Reaction Engineering for Pollution Prevention by Martin A. Abraham, Robert P. Hesketh, Robert P. Hesketh (Editor) • ISBN: 0444502157 • Pub. Date: February 2000 • Publisher: Elsevier Science & Technology Books Preface In 1997, the Catalysis and Reaction Engineering division of the American Institute of Chemical Engineers was initiated to afford researchers in the reaction engineering community a greater opportunity to participate in the national discussion. It was decided that one of the initial programming events of the new division would be a Topical Conference on Environmental Reaction Engineering and Catalysis. Shortly thereafter, the division teamed up with the North American Catalysis Society to organize the Second World Congress on Environmental Catalysis, and the Topical Conference on Environmental Reaction Engineering became a separate entity. This Topical Conference took place at the AIChE 1998 Annual meeting in Miami Beach, Florida. We would like to acknowledge the members of the topical conference organizing committee, who helped to develop the technical sessions on which this book is based: John C. Friedly, MIT Practice School, Jan J. Lerou, Dupont USA, Yuri Matros, Matros Technologies, Jonathan Phillips, The Pennsylvania State University, Peter Smimiotis, University of Cincinnati, and Theodore Tsotsis, University of Southern California. Coordinated by Michael Harold, V^ Vice-Chair of the division and Martin Abraham, Topical Conference Programming Chair, six separate sessions were organized, with over 50 technical presentations. Authors of these presentations were then invited to prepare their work as a full-length manuscript for publication. Each manuscript was carefully reviewed by experts in the field and revised based on the reviewer's comments before inclusion in this volume. In the context of this book, we define environmental reaction engineering as the use of reaction engineering principles, including reactor design, for the development of processes that provide an environmental benefit. With regard to pollution prevention, we focus primarily on new reaction and reactor technologies that minimize the production of undesirable side-products (pollutants), but also consider the use of reaction engineering as a means of treating wastes that are produced through other means. Thus, we cover topics ranging from reactive distillation (for a cleaner production of MTBE) to photocatalytic oxidation (for treatment of air pollutants). Environmental reaction engineering is distinct from environmental catalysis - here we are focused on the reaction or the reactor whereas environmental catalysis focuses more closely on the development of the catalyst and the underlying surface science. The papers contained within this book have been classified into topics that are related to those of the individual sessions from the AIChE meeting. We begin with a section on environmentally benign combustion. The three papers discuss methods of reducing the formation of PAHs and NOx, as well as other environmentally sensitive combustion products. Next is a contribution from Heavy Industries Co. in Japan describing their efforts to capture the combustion exhaust gases for recycle into the combustion process. This paper serves as a bridge to a series of three papers on CO2 sequestration, including contributions from two U.S. national laboratories. Our inclusion of CO2 sequestration represents our recognition of the importance of the growing concentration of carbon dioxide in the atmosphere, and the role the chemical reaction engineering has on contributing to these increased levels. The next section contains a collection of contributions that involve the use of a catalyst to support the reaction. We begin with a paper describing catalytic reforming of methane using CO2, a process with implications to the carbon dioxide sequestration issue of the previous section. Two papers on unsteady catalysis follow, one involving the selective catalytic reduction of NOx the other involving oxidation of VOCs. Continuing the theme of VOC oxidation, we then present two papers on photocatalytic oxidation of VOCs, followed by two papers on photocatalysis for the treatment of organic compounds in wastewater. Next is a section on the use of supercritical fluid solvents as environmentally friendly media for chemical reactions. Three papers involve reaction in supercritical CO2, all discussing the potential for selective chemistry within this benign medium. A final paper in this section considers the use of supercritical water as a medium for the conversion of cellulose to useful chemicals. This process is beneficial not only for its use as a benign reaction solvent but also because of the possibility of converting renewable resources into valuable chemical feedstocks. Finally, a