Chemical Reactor Technology for Environmentally Safe Reactors and Products

NATO ASI Series Advanced Science Institutes Series

A Series presenting the results of activities sponsored by the NATO Science Committee, which aims at the dissemination of advanced scientific and technological knowledge, with a view to strengthening links between scientific communities.

The Series is published by an international board of publishers in conjunction with the NATO Scientific Affairs Division

A Life Sciences B Physics

C Mathematical and Physical Sciences

D Behavioural and Social Sciences E Applied Sciences

F Computer and Systems Sciences G Ecological Sciences H Cell Biology I Global Environmental Change

Plenum Publishing Corporation London and New York

Kluwer Academic Publishers Dordrecht, Boston and London

Springer-Verlag Berlin, Heidelberg, New York, London, Paris and Tokyo

NATO-PCO-DATA BASE

The electronic index to the NATO ASI Series provides full bibliographical references (with keywords and/or abstracts) to more than 30000 contributions from international scientists published in all sections of the NATO ASI Series. Access to the NATO-PCO-DATA BASE is possible in two ways:

- via online FILE 128 (NATO-PCO-DATA BASE) hosted by ESRIN, Via Galileo Galilei, I-00044 Frascati, Italy.

- via CD-ROM "NATO-PCO-DATA BASE" with user-friendly retrieval software in English, French and German (© WTV GmbH and DATAWARE Technologies Inc. 1989).

The CD-ROM can be ordered through any member of the Board of Publishers or through NATO-PCO, Overijse, Belgium.

Series E: Applied Sciences - Vol. 225

Chemical Reactor Technology for Environmentally Safe Reactors and Products

edited by

H. I. de Lasa Faculty of Engineering Science, The University of Western Ontario, London, Ontario, Canada

G. Dogu Gazi University, Maltepe, Ankara, Turkey

and

A. Ravella Imperial Oil Ltd., Research Department, Sarnia, Ontario, Canada

SPRINGER-SCIENCE+BUSINESS MEDIA, B.V

Proceedings of the NATO Advanced Study Institute on Chemical Reactor Technology for Environmentally Safe Reactors and Products London, Ontario, Canada 25 August - 4 September 1991

Librar y of Congres s Cataloging-in-Publicatio n Data

C h e m i c al r e a c t o r t e c h n o l o g y f o r e n v i r o n m e n t a l l y s a f e r e a c t o r s an d p r o d u c t s / e d i t e d b y H . I . d e L a s a , G. Dogu , A . R a v e l l a .

p. cm. — (NAT O AS I s e r i e s . S e r i e s E , A p p l i e d s c i e n c e s ; no . 225)

I n c l u d e s i n d e x .

1. C h e m i c a l r e a c t o r s — E n v i r o n m e n t a l a s p e c t s . I . De L a s a , Hug o I . I I . D o g ü , G. I I I . R a v e l l a , A . IV . S e r i e s . TP157.C418 199 2 6 6 0 ' . 2 8 3 — d c 2 0 92-3659 1

ISBN 978-94-010-5219-1

Printed on acid-free paper

All Rights Reserved © 1992Springer-Science+Business Media Dordrecht

Originally published byKluwer Academic Publishers and copyright holders as spe-cified on appropriate pages within in 1992 Softcover reprint of the hardcover 1st edition 1992 No part of the material protected by this copyright notice may be reproduced or utilized in any form or by any means, electronic or mechanical, including photo-copying, recording or by any information storage and retrieval system, without written permission from the copyright owner.

ISBN 978-94-010-5219-1 ISBN 978-94-011-2747-9 (eBook)DOI 10.1007/978-94-011-2747-9

Table of Contents

Hugo I. de Lasa

Preface

I. Fuels of the Future and Changing Fuel Needs

A. Ravella

How Should Environmentally Benign Gasolines be Formulated?

