing more than 90 wt% of an IL was almost same as that of the supported ionic liquid membrane. The superior gas permeability of the ion gel membranes stem from the fact that there is almost no diffusion resistance in the ion gel owing to its low polymer content.

J226 Nanoporous zeolite and MOF filled mixed matrix membranes for gas separation
Yongsheng LIU, Kyosuke TAKAKA, Yu MUKAI, Hidetoshi KITA, Kazuhiro TANAKA
Graduate School of Sciences and Technology for Innovation, Yamaguchi University, 2-16-1 Tokiwadai, Ube-shi, Yamaguchi 755-8611, Japan

Membrane separation technology has been investigated and applied into purify natural gas, especially removing CO2 from CH4 to reduce the pipeline corrosion and increase heating value. Polymer membrane has easy processability, high reproducibility but reaches a limit in a trade-off between permeability and selectivity (Robeson upper bound line). Inorganic membrane owns excellent separation property and mechanical stability, while its high-cost membrane fabrication demands improvement. Blending inorganic particles into the polymer matrix to prepare mixed matrix membranes (MMMs) could be considered as an appropriate method due to it could combine both advantages of polymer membrane and inorganic membrane.
In this study, nanoporous SAPO-34 zeolite (~0.38 nm) and ZIF-8 particles (~0.42 nm) were severally added into polyimide (6FDA-TrMPD and 6FDA-mDAT) and polyethersulfone (PES) to prepare MMMs for CO2/CH4 separation. The filler, polymer and N-methyl pyrrolidone (solvent) were mixed to form a homogeneous solution with filler content in polymer about 0 wt.% ~ 40 wt.%. The solution was cast on a glass plate and the formed MMMs were peeled off after drying. The single gas permeation through the membranes was tested by vacuum method at 1 atm and 35 °C.
According to the figure, 6FDA-TrMPD/SAPO-34 MMMs (T-S-0~40) and 6FDA-TrMPD/ZIF-8 MMMs (T-Z-20~40) possessed the highest CO2 permeability. The 6FDA-mDAT/SAPO-34 MMMs (M-S-0~40) provided the best CO2/CH4 ideal selectivity. Addition of SAPO-34 could both increase the gas permeability and selectivity of PES/SAPO-34 MMMs (P-S-0~30) and 6FDA-mDAT MMMs. In term of 6FDA-TrMPD MMMs, all the SAPO-34 and ZIF-8 could only enhance the gas permeability at a slight loss of selectivity. Nevertheless, the separation performance of 6FDA-TrMPD MMMs containing 30%~40% SAPO-34 (T-S-30 and T-S-40) still exceeded the Robeson upper bound line (2008) of the polymer membrane, which was the same as the 6FDA-mDAT MMM with 40% SAPO-34 zeolite (M-S-40).

O201 Effect of polysaccharide-protein interaction on membrane fouling caused by microbial metabolite
Nagoya University, Nagoya, Aichi, Japan

In recent years, microfiltration is used in wastewater and drinking water treatments, and food and pharmaceutical industries. In the process of using microorganisms, the feed solution is a complex mixture comprising bacterial flocks and microbial metabolite. Therefore, it is essential to clarify the mechanism of flux decline behaviors in microfiltration of microorganism and its metabolite. The key objective of this study is to examine the effect of polysaccharide-protein interaction on membrane fouling caused by microbial metabolite since the microbial metabolite is composed mainly of polysaccharides and proteins. Microfiltration experiments were performed in a dead-end filtration mode using various types of solutions at pH of 4.5 and 6.5 under constant pressure condition. Sodium alginate (SA) with the molecular weight (MW) of 129 kDa was used as model polysaccharide, and lysozyme with the MW of 14.3 kDa, the isoelectric point (pI) of 11.0 and bovine serum albumin (BSA) with the MW of 67 kDa, the pI of 5.1 were used as model protein in this study. The flux decline behaviors were observed in the case of mixture of polysaccharide and protein, and in particular, the filtration rate of solution containing SA and BSA was influenced by the solution pH. The BSA molecule is negatively charged at pH 6.5 and positively charged at pH 4.5, while at both pH values, the lysozyme molecule has a net positive charge, and SA molecule has a negative charge. It is obvious that the effect of the surface charge of protein on the filtration resistance should be considered.