series of papers is presented in which novel reactor designs are utilized to obtain product yields not possible in conventional reactor systems. These include the use of reactor-absorber system, reactive distillation, and reactive membranes. The book concludes with a chapter that was contributed by the editors and discusses the educational aspects of pollution prevention. We have included this chapter because we believe that it is necessary for future generations of engineers to be trained to design processes that are inherently environmentally benign. This can only be achieved by assembling resource materials for educators. The chapter describes some of the materials that are available and provides direction onto where the interested reader should go for further information. It is our hope that this last chapter will spark the creative instincts of the researchers using the materials contained within this book to develop new resources for pollution prevention education. It is our hope that this book provides a reasonable cross-section of the field of environmental reaction engineering at this point in time. Certainly, the broad spectrum of topics included indicates the diversity of this area, and the vibrant nature of the ongoing research. As the field continues to grow, we expect to see continued interest in pollution prevention and benign processing, and expect reaction engineers to be at the forefront of developments in this area. One can only do so much to treat a waste in an effluent stream. However, the possibilities of producing desirable products without the formation of waste byproducts is bounded only by the creativity of the reaction engineer. In closing, we would like to take this opportunity to thank all of the individuals who have contributed to this effort. Specifically, we thank all of the individuals who contributed papers to this book, and all of those who took time from their busy schedules to review these papers and provide comments for the authors. We thank the Catalysis and Reaction Engineering division of the AIChE, and the AIChE itself, for providing us with the permission to produce this book based on the Topical Conference. We also recognize the efforts of the individual session organizers, who made the Topical Conference a valuable compilation of research in this area. Finally, we recognize Elsevier Science for providing us the opportunity to organize this book. Martin Abraham Professor, Chemical and Environmental Engineering The University of Toledo Robert Hesketh Associate Professor, Chemical Engineering Rowan University LIST OF CONTRIBUTORS Martin A. Abraham Arun C. Bose Dept. of Chemical & Environmental US Department of Energy Engineering Federal Energy Technology Center The University of Toledo Pittsburgh, PA 15236-0940 2801 W.Bancroft St. USA Toledo, OH 43606 USA G. A. Bunimovich Matros Technologies, Inc. Tadafumi Adschiri 14963 Green Circle Dr. Dept. of Chemical Engineering Chesterfield, MO 63017 Tohoku University USA Aoba-ku, Sendai 980-8579 JAPAN Darryl P. Butt Los Alamos National Laboratory K. Arai Mail Stop H846 Dept. of Chemical Engineering Los Alamos, NM 87545 Tohoku University USA Aoba-ku, Sendai 980-8579 JAPAN G. B. Combes University of New South Wales N. Arai School of Chemical Engineering Research Center for Advanced Energy Sydney, NSW 2052 Conversion AUSTRALL\ Nagoya University Nagoya S. N. Danov JAPAN Research Center for Advanced Energy Conversion G. Balasubramanian Nagoya University Dept. of Civil and Environmental Nagoya Engineering JAPAN 741 Baldwin Hall University of Cincinnati Hugo de Lasa P.O. Box 210071 University of Western Ontario Cincinnati, OH 45221-0071 Faculty of Engineering Science USA Chemical Reactor Engineering Center London, Ontario I. Baudin CANADA N6A 5B9 Lyonnaise Des Eaux CIRSEE F. Dehghani Le Pecq University of New South Wales France School of Chemical Engineering Sydney, NSW 2052 Eric J. Beckman AUSTRALL\ University of Pittsburgh 1249 Benedum Hall Chemical Engineering Dept. Pittsburgh, PA 15261 USA A. K. Dillow T. Furuhata University of Minnesota Research Center for Advanced Energy Dept. of Chemical Engineering and Conversion Materials Science Nagoya University Minneapolis, MN 55455 Nagoya USA JAPAN Dionysios D. Dionysiou Shigeo Goto Dept. of Civil and Environmental Nagoya University Engineering Dept. of Chemical Engineering 741 Baldwin Hall Furo-cho, Chikusa-ku University of Cincinnati Nagoya, Aichi-ken 464-8603 P.O. Box 210071 JAPAN Cincinnati, OH 45221-0071 USA D. Hancu University of Pittsburgh Can Erkey 1249 Benedum Hall Department of Chemical Engineering Chemical Engineering Dept. University of Connecticut Pittsburgh, PA 15261 Storrs, CT 06269-3222 USA USA Robert P. Hesketh Z. Fang Dept. of Chemical Engineering Dept. of Chemical Engineering Rowan University Tohoku University 