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Workshop on Supercritical Fluids and Energy workshop on supercritical fl uids and energy ESTA OBRA FOI IMPRESSA EM PAPEL RECICLATO 75% PRÉ-CONSUMO, 25 % PÓS-CONSUMO, A PARTIR DE IMPRESSÕES E TIRAGENS SUSTENTÁVEIS. CUMPRIMOS NOSSO PAPEL NA EDUCAÇÃO E NA PRESERVAÇÃO DO MEIO AMBIENTE. workshop on supercritical fl uids and energy Dados Internacionais de Catalogação na Publicação (CIP) (Câmara Brasileira do Livro, SP, Brasil) Workshop em fluídos supercríticos e energia / M. Angela A. Meireles e Erdogan Kiran. (organizadores). – Campinas, SP : Mercado de Letras, 2013. – (Mercado de Letras Temas) ISBN 978-85-7591-301-7 1. Biocombustíveis 2. Energia – Fontes alternativas 3. Fluídos supercríticos I. Meireles, M. Angela A. II. Kiran, Erdogan III. Série. 13-12026 CDD-541.34 Índices para catálogo sistemático: 1. Fluídos supercríticos e energia 541.34 Capa e Projeto Gráfico: Vande Rotta Gomide Layout e Editoração: André S. Tavares da Silva Revisão: Gabriela Lopes Adami DIREITOS RESERVADOS PARA A LÍNGUA INGLESA: © MERCADO DE LETRAS EDIÇÕES E LIVRARIA LTDA. Rua João da Cruz e Souza, 53 Telefax: (19) 3241-7514 – CEP 13070-116 Campinas SP Brasil www.mercado-de-letras.com.br [email protected] 1a edição dezembro/2013 IMPRESSÃO DIGITAL IMPRESSO NO BRASIL Esta obra está protegida pela Lei 9610/98. É proibida sua reprodução parcial ou total sem a autorização prévia do Editor. O infrator estará sujeito às penalidades previstas na Lei. CONTENTS Preface. 7 Presentation . .13 Goals . 15 Committee . 17 OVERVIEW/PLENARy LECTURES ON ThE ROLE OF SUPERCRITICAL FLUIDS AND TEChNOLOGy (SCFs&T) State of SCFs&T — Future Directions and Progress in Commercialization. .19 SCFs&T for Bio-based Fuel processes . 39 SCFs&T for New Materials and Materials Processing. .49 SCFs&T for Green Chemistry and Sustainable Technology . 69 SCFs as Working Fluids and Process Technology. 83 PANEL PRESENTATIONS Panel I: Bio-based fuel processes. .103 Panel II: New Materials and Materials Processing. 129 Panel III: Green Chemistry and Sustainable Technology . .159 Panel IV: SCFs as Working Fluids / Process Technology and Design. .187 Panel V: Process Technology and Future Direction. .215 POSTERS. 243 Index. 387 PREFACE It is with pleasure that we present this book of abstracts of the lectures and posters that will be presented at the Workshop on Supercritical Fluids and Energy. The idea of organizing a workshop on supercritical fluids with a focus on energy emerged during the course of casual exchanges between the co-directors of this work- shop who shared the same dinner table at the Gala Dinner at the 10th International Symposium on Supercritical Flu- ids held in San Francisco in May 2012. The discussions had initially started with commentaries on the ongoing symposium and on the current status and future directions of the supercritical fluid science and technology. One of the questions that immediately surfaced was “how come no industrial plants that employ supercritical fluids had been built in Brazil or in South America despite decades of ongoing active research by many in the region?” The discussion quickly expanded and the questions became broader. Brazil having played such an important role in bio-ethanol production, and there being an ever increasing interest in alternative fuels around the world, we ques- tioned how new opportunities could be developed for the supercritical fluid-based technologies to make an impact in Brazil and elsewhere. What were the limitations? Where were the bottlenecks? What was missing on fundamental data? Were there misconceptions, if any, that needed to be overcome to raise the level of interest for industrial implementation? Were there a critical mass of trained en- 7 8 SFE 2013 | WORKShOP ON SUPERCRITICAL FLUIDS AND ENERGy gineers who could take charge of such facilities and run them safely if they were to be built? Furthermore, since supercritical fluid research could impact “energy” use or savings in many other ways than just developing new ap- proaches to generate alternative fuels, additional questions were raised on the impact of using supercritical fluids as working fluids in power cycles; the energy saving potential in materials processing, or forming new materials ranging from particles, to fibers, to foams and aerogels with super- critical fluids. It immediately became clear that addressing these questions would greatly benefit our greater commu- nity. When viewed under such a broad umbrella, the ap- peal of a Workshop, rather than a traditional conference or symposia became extremely high as it would then be attractive to colleagues with different backgrounds; with everyone easily contributing by sharing their perspectives of what is known, what is needed, and where the future trends in the field lie from their own strength areas, while gaining new perspectives in others. With this background, we started to seek funding for the Workshop. The goal was to generate sufficient funds to facilitate participation not only by experts but also by young scientists. The Journal of Supercritical Fluids made an early commitment to sup- port the idea