O202 Efficient dewatering of microalgae suspension by cake filtration
Toru ARAMAKI1, Ryozo NOGUCHI2,3, Makoto M. WATANABE2,3, Mitsutoshi NAKAJIMA2,3, Sosaku ICHIKAWA2,3
1 Graduate School of Life and Environmental Sciences, the University of Tsukuba, Ibaraki, Japan
2 Faculty of Life and Environmental Sciences, the University of Tsukuba, Ibaraki, Japan
3 Algae Biomass and Energy System R & D Center, the University of Tsukuba, Ibaraki, Japan

Algal bio-fuel as alternative to fossil fuel has been attracting lots of attention due to the global warming and depleting natural fuel resources. However, the cost of bio-fuel production is relatively high. Especially, harvesting and dewatering of microalgae suspension are reported to account for 20 - 30 % of the total cost, because suspended solid (SS) concentration of microalgae culture is low with 0.02 - 0.06 wt%. Therefore, efficient dewatering process is required. This study examined the performance of dewatering of microalgae suspension by cake filtration using filter cloth.
Two hundred milliliter of microalgae suspension with 0.02 wt%-SS was filtered at constant pressure (70 kPa) using filter cloths (24.4 cm2 of effective area) made from polypropylene, which have different pore size 0.8 - 14 μm. Average permeate flux was increased from 5.9 to 2600 L/(m2 h) with the increase in pore size, while SS rejection was decreased from 94 to 53 %. The filtration behavior was analyzed by existing filtration models. As a result, when filter cloths with smaller pore size than algal cell size (about 8 μm) were used, filtration mode was finally settled into cake filtration. On the other hand, for the filtration using filter cloth with 14 μm of pore size, filtration mode was not settled into cake filtration. Then, in order to conduct cake filtration using filter cloth with 14 μm of pore size for expecting high permeate flux, pre-concentrated suspension (0.1 wt%-SS) was filtered with the intention of forming a cake layer quickly by the deposition of many algal cells on the filter surface. Consequently, microalgae suspension was successfully concentrated up to 18 wt%-SS with 360 L/(m2 h) of average permeate flux and 99 % of SS rejection. These results suggest the potential of microalgae dewatering by cake filtration with high flux and rejection.

O203 Potential of electrokinetic response for the analysis of solid-liquid mixture during mechanical expression
Masashi IWATA1, Kazuya SHIMOIZU1, Tomohiro IWASAKI1, Mohammed Saedi Jami2
1 Osaka Prefecture University, Sakai, Japan
2 International Islamic University Malaysia, Kuala Lumpur, Malaysia

Expression is the separation of liquid from a solid/liquid system by compression due to the movement of the retaining walls of the filter chamber. In the expression of slurry material, the application of mechanical pressure to the retaining walls causes a sudden increase of hydraulic pressure uniformly throughout the slurry. Initially, the process of expression proceeds based on the principle of filtration, where the thickness of filter cake increases over time. Filtration terminates when the whole slurry forms a layer of filter cake, and the consolidation of the cake follows. Exact identification of the time when the chamber is filled with the cake is essential for an effective expression operation. The electrokinetic response of expressed material provides us with some information on the status of the filter chamber. In this work, we have measured the time course of electric potential difference (EPD) between the retaining walls to elucidate the electrokinetic aspects of mechanical dewatering. The experimental apparatus used in this study consists essentially of a piston press with a cylinder and a piston. Filter media are placed at the cylinder bottom and the very end of the piston. EPD between the filter media was monitored during the experiment. As can be seen from the figure, the absolute value of EPD increases with the progress of the filtration period, followed by the decrease during the consolidation period. It was observed that the time when the absolute value of EPD began to decline coincides with the time when the filtration period ended. We have derived a theoretical equation of streaming potential for a flow path of the expressed material and combined it with filtration and consolidation theories to calculate the theoretical time course of EPD of expressed material. It has been found that EPD reflects liquid pressure variation throughout the solid/liquid mixture.