G.L. Haning, H. Shannon Oxygenates as Gasoline Blending Components

D. King Engineering of Fluidized Catalytic Crackers

A. W. Peters, W-C Cheng, T. G. Roberie

Scientific Aspects of Novel Catalysts for FCC

H. de Lasa, D. Kraemer

Novel Techniques for FCC Catalyst Selection and Kinetic Modelling

A. Pekediz, D. W. Kraemer, J. Chabot, H.!. de Lasa Mixing Patterns in a Novel Riser Simulator

P.H. Schipper, A. V. Sapre, Q.N. Le

Chemical Aspects of Clean Fuels Production

II. Alternative Sources

J.e. w. Kuo Evaluation of Direct Methane Conversion Processes

ix

1

7

17

51

71

133

147

183

vi

M.M. G. Senden, S. T. Sie, M.F.M. Post, J. Ansorge Engineering Aspects of the Conversion of Natural Gas

Into Middle Distillates

J. Rostrup-Nielsen, I. Dybkjaer, L.J. Christiansen Steam Reforming Opportunities and Limits of the Technology

M. Baerns Oxidative Coupling of Methane for the Utilization of

Natural Gas

O. Altin, I. anal, T. Dogu, J.B. Butt Dysprosium Oxide for Oxidative Coupling of Methane

F. Berruti, L.A. Behie Ultrapyrolysis of Heavy Oils: Reaction Kinetics and

Reactor Technology

M.P. Dudukovic, N. Devanathan Bubble Column Reactors: Some Recent Developments

F. Berruti, R. Wong Strategies for Low Emissions From Circulating

Fluidized Bed Boilers

G.F. Froment

Kinetic Modelling of Complex Processes. Thermal Cracking and Catalytic Hydrocracking

P. Trambouze Engineering of Hydrotreating Processes

227

249

283

317

325

353

379

409

425

III. Emission Control, Chemical Reactor Safety and Engineering

G. Cao, M. Morbidelli, A. Varma Thermal Sensitivity and Runaway in Chemical Reacting Systems 443

G. Dogu, T. Dogu

Kinetics of Capture of Sulfur Dioxide and Applications to 467 Flue Gas Desulfurization

G. Dogu, G. Olmez, T. Dogu

Removal of S02 with Lime Slurry in a Spray Dryer 499

C. Brereton, J.R. Grace, C.J. Lim, J. Zhu Engineering Aspects of Recirculating Fluidised Bed Combustion

B.P.A. Grandjean, J. Chaouki Application of a Monte Carlo Method to the Solid Flow Pattern

Visualization in CFB

J.P. Leclerc, D. Schweich Modeling Catalytic Monoliths for Automobile Emission Control

E. Pelizzetti, C. Minero, E. Pramauro Photocatalytic Processes for Destruction of Organic Water

Contaminants

I. Poulios, A. Avranas Heterogeneous Photocatalytic Degradation of the Cationic

Surfactants Cetyldimethylbenzylammonium Chloride and Cetylpyridinium Chloride

J.J. Lerou, L.E. Manzer Progress in the Development of Chlorofluorcarbon

(CFC) Alternatives

Index

vii

507

537

547

577

609

617

625

Preface

If the decade of the 70's and mid 80's were influenced by two energy crisis and the related concerns about adequate and secure supply of hydrocarbons and fossil fuels, the decade of the 90's will be one of environmental concerns. The chemical and energy industry worldwide are at the basis of these concerns. However, it is expected that the actual utilization of some of the processes used and products produced and marketed, such as gasolines of different kinds, and/or processes for the conversion of various fossil fuels will presumably continue evolving during the 90's and the next century. A drastic reduction of some of these products would translate into a significant lowering of living standards not likely to be accepted by the Western world. The challenge is not how to phase out processes and products but how to adapt these products to meet more rigorous environmental standards. This is certainly an outstanding challenge for the new generation of chemical engineering researchers and an area where reactor engineering could significantly contribute.

Therefore, Chemical Reactor Engineering, as a discipline, has a central role to play in helping with the development of adequate strategies and technologies that can effectively deal with the concerns of to day's society. There is a need to reflect about these matters and to exchange views and experiences.

With these facts in mind, a NATO-ASI conference was planned considering that could help conceptualize new approaches and novel technologies. It was perceived that this was a time for reflection and action. It was also perceived that the NATO-AS I was calling on the cord of researchers' social responsibility bringing them together to plan and visualize new technologies.