201 Mullica Hill Rd. Aoba-ku, Sendai 980-8579 Glassboro,NJ 08028-1701 JAPAN USA Pio Forzatti H. Ibrahim Politecnico di Milano University of Western Ontario Piazza Leonardo da Vinci 32 Faculty of Engineering Science 20133 Milano Chemical Reactor Engineering Center ITALY London, Ontario CANADA N6A 5B9 Neil R. Foster University of New South Wales H. Itoh School of Chemical Engineering Nagoya University Sydney, NSW 2052 Dept. of Chemical Engineering AUSTRALL\ Furo-cho, Chikusa-ku Nagoya, Aichi-ken 464-8603 Y. Fukushima JAPAN Dept. of Chemical Engineering Tohoku University Jifi Jirat Aoba-ku, Sendai 980-8579 Prague Institute of Chemical Technology JAPAN Dept. of Chemical Engineering Technika 5 166 28 Prague 6 CZECH REPUBLIC T. Kiga Yu. Sh. Matros Ishikawajima-Harima Heavy Industries Co. Matros Technologies, Inc. 2-16 Toyosu 3-Chome, Koto-ku 14963 Green Circle Dr. Tokyo 135-8733 Chesterfield, MO 63017 JAPAN USA Milan Kubicek Ivan Milosavljevic Prague Institute of Chemical Technology Air Liquide Dept. of Mathematics 1, chemin de la Porte des Loges Technicka 5 Les Loges en Josas 166 28 Prague 6 78353 Jouy en Josas Cedex CZECH REPUBLIC FRANCE Klaus S. Lackner S. Miyamae Los Alamos National Laboratory Ishikawajima-Harima Heavy Industries Co. Mail Stop H846 2-16 Toyosu 3-Chome, Koto-ku Los Alamos, NM 87545 Tokyo 135-8733 USA JAPAN J. M. Laine Harvey M. Ness Lyonnaise Des Eaux US Department of Energy CIRSEE Federal Energy Technology Center Le Pecq Pittsburgh, PA 15236-0940 France USA Luca Lietti Isabella Nova Politecnico di Milano Politecnico di Milano Piazza Leonardo da Vinci 32 Piazza Leonardo da Vinci 32 20133 Milano 20133 Milano ITALY ITALY G. Q. (Max) Lu M. Okawa Department of Chemical Engineering New Energy and Technology Dev. Dept. The University of Queensland Electric Power Development Co., Ltd. St. Lucia, QLD 4072 6-15-1, Ginza, Chuo-ku AUSTRALL\ Tokyo 104-8165 JAPAN F. P. Lucien University of New South Wales Nesrin Olten School of Chemical Engineering University of California, Los Angeles Sydney, NSW 2052 5531 Boelter Hall AUSTRALL\ Los Angeles, CA 90095 USA Milos Marek Prague Institute of Chemical Technology D. R. Palo Dept. of Chemical Engineering Department of Chemical Engineering Technika 5 University of Connecticut 166 28 Prague 6 Storrs, CT 06269-3222 CZECH REPUBLIC USA Sean I. Plasynski Frantisek Stepanek US Department of Energy Prague Institute of Chemical Technology Federal Energy Technology Center Dept. of Chemical Engineering Pittsburgh, PA 15236-0940 Technika 5 USA 166 28 Prague 6 CZECH REPUBLIC Pluton Pullumbi Air Liquide Vadim O. Strots 1, chemin de la Porte des Loges Matros Technologies, Inc. Les Loges en Josas 14963 Green Circle Dr. 78353 Jouy en Josas Cedex Chesterfield, MO 63017 FRANCE USA A. T. Quitain M. T. Suidan Nagoya University Dept. of Civil and Environmental Dept. of Chemical Engineering Engineering Furo-cho, Chikusa-ku 741 Baldwin Hall Nagoya, Aichi-ken 464-8603 University of Cincinnati JAPAN P.O. Box 210071 Cincinnati, OH 45221-0071 Ajay K. Ray USA National University of Singapore Dept. of Chemical and Environmental K. Suzuki Engineering Ishikawajima-Harima Heavy Industries Co. 10 Kent Ridge Crescent 1 Shinnakahara, Isogo-ku, Yokohama Singapore, 119260 Kanagawa 235-8501 JAPAN C. R. Roach Monsanto Enviro-Chem Systems, Inc. H. Teng P.O. Box 14547 National Institute of Materials and Chemical St. Louis, MO 63178 Research USA 1-1 Higashi, Tsukuba 305 JAPAN M. Sasaki Dept. of Chemical Engineering Enrico Tronconi Tohoku University Politecnico di Milano Aoba-ku, Sendai 980-8579 Piazza Leonardo da Vinci 32 JAPAN 20133 Milano ITALY Daniel J. Seery United Technologies Research Center Savvas Vasileiadis East Harford, CT 06108 ZiVaTech USA 15549 Dearborn St. North Hills, CA 91343 Selim M. Senkan USA University of California, Los Angeles 5531 Boelter Hall M. Wakatsuki Los Angeles, CA 90095 University of Tokyo USA 7-3-1 Hongo, Bunkyo-ku Tokyo, 113-8656 JAPAN Shaobin Wang Hiroshi Yamashita Department of Chemical Engineering Dept. of Mechanical Engineering The University of Queensland Nagoya University St. Lucia, QLD 4072 Furo-cho, Chikusa-ku AUSTRALIA Nagoya, Aichi 464-8603 JAPAN Christopher H. Wendt Los Alamos National Laboratory Y. Yanagisawa Mail Stop H846 University of Tokyo Los Alamos, NM 87545 7-3-1 Hongo, Bunkyo-ku USA Tokyo, 113-8656 JAPAN K. Yamada University of Tokyo D. Zhao 7-3-1 Hongo, Bunkyo-ku New Energy and Industrial Technology Tokyo, 113-8656 Development Organization JAPAN Nagoya JAPAN Toshihiko Yamada Ishikawajima-Harima Heavy Industries Co. Zoe Ziaka 2-16 Toyosu 3-Chome, Koto-ku ZiVaTech Tokyo 135-8733 15549 Dearborn St. JAPAN North Hills, CA 91343 USA Akihiro Yamasaki University of Tokyo Hans-J. Ziock 7-3-1 Hongo, Bunkyo-ku Los Alamos National Laboratory Tokyo, 113-8656 Mail Stop H846 JAPAN Los Alamos, NM 87545 USA