O204 Application of electrokinetic phenomena in filtration processes
Yokohama National University, Yokohama, Japan

The application of membrane filtration processes has been increased because of global shortage of water. Membrane fouling is considered as a major factor limiting the use of the membrane filtration process and is the irreversible alternation in the membrane caused by specific physical and chemical interactions between membrane and various components present in the process stream. The fouling configuration can be classified into three simple mechanisms: pore narrowing by adsorption, pore blocking/plugging and cake/gel layer formation. In many actual processes the species causing the dominant fouling effects is not always known because of the complexity of the feed stream. Identifying the foulant and understanding fouling phenomena are required for adopting countermeasures for the fouling. Electrostatic and hydrophobic interactions are recognized as the major interactions causing fouling. The zeta potential of the foulant or the membrane, that is, the electrical potential at the surface of shear between the solid and the liquid, can be useful for the prediction of the electrostatic interaction. Adsorption is a major cause of membrane fouling in microfiltration of macromolecule containing solutions. The change ratio of zeta potential by protein adsorption is directly proportional to the surface coverage regardless of pH. In pore blocking or cake formation caused by fine particles the location of pressure drop in the system depends on the fouling configuration. The zeta potential reflected the local pressure drop part, where the gap between particle and pore in pore blocking filtration and the gap between particles in cake filtration. These observations shows the zeta potential will useful for monitoring the fouling configuration during the filtration operation.

O205 [Keynote] Challenges in centrifugal separation in biotechnology
Wallace Woon-Fong LEUNG
The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong

Traditional pharmaceuticals have been made from chemical processes. Today, a significant fraction of valuable pharmaceuticals, such as hormones, insulin, growth factors, interferon, enzymes, drug intermediates, etc. are replaced by biotechnology processes. One of the building blocks is to make protein out of recombinant processes where extracellular or intracellular protein can be “engineered” and secreted from host biological cells which have been inserted with vectors carrying human genes. The host cells, e.g. the mammalian cells, bacteria and yeast can secret high amounts of recombinant protein in a bioreactor or fermenter. For extracellular protein, the first step in harvesting protein is to separate the protein from the cells. On the other hand for intracellular protein, the bacteria cells have to be lysed first before releasing the protein in form of inclusion body, for which separation follows. Disk stack and tubular centrifuges operating between 4,000–15,000 times gravity are popular choices to make separation of cells, cell debris, and proteins from the broth. We will discuss the various scenarios of centrifugal separation of protein in clarification, separation, classification and purification by washing during protein harvest. This is an extremely important step that affects yield and downstream processes, e.g., purification by chromatography. We will also discuss testing, modelling and prediction of protein separation in protein harvesting. Further, new technologies on separation of flocculated bio-solids and other popular biotech separation processes by centrifugation will also be discussed.

O213 Separation of colloidal particle using elastic-gel-packed column
Hidetaka KAWAKITA, Kaori YOKOYAMA, Shohei ESAKI, Shintaro MORISADA, Keisuke OHTO
Saga University, Japan

A deformable gel-packed chromatographic column was used to separate as-synthesized graphite oxide with different sizes. The synthesized gel (56 micrometer) was deformed by pressure of the fluid flow and the gaps in the gels showed a range of sizes. A suspension of graphene oxide (0.1 g/L, 10 mL) was injected, and graphene oxide in the elution had a size at 0.56 micrometer and 0.14 micrometer, whereas in half upper and bottom domain of the gel layer graphene oxide had a size at 33 micrometer and 2.9 micrometer, respectively, demonstrating that graphene oxide suspension was separated by size through gel layer. On behalf of graphene oxide, suspension of silica particle produced by dry process was also injected to the elastic gel -layer to separate silica particles due to their size and morphology.
To elute the filtered colloidal particle among the gel, the elastic gel layer was compacted and extended by the change of the applied pressure of water. At that time due to the dynamic change of the gel layer, the filtered particles was gradually eluted by the expansion of the gel's gaps as well as the convection of the fluid flow. The recovery percentage of the silica particles filtered was increased with increasing the repeated time of compaction and extension of the elastic gel layer.

O214 Effect of Solute on Freeze Concentration Efficiency with Ultrasonic Irradiation
Ehime University, Matsuyama, Japan

The capture of solute into freezing part is difficult by the vigorous agitation of the freezing interface during the fast freezing of solution. We have been studying the applicability of ultrasonic irradiation (frequency: 20 kHz) to the agitating method, and found that the freeze concentration efficiency of solutes is improved greatly by this irradiation. In this paper, the effect of the frequency of ultrasonic irradiation on the freeze concentration characteristics for multiple solutes is examined.
Using three kind of solutions containing only one solute (Histidine, Vitamin C, and saccharose (these can widely be found in the food materials), 0.03 mol/L), we examined the freeze concentration characteristics with ultrasonic irradiation. The frequencies of ultrasonic irradiation were 20 kHz and 200 kHz, which were adjusted to the same output (11.8 W). From the experimental results, decreasing dissolved oxygen concentration (DO) can increase the concentration efficiency of all solutes in the case of 20 kHz ultrasonic frequency. On the other hand, in the case of 200 kHz ultrasonic frequency, increasing DO may increase the concentration efficiency. The DO dependence of the concentration efficiency differs depending on the frequency of ultrasonic irradiation and solute type.

