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New Catalysts for Clean Environment 2Nd Symposium of the VTT Research Programme on Chemical Reaction Mechanisms

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New Catalysts for Clean Environment 2Nd Symposium of the VTT Research Programme on Chemical Reaction Mechanisms VTT SYMPOSIUM 163 UDC 66.097.3:504:061.3 Keywords: catalysts, biocatalysts, enzymes, reaction mechanisms, catalytic antibodies, natural fibers, baking, methane activation, gas cleaning, chemical industry, pulp and paper industry, energy production &OAJF-?<bo//£% New catalysts for clean environment 2nd symposium of the VTT Research Programme on Chemical Reaction Mechanisms Espoo, January 29-30, 1996 Edited by Aila Maijanen & Anneli Hase VTT Chemical Technology Organized by VTT Chemical Technology & VTT Research Programme on Chemical Reaction Mechanisms jPgffiigtiiKX* OF "ftBS DOCUMENT IS UNLBlrfED "#T TECHNICAL RESEARCH CENTRE OF FINLAND ESPOO 1996 ISBN 951-38 —4554-0 ISSN 0357-9387 Copyright © Valtion teknillinen tutkimuskeskus (VTT) 1996 JULKAISIJA - UTGIVARE - PUBLISHER ' Valtion teknillinen tutkimuskeskus (VTT), Vuorimiehentie 5, PL 2000,02044 VTT puh. vaihde (90) 4561, telekopio (90) 456 4374 Statens tekniska forskningscentral (VTT), Bergsmansvagen 5, PB 2000,02044 VTT tel. vaxel (90) 4561, telefax (90) 456 4374 Technical Research Centre of Finland (VTT), Vuorimiehentie 5, P.O.Box 2000, FIN-02044 VTT, Finland phone intemat. + 358 0 4561, telefax + 358 0 456 4374 VTT Kemiantekniikka, Prosessitekniikka, Biologinkuja 7, PL 1401, 02044 VTT puh. vaihde (90) 4561, telekopio (90) 460 041 VTT Kemiteknik, Processteknik, Biologgranden 7, PB 1401, 02044 VTT tel. vaxel (90) 4561, telefax (90) 460 041 VTT Chemical Technology, Process Technology Biologinkuja 7, P.O. Box 1401, FIN-02044 VTT, Finland phone intemat. + 358 0 4561, telefax + 358 0 460 041 VTT OFFSETPAINO, ESPOO 1996 DISCLAIMER Portions of this document may be illegible in electronic image products. Images are produced from the best available original document PREFACE VTT launched a Research Programme on Chemical Reaction Mechanisms (CREAM) in 1993. The three-year programme (1993-1995) has focused on reaction mechanisms relevant to process industries and aimed at developing novel catalysts and biocatalysts for forest, food, and specialty chemicals industries as well as for energy production. The preliminary results of this programme have already been presented in the first symposium organized in Espoo in September 1994. To conclude the programme the second symposium is organized in Otaniemi, Espoo on January 29 - 30, 1996. Papers by 19 speakers and 17 poster presentations of the 1996 Symposium are included in this book. The authors are mostly VTT researchers who have participated in the CREAM programme. However, many other scientists who work in related research fields in industry, universities, VTT, and research establishments outside VTT have brought a remarkable contribution to this symposium as speakers, poster presenters, keynote speakers, and as session chairmen. The Symposium consists of four sessions: Session I: Biotechnology for Natural Fibers Processing Session II: New Biocatalysts Session m Catalysts for Clean Energy Session IV: New Opportunities for Chemical Industry The Symposium Programme Committee members are: Prof. Markku Auer, Research Director, VTT Chemical Technology (Chairman) Dr. Lars Gadda, Vice President, Neste Corporation Technology Martti Aijala, Technology Manager, Imatran Voima Oy Prof. Anneli Hose, CREAM Programme Manager, VTT Chemical Technology Matti Huuska, Research Scientist, VTT Chemical Technology Pekka Simell, Research Scientist, VTT Energy Prof. Kai Sipild, VTT Energy Prof. Hans Soderlund, VTT Biotechnology and Food Research Dr. Tuula Teeri, Chief Research Scientist, VTT Biotechnology and Food Research Dr. Maija Tenkanen, Senior Research Scientist, VTT Biotechnology and Food Research Prof. Liisa Viikari, VTT Biotechnology and Food Research Aila Maijanen, Research Scientist, VTT Chemical Technology (Secretary) Expertise assistance for the Symposium arrangements has been given by Ms. Kristiina Kivimaa, Ms. Maija Korhonen, and Ms. Annika Stenman. Technical assistance by Mr. Matti Jantti, Lie. Tech., in editing this book is also gratefully acknowledged. 