as the timing of the workshop would nicely coincide with and mark the 25th anniversary of the Journal being in publication. LASEFI was also immediately on board. One of us (E. Kiran) discussed the idea with the program managers for “Environmental Sustainability” and “Energy and Sustainability” at the National Science Foun- dation at the 2012 AIChE Annual Meeting in Pittsburg in November 2012, and then submitted a proposal to NSF which was funded. Simultaneously, a similar project was submitted (by M.A.A. Meireles) to CNPq (Conselho Nacio- PREFACE 9 nal de Desenvolvimento Científico e Tecnológico/ Nation- al Council for Scientific and Technological Development) in Brazil which was also funded. With a sound base-funding secured from NSF, LASEFI, CNPq and the Journal of Supercritical Fluids, the workshop was formally announced at the 3rd Iberoamer- ican Conference on Supercritical Fluids that was held in Cartagena, Colombia in April 2013. Our initial plans were to organize a modest work- shop with a total of about 50-60 participants consisting of 25-30 experts and 25-35 postdoctoral fellows or senior grad- uate students. However, the interest in the workshop far exceeded our initial expectations. We are extremely pleased that we have a total of 104 participants from 20 different countries. The first day of the technical sessions of the work- shop is devoted to a total of 21 overview/plenary lectures that are grouped under 1. State of the supercritical fluid science and technol- ogy — future direction and status of commercial- ization, 2. Supercritical fluid science and technology for bio- based fuel processes, 3. Supercritical fluid science and technology for new materials and materials processing, 4. Supercritical fluid science and technology for green chemistry and sustainable technology and 5. Supercritical fluids as working fluids and process technology. The second day of technical sessions is devoted to 37 lectures on the role of supercritical fluid science and 10 SFE 2013 | WORKShOP ON SUPERCRITICAL FLUIDS AND ENERGy technology that will be presented and discussed in five parallel-run Panel sessions grouped under: 1. Bio-base fuel processes 2. New materials and materials processing 3. Green chemistry and sustainable technology 4. Supercritical fluids as working fluids / process tech- nology and design 5. Process technology and future directions. Also scheduled for the second day of the workshop is the afternoon Poster Session that will have 42 presen- tations by junior faculty members, postdoctoral fellows, research associates, or senior graduate students. The third day of the workshop is devoted to the presentations and the discussions of the panel outcomes by all participants. This book of abstracts includes all the abstracts of the overview and the panel lectures and the poster pre- sentations which we trust you will find of value as a future reference. We would like to take this opportunity to thank all the participants for their willingness to come to this work- shop and share their knowledge, and their commitment to the advancement of our field. We are optimistic that this workshop will lead to new interactions and collabo- rations, and in particular will help the next generation of scientists to be connected with our greater community. We are grateful to our international and local organizing committee members, Drs. Gerd Brunner, Richard Smith, Flávio C. Albuquerque, Sandra R. S. Ferreira, Camila G. Pereira, Hosiberto B. Sant’Ana and Diego T. Santos for their valuable insight in organization and help with the logistics. PREFACE 11 We would also like to thank the various government and private organizations which have provided additional financial support to make this workshop possible. Our spe- cial thanks go to Drs. Bruce Hamilton and Ram Gupta of the National Science Foundation, CNPq, CAPES-PROEX, Dr. Angela Welch of Elsevier and the Journal of Supercrit- ical Fluids, Dr. J. W. King of the Supercritical Fluid Sym- posia, Dr. Jacques Fages of the International Society for Advancement of Supercritical Fluids, Volkmar Steinhagen of UHDE, Chris Spilsbury of the BG Group, and Kenneth R. Krewson of Supercritical Fluid Technologies. M. Angela A. Meireles Erdogan Kiran Workshop Directors PRESENTATION Supercritical fluids are a unique class of process fluids and solvents, which display tunable properties. They are employed at conditions beyond the thermodynamic vapor- liquid critical point. At those conditions, properties of su- percritical fluids can be changed over a wide range, and adapted to process needs. They are attractive process fluids in combining a set of unique properties like low viscosity, high diffusivity, zero surface tension, and a high compress- ibility. Water, for example, is used extensively as working fluid in power generation processes, at conditions below the critical point and increasingly at supercritical condi- tions. Carbon dioxide and ammonia are utilized in a similar way. Supercritical fluids modify the properties of com- pounds in mixtures. They dissolve components far beyond their vapor pressure.
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