O215 Development of a new drying method using ultrasonic wave
Tomoki OKADA, Noriaki SANO
Kyoto University, Kyoto 615-8510, Japan

Ultrasonic wave is applied in many situations, for example cleaning glasses, sensors, dispersion. In cleaning glasses, the frequency of ultrasonic is about 100 kHz. When the frequency of sonication increases to about 2 MHz and vibrates water, water becomes mist and flies away. This phenomenon is ultrasonic atomization. In this research, we applied this atomization to drying particles that is useful in chemical processes. This drying method is called ultrasonic drying.
It is expected that ultrasonic drying will be faster and consume less energy than drying by heat. We had three experiments to prove them. First was testing whether ultrasonic can dry wet particles. I tried to dry fly ash by ultrasonic and observed how humidity of fly ash changed. Next is measuring the rate of ultrasonic drying. We prepared three kinds of particles, alumina, silica and fly ash. I moreover prepared three different diameter of alumina and two different diameter of silica to see whether the rate of ultrasonic drying depends on the diameter of particles. Last is comparing efficiencies of ultrasonic drying and traditional drying. We measured the loss of weight of materials by drying and the consumption of electronic energy. Efficiency of drying, as shown in Fig. 1, is defined by the weight loss divided by the electric energy consumption.
The result of first experiment was that mist appeared from the surface of particles, so we were sure that ultrasonic can dry materials. Second experiment suggests that the rate of ultrasonic drying has positive dependence on diameter of particles. This experiment, however, cannot show difference in dying rate among different particles. Efficiency of ultrasonic drying gotten in last experiment is approximately 100 times better than one of drying by heat. Considering by those outcomes, ultrasonic drying will replace some current drying methods in a few decades.

O216 Isolation of Lignin from Rice Straw Residue in Ethanol Cellulosic Process Using Microwave-assisted Method
Reo A. MAHESA, Ho-Shing WU
Yuan Ze unversity, Taoyuan, Taiwan

Consumer products largely originate from fossil resources which will be depleted sooner or later and contribute to CO2 emissions and climate change. Alternatives are sought with low carbon emissions and these are inexhaustible resources like plant derived biomass. Our motivation is to optimize the extraction process of lignin. The only water pre-treatment process and combination with organic solvent Soxhletation was carried out in the first stage to reduce impurities. Soda process and diluted acid process were chosen for extraction methods and microwave-assisted as the main instrument for heating up solution.
The results showed that pre-treatment process by using water following with isopropanol-hexane was given the best result. Water helped to extract sugar, alcohol, and some water soluble impurities. When isopropanol extracted the rest of polar impurities that water could not be done, Hexane was extracted non-polar impurities such as lipid. It could have extracted about 5.3 % weight loss of impurities without changed the lignin structure significantly due to TGA and FTIR results. This study aims to extract lignin in moderate temperature, pressure, and power in as little concentration and time as we could achieve. The process was done with soda process for 2 wt% NaOH concentration at 130 oC with 30-min extraction process as the best result rather than diluted acid process. The amount of lignin obtained about from this process was relatively higher both in 99.7% yield and 94.6% purity compared to other studies result. This type of lignin has similar characteristic to commercial dealkaline lignin.

O217 Phytoremediation of Water Environment Contaminated by Antibiotics Using Aquatic Plant
Hiroaki HABAKI1, Zhuoheng LI1, Shuyang WANG1, Jack ZHANG2, Ryuichi EGASHIRA1
1 Tokyo Institute of Technology, Tokyo, Japan
2 The University of British Columbia, Vancouver, Canada