3 The CREAM programme has tried to foresee solutions for the problems challenged by the public concern on environmental aspects, especially dealing with industrial processes and novel use of raw materials and energy. The programme has followed the basic routes that can lead to natural and simple solutions to develop processes in the fields of forest, food, fine chemicals, and energy industry. The expertise in these fields has increased remarkably giving a clearer view on reality - often valued as wisdom. This symposium presents the results of the programme to learn and further discuss together with the international excellence that has been invited as keynote speakers. The CREAM programme has afforded a great chance for different VTT groups and units to work together and get inspired by encountering different views on familiar problems. The programme has served as a necessary contact surface for benchmarking in the VTT polytechnic organization. It has also offered the participants new possibilities for research, learning, and international and domestic contacts. I wish to thank the programme participants and all the symposium speakers and poster presenters, especially our international speakers, who have been interested in breaking their daily duties and travelled to this scenic but cold country to share our January darkness. Espoo, December 20,1995 Anneli Ease Programme Manager, CREAM Research Professor, VTT Chemical Technology 4 CONTENTS PREFACE 3 Session I: Biotechnology for natural fibres processing 9 Chairman: Jyrki Kettunen, Finland Biocatalysts for the pulp and paper industry 11 Liisa Viikari, Finland Enzyme-aided analysis of fibre surfaces 21 Anna Suumakki. Maija Tenkanen, Johanna Buchert and Liisa Viikari, Finland Cellulolytic enzymes in biofinishing of cellulosic fabrics 29 Pia Sarkkd and Pirkko Suominen . Finland Cell wall degrading enzymes in baking 37 Helena Harkonen. Tarn Laurikainen, Karin Autio, Maija Tenkanen and Kaisa Poutanen, Finland How do enzymes degrade crystalline cellulose? 45 Tapani Reinikainen. Anu Koivula, Laura Ruohonen, Markus Linder, Malee Srisodsuk, Janne Lehtid, T. Alwyn Jones and Tuula T. Teeri, Finland Session II: New biocatalysts 51 Chairman: Olle Teleman, Finland Reaction mechanisms of carbohydrases 53 Torbiom Drakenbere. Vesa Harjunpaa and Anita Teleman, Finland Tailor-made selective catalysts - catalytic antibodies 61 Daniel Thomas, France Enzymes in organic synthesis 63 Liisa T. Kanerva, Finland Control of regioselectivity, diastereoselectivity and enantioselectivity in the antibody-catalysed Diels-Alder reaction 69 Jari Yli-Kauhaluoma, Finland Session HI: Catalysts for clean energy 75 Chairman: Martti Aijala, Finland BASF catalysts for the removal of NOx and dioxin in various applications 77 Bemd Morsbach, Peter Odermatt and Roland Spahl, Germany 5 Long-time experience in catalytic flue gas cleaning and catalytic NOx reduction in biofueled boilers 95 Minna Ahonen, Finland A novel zeolite process for clean end use of hydrocarbon products 111 Kari M. Keskinen, Finland New catalysts for exhaust gas cleaning 117 Matti Harkonen, Finland Catalytic hot gas cleaning 123 PekkaSimell, Finland Selective catalytic oxidation of ammonia 131 Jukka Leppalahti and Tiina Koljonen, Finland Session IV: New opportunities for chemical industry 139 Chairman: Lars Gddda, Finland New catalysts for polymer synthesis 141 Hans-Herbert Brintzinger, Germany Enzymes as polymerisation catalysts 143 Alovs Huttermann andAlireza Kharazipour, Germany Recent advances in methane activation 149 Matti Huuska and Kirsi Kataja, Finland A biomimetic methane-oxidising catalyst 155 Howard Dalton, UK Towards molecular design of metallocene catalysts 163 Lars-Olof Pietila a nd Lisbeth Ahiopalo. Finland Posters: 167 Recent advances in AFB biomass gasification pilot plant with catalytic reactors in a downstream slip flow 169 M.P. Aznar, J. Gil, J.A. Martin, E. Frances, A. Olivares, M.A. Caballero, P. Perez and J. Corella, Spain Criteria for selection of dolomites and catalysts for tar elimination from gasification gas; kinetic constants 177 Jose Corella, Ian Narvaez, Alberto Orio, Spain Effectiveness factors for a commercial steam reforming (Ni) catalyst and for a calcined dolomite used downstream biomass gasifiers 185 Jose Corella, Ian Narvaez, Alberto Orio, Spain 6 An investigation of the zirconocene/alumoxane system 191 J. Enqvist, J. Yli-Kauhaluoma, L. Ahjopalo, L.-0. Pietila and O. Orama, Finland Selective catalytic reduction of nitric oxide by ethylene over metal-modified ZSM-5- and Y-AI2O3 -catalysts 197 Kari Erdnen, Narendra Kumar and Lars-Eric Lindfors, Finland Progress-curve analysis of cello-oligosaccharide hydrolysis by cellobiohydrolase II from Trichoderma reesei 203 Vesa Harjunpad, Anita Teleman, Anu Koivula, Tuula T. Teeri, Olle Teleman and Torbjdm Drakenberg, Finland Effect of H2S on catalytic decomposition of tar and ammonia with dolomite and sintered iron ore in synthetic gasification gas 209 JoukoHepola, Finland Methane activation on palladium and mercury loaded solid supports 217 Kirsi Kataja, Matti Huuslca, Kimmo Karinto, Aila Maijanen, Matti ReiniJcainen, Jari Kiviaho and Anneli Hase, Finland Catalytic mechanism of Trichoderma reesei cellobiohydrolase H (CBHII) 223 Anu Koivula, Laura Ruohonen, Tapani Reinikainen, Marc Claeyssens, T. Alwyn Jones and Tuula T. Teeri, Finland High quality flax pulp. An opportunity for non-food agroindustrial production 229 Anja Leminen, Allan Johansson and Kai Sipila, Finland Characterization of a recombinant dimeric cellulose-binding domain 235
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