This study aimed the treatment of the aqueous solution contaminated by antibiotics with duckweed, Lemna minor, which was reported to uptake organic compounds in the aqueous solution, and the removal of the antibiotics in the aqueous solution with duckweed under various conditions was measured to study the mechanism of antibiotics removal from contaminated solution. Firstly, it was confirmed that the molar concentrations of ciprofloxacin and sulfamethoxazole, which were selected as model antibiotics to be treated because of most popular antibiotics causing aquatic environmental pollution, could be reduced due to the mechanisms of hydrolysis, photo-degradation and uptake by duckweed. Ciprofloxacin was more degradable due to hydrolysis and photo-degradation in the aqueous solution than sulfamethoxazole, and the degrees of the molar concentration reduction due to uptake by duckweed were comparable for both antibiotics. In the cases of the treatment of ciprofloxacin of the initial molar concentration at 1×10-5mol/L, the reduction of the molar concentration due to the hydrolysis and photo-degradation shared 0.6 relative to the total reduction of the molar concentration, and the ratio of reduction due to uptake relative to the total reduction was 0.4. On the other hand, the molar concentration reduction of sulfamethoxazole due to the uptake relative to the total concentration reduction was 0.95, and the contribution of the hydrolysis and photo-degradation to the total reduction of ciprofloxacin concentration was so small. When the initial molar concentrations of both antibiotics increased up to 5×10-5mol/L, the contributions of these three factors to the antibiotics reduction were similar to the cases with the initial concentration as 1×10-5mol/L. Accordingly the uptakes of both antibiotics by duckweed were so influential to reduce the molar concentrations in the aqueous solution, especially for sulfamethoxazole, and this treatment method might have a potential to remediate the aquatic environment polluted by antibiotics.

O218 Optimization on Surfactant-Enhanced Extraction of Tea Tree Oil by Hydrodistillation using Response Surface Methodology
Yen-Ju CHEN, Jung-Hsuan CHOU, Pei-Tzu YANG, Bing-Hung CHEN
National Cheng Kung University, Tainan, Taiwan

The response surface methodology was applied to study and to optimize the surfactant-enhanced extraction of tea tree oil (TTO), i.e. the essential oil of Melaleuca alternifolia, by hydrodistillation method. Both Tween 20 and Tween 80 were used as surfactants added in the hydrodistillation vat with an aim to enhance the extraction yield of TTO. In principle, this study evaluated the relevance of several independent parameters, including the concentration of surfactant, extraction time, and liquid/solid ratio, against TTO yield with a design of experiment (DOE) based on response surface methodology. Central composite design (CCD) was used to optimize the processing condition of TTO extraction. The chemical compositions of tea tree oil were analyzed and quantized by GC-FID and were referred with the international standard "ISO 4730". Additionally, TTO obtained from optimal condition was examined on the stability of its microemulsion formulations as well as the antibacterial property, compared with the commercial TTO. The microemulsion stability was mainly determined by the particle size measurement with dynamic light scattering (DLS), whereas the antibacterial assay was carried out by agar disk diffusion method with Escherichia coli and Staphylococus aureus.
Keywords: Melaleuca alternifolia; Extraction; Design of experiment (DOE); Optimization

O221 [Keynote] Development of new extractants for platinum group metals and analysis of the extraction mechanism
Hirokazu NARITA, Mikiya TANAKA
Environmental Management Research Institute, National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba, Ibaraki 305-8569, Japan

Solvent extraction (SX) is generally used for separation and purification of platinum group metal (PGM) in hydrometallurgical processes. The development of a successful SX process depends on the choice of appropriate extractants. Therefore, we have been studying the extraction behavior of PGM with newly synthesized extractants in addition to the structural properties of PGM complex anions extracted in the organic phase.
We have developed a new palladium extractant, thiodiglycolamide (TDGA), which can rapidly extract Pd(II) from HCl solution with a good selectivity and has a high oxidation resistance, compared with an industrial palladium extractant, di-n-hexyl sulfide (DHS). Currently, TDGA has been commercially available and already put to practical use in a PGM separation plant.
To date, there have been no effective practical extractants for rhodium in acidic chloride media, because the dominant rhodium species in relatively concentrated HCl solutions ([RhClx(H2O)6–x]3–x (x ≥ 4)) are poorly extracted into an organic phase. We have found that amide-containing tertiary amine (ACTA) compounds show a higher efficiency for the Rh(III) extraction from HCl solution than the conventional tertiary amine extractant, tri-n-octyl amine. The protonated ACTA molecules extract the mono-aquated dianion [RhCl5(H2O)]2– through the formation of an outer-sphere assembly, which was characterized by slope analysis, FT-IR, EXAFS, SANS, computational modeling, etc.

O223 Direct leaching approaches in single and two-stages for the recovery of rare earth elements from coal fly ash: A comparative study
Vannie Joy RESABAL1, Richard ALORRO2, Junnile ROMERO1, Elaiza Ruth DIAMOS1, Felny INTELEGANDO1
1 Mindanao State University - Iligan Institute of Technology, Philippines 9200
2 Western Australia School of Mines, Curtin University Kalgoorlie, 6430 West Australia

Prices of strategic metals and rare earth elements (REEs) have been rising over the past decade due to the global shortages in supply and increasing demands. These metals are essential components of advanced and emerging technologies associated with transport, environment, energy, defense, electronics, information and aerospace. With the utility of REEs projected to increase in the next decade, it is important to find alternative sources to conventional mining to cope with the demand. There are a few studies conducted on the potential of coal fly ashes as secondary resource of REE. Coal fly ash are waste products from coal burning in a coal power generation plants.
This research is aimed at extracting rare earth elements from coal fly ash by hydrochloric acid leaching. The purpose of this study is to explore the amenability of coal fly ash to metallurgical processing for the extraction of rare earth elements. Three process parameters were investigated in this study, namely, hydrochloric acid concentration, leaching time, and the leaching method. Results of the experiment showed that the recovery of rare earth elements increased with increasing hydrochloric acid concentration. Direct leaching method achieved higher recovery values for REEs compared to sequential leaching. Maximum recovery value for REEs was obtained at 1 h leaching time.

O224 Solvent Extraction of Scandium and Yttrium Using Carboxylic Acid
Jeong-yi MOON, Syouhei NISHIHAMA, Kazuharu YOSHIZUKA
The University of Kitakyushu, Kitakyushu, Japan

Scandium (Sc) is rare and expensive metal in high demand, providing excellent characteristics for various industrial applications. Since Sc is commonly found in crustal together with Y owing to its small ionic radius, the separation of Sc from yttrium (Y) and other rare earths is required. In the present work, separation and recovery of Sc in an aqueous chloride media was investigated by solvent extraction with carboxylic acid, Versatic acid 10.
The aqueous chloride solutions of rare earths were prepared by dissolving their oxides in 1 or 2 mol/L HCl solution. Organic solution was prepared by diluting Versatic acid 10 in IP Solvent 2835. Extraction of Sc and Y was carried out by shaking the organic and aqueous solutions at volume ratio of 1 : 1 at 25oC for more than 6 h. Concentrations of the metals in the aqueous solutions were determined by ICP-AES and those in the organic solutions were calculated based on material balance.
Figure 1 shows the effect of pH on the extraction yields of Sc and Y from the binary solution. Extraction of Sc proceeds from pH 3, and is increased with pH, while the extraction of Y proceeds from pH 4.5. Separation of Sc and Y is therefore easily achieved with Versatic acid 10. The conventional slope analysis of Sc with Versatic acid 10 revealed that the extraction is based on the cation exchange mechanism and the stoichiometry of Sc and the dimeric extractant of Versatic Acid 10 was 1 : 3.

O225 Recovery of lithium from seawater with two derivatives of macrocycles using microreactor system
Keisuke OHTO1, Yehezkiel Steven KURNIAWAN1, Ramachandra Rao Sathuluri1,2, Wataru IWASAKI2, Hidetaka KAWAKITA1, Shintaro MORISADA1, Masaya MIYAZAKI2,3, Jumina4
1 Saga University, Saga, Japan
2 National institute of advanced science and technology, Tosu, Japan
3 Hokkaido University, Sapporo, Japan
4 Universitas Gadjah Mada, Yogyakarta, Indonesia

Two derivatives of p-t-octylcalix[4]arene were prepared to investigate extraction behavior of alkali metal ions. Tripropyl-monoacetic acid derivative (1) exhibited lithium selectivity among alkali metal ions, while Triacetic acid-monopropyl one (2) showed sodium selectivity. Then, they were employed for individual and stepwise recovery of alkali metal ions using microreactor system. Finally, they were employed for Li recovery from the seawater. Compound 1 was applied for Li recovery to concentrate Li ion at the 1st step and to strip the loaded metal ions, and compound 2 was employed to remove sodium ion for Li purification. Lithium ion was successfully completely recovered form seawater with two derivatives using microreactor system. Flow sheet for Li recovery with two derivatives using microreactor system is shown in Figure.

J301 Selective membrane separation In(III), Ga(III) over Zn(II) from wastes solar panel using PIMs
Takahiro ITO, Shintaro KANEMARU, Yoshinari BABA1, Yukie O'BRYAN, Ines Sa ALMEIDA, Spas D. KOLEV2
1 Miyazaki University, Miyazaki, Japan
2 Melbourne University, Melbourne, Australia

The polymer inclusion membranes (PIMs) composed by polymer and carrier without plasticizer have been used in this study. The extractant used in this study is containing in long alkyl chains and double bond. The great benefits of PIMs are to be used a small amount of extractant and less organic solvent and also are less leak of the extractant out of the membranes.
In the near future, it is expected that a large amount of wastes of used solar panels containing In(III), Ga(III) and Zn(II) is discharged. In this research, we were interested in alkyl-derivatives of sarcosine as an extractant to selectively separate In(III) and Ga(III) from Zn(II). Accordingly, a comparison of the metals(In(III), Ga(III) and Zn(II)) extraction was performed using four kind of extractants (two types of carboxylic acid and two types of sarcosine) and three polymers. Among them, We found the membrane containing poly(vinylidenefluoride-cohexafluoropropylene) (PVDF-HFP) as a polymer skeleton and N-oleoylsarcosine as a carrier. This membrane exhibited highly selective to In(III) and Ga(III) in hydrochloric acid solution. Finally we found that the PIM containing N-oleoyl sarcosine could perform the selectively separate In(III) and Ga(III) from Zn(II) from hydrochloric acid. In addition, we succeed in containing 60 % w/w N-oleoylsarcosine in the membrane.

J302 Development of a novel positively-charged nanofiltration membrane by plasma graft polymerization method
Kazuki AKAMATSU1, Yukino IGARASHI1, Takashi MARUTANI1, Takuji SHINTANI2, Shin-ichi NAKAO1
1 Kogakuin University, Hachioji, Japan
2 Kobe University, Kobe, Japan

We successfully developed a novel nanofiltration membrane that enables the separation of Mg2+ and Ca2+ from effluents in the electrodialysis process in salt productions. For that purpose, we first fabricated the polyamide layers using piperazine and trimesoyl chloride onto microfiltration membranes as supports, and then immobilized poly(2-methacryloyloxyethyl)trimethylaminium chloride) (polyMTMA) covalently on the surfaces and the pore walls of the polyamide layers by the plasma graft polymerization method. The polyMTMA grafted on the substrates made the membranes surface positively-charged, and at the same time reduced the pore sizes. Throughout the systematic nanofiltration experiments using various single salts with concentrations of 1.9 x 103 ppm, a membrane with a grafting amount of 0.24 mg cm-2 showed the following rejection performances that positively-charged nanofiltration membranes typically exhibit; the observed rejections (Robs) for NaCl, CaCl2, MgCl2, Na2SO4, CaSO4, MgSO4 were 0.20, 0.64, 0.65, 0.21, 0.35, 0.44, respectively. We also carried out Mg2+ separation tests from Na+-rich solutions by using aqueous solutions containing NaCl and MgCl2 with the ratios of 9:1, 14:1, and 19:1 as feed. The results indicated that around half of Mg2+ ions were retained with the permeation of more than 80% of Na+ ions.
Acknowledgement: Part of this study was financially supported by a grant from the Salt Science Research Foundation, Japan.

J303 Preparation of silica-decorated aliphatic polyketone membrane with high performance for oil/water separation
Center for Membrane and Film Technology / Department of Chemical Science and Engineering, Kobe University, Kobe, Japan

Oil/water separation has attracted more attention in both of academia and industry due to the increased amount of oily wastewater from the industrial process and frequent oil spill accidents, causing fatal damage to ecosystem and people's health. How to treat the oily wastewater has become a big challenge all over the world. In this work, an innovative aliphatic polyketone (PK) membrane surrounded by hydrophilic silica nanoparticles with hierarchical micro/nanoscale structure was developed by a APTES-assistance deposition process. With the APTES help to make the PK membrane positive charged, the negative charged silica was uniformed deposited on the membrane surface. The resultant silica-d-PK membrane displays superhydrophilicity, ultralow oil-adhesion underwater superoleophobicity, and distinctive self-cleaning ability, as well as excellent solvent resistance. More important, the membrane shows ultrafast and anti-oil-fouling separation performances for different oil-in-water emulsions. Therefore, it is very promising for large-scale applications.

J304 Facile modification of commercial PVDF membrane with poly(tetrafluoride ethylene-r-vinylpyrrolidone) for fouling tolerance and highly efficient separation of oil/water emulsion
Yuchen SUN, Yuqing LIN, Lei ZHANG, Liang CHENG, Lifeng FANG, Hideto MATSUYAMA*
Center for Membrane and Film Technology., Kobe University, Kobe 657-8501, Japan

Fouling problem caused by oil and other pollutants is one of the most severe challenges for membranes used for the purification of comprehensive oil-in-water emulsions. Poly(tetraflouride-r-vinylpyrrolidone) (F-VP) with low-adhesive superleophobicity is a class of novel material for fouling-repellent membrane modification to achieve highly-efficient separation of complex oily wastewater. In this work, the construction an ultrathin F-VP layer with a controllable thickness of 2 μm supported by polyvinylidene difluoride (PVDF) substrate was achieved, via an extremely simple, scalable and one-step surface modification process. Benefiting from the ultrathin fouling-resistant skin layer, the resultant F-VP/PVDF membrane exhibited a superior comprehensive fouling-resistant and fouling releasing property, while maintained a highly mass-transfer efficiency without significant flux sacrificing. The intrinsically non-fouling nature of F-VP modification layer endowed the F-VP/PVDF membrane with superoleophobic property to various oils, superhydrophilic/under oil superhydrophilic properties, and excellent antifouling property for comprehensive oil-in-water emulsions. It is capable of efficiently separating the oil-in-water emulsions with a high water permeability of 4612 L m-1 h-1 bar-1, high emulsion permeability (10000 ppm soybean oil-in-water emulsion) of 461 L m-1 h-1 bar-1 with high rejection ratio of >99.9%, and an outstanding stable fouling-resistant and fouling-releasing property of ~93% flux recovery, over 5-time continuous cyclic tests. Overall, this work provides an insight into a facile preparation of advanced composite membrane with ultralow fouling-propensity property, which shows a great potential in treating practically challenging emulsified wastewater.

J305 Development of low energy consumption MBR
Satoshi KATO1, Yoshiki OKAMOTO1, Kyaing Kyaing Latt2, Shigehisa HANADA1, Masahiro KIMURA1
1 Toray Industries, Inc.
2 Toray Singapore Water Research Center

Membrane bioreactor (MBR) technology has many advantages from the views of high product water quality, small footprint and high possibility of treated water reuse. The critical challenges of MBR are membrane fouling and high energy consumption. Membrane air scouring is the main cause of high energy consumption in MBR. In fact, overall energy consumption can be reduced by operating at high flux or low air flow, on the other hand, serious membrane fouling will occur under high suction pressure. We investigated the fouling mechanism and main foulant type in high flux operation (42 LMH) comparing with low flux (25 LMH). The total amount of protein and polysaccharide clogged in the membrane at high flux operation was 2 times higher than that at low flux operation. Those clogging foulants in membrane pores were considered to be responsible for serious fouling at high flux operation. In order to mitigate those foulants, low concentration chemical cleaning, so-called maintenance cleaning (MC) was applied.
Additionally, we focused scouring efficiency to remove foulant from the membrane at low air flow operation. In order to increase scouring efficiency, new MBR structure that has 3 times higher scouring efficiency than the current MBR structure was developed. Scouring efficiency was improved by increase of the probability of contact of air and membrane in the new MBR.
A verification test using new membrane module at high flux and low air flow was conducted for a month with periodic MC every 3-7 days (Figure). The base membrane TMP (Trans Membrane Pressure) increasing rate was maintained at less than 0.05 kPa/d. The aeration energy consumption per product water was reduced 80% in high flux and low air flow operation.

J306 Surface modification of beta zeolites to evaluate catalytic performance in transalkylation reaction
Sanghamitra Barman, Ruchika THAKUR
Thapar Institute of Engineering and Technology, Patiala, Pin-147004, Punjab, India

Aromatics have numerous applications in the chemical and petrochemical industries (Odedairo and Al-Khattaf 2011). Transalkylation which includes transfer of alkyl group from one molecule to another is one of the prominent catalytic processes for the conversion of aromatics, especially for the production of industrially important products like xylenes, ethylbenzene, c