With this general background, a NATO-Advanced Study Institute on Chemical Reactor Technology for Environmentally Safe Reactors and Products was proposed to the NATO Scientific Branch in July 1990 by the Chemical Reactor Engineering Centre-University of Western Ontario (CREC-UWO). The NATO-Advanced Study Institute Conference was held between August 25, 1991 and September 4, 1991 in Spencer Hall, London, Ontario. More than 75 participants, including several worldwide leading authorities in the field of Chemical Reactor Engineering from academia, research institutes and industries participated in this event. A total of 17 countries from Europe, North America, South America and Asia were represented.

Ten intensive working days were planned for this NATO-AS I conference, covering as major themes: Fuels of the Future and Changing Fuel Needs, Alternative Sources, Emission Control and Safety. During most of the morning and afternoon sessions, the selected format was of the lecture type; presentation and question periods.

ix

x

In addition, three panel discussions on particularly critical and pressing environmental issues closely related to the chemical engineering industry were planned. These panel discussions, chaired by highly involved scientists, were: 1) Strategies for Low Emissions from Circulating Fluidized Bed Boilers (professor F. Berruti, University of Calgary), 2) How Should Environmentally Benign Gasolines be Formulated? (Dr. A. Ravella, Imperial Oil Ltd., Sarnia, Canada) and 3) Fluorocarbon Chemical Substitutes to Reduce Ozone Depletion (Dr. 1. Lerou, Dupont, USA).

The intensive program of technical activities for the NATO-AS I conference expanded to the dinners at Spencer Hall with special invited speakers. Dr. G. Donati, Enichem, discussed: "DMC: a Product/Technology for Future Environmentally Safe Processes", Dr. 1. Christie, Manager Power Train Design, General Motors of Canada Limited reviewed" Automotive Engine and Future Fuels", Mr. P.J. Allen, Manager, CANDU 3 Safety and Licensing, Atomic Energy of Canada, considered "Strategies for Safety in Nuclear Reactors/Power Plants".

In addition to this extensive theoretical program, a visit to the Sarnia Chemical Valley, the heart of the Canadian petroleum and petrochemical industry was planned. Three major refineries (Esso's, Shell's and Suncor's), a number of petrochemical plants (Nova's, Dow's, BASF's) and other chemical industries (AKZO, LINDE, etc.) constitute a unique concentration of chemical "hardware" which makes Sarnia the ideal location for a full one day trip during the Conference. Such concentration of chemical industrial sites creates the need for very stringent controls on emissions, losses and environmental issues which were discussed during the visit. The trip to Sarnia included a visit to Esso Petroleum Canada Refinery and Dow Chemical's Petrochemical Plant, followed by presentations at Esso's Sarnia Research Department on "Strategies on Air Quality Control". The closeness of CREC-UWO to a major petrochemical site and industrial research facilities created another major justification for the development of the NATO-AS I in such a strategic location as London, Ontario.

Furthermore, in order to stimulate discussions and favourize the exchange of novel ideas and concepts related to various areas of chemical engineering, the participants were invited to contribute to the Conference during the Poster Presentation Session chaired by Professor J. Arandes, from the Universidad del Pafs Vasco, Spain. Over 20 poster presentations were displayed at this session.

A more practical note was added to the conference during the laboratory experiment demonstrations session. The participants were invited to attend various demonstrations in the laboratories of the Chemical Reactor Engineering Centre of the University of Western Ontario. These demonstrations served the double purpose of providing the various participants with the opportunity to discuss more extensively the technical aspects of the various research projects in progress and to note the calibre and vigour of the research activities of the CREC.

The various participants also had the opportunity to get a flavour of the Canadian landscape and have a glance at the artistic life in Canada. An afternoon in the theatre at Stratford, as well as a visit to Niagara falls, Niagara-on-the Lake and Fort George were part of the conference program. These activities presented an opportunity for the participants to pursue discussions in a more relaxed atmosphere.

xi

In summary, the second NATO-ASI was a massive learning experience where lecturers and participants found a most appropriate atmosphere for fruitful technical exchanges and for visualizing technological innovations for reactor technologies. It also provided an opportunity for participants to consider new or anticipated environmental regulations and concerns.

I would like to express here my gratitude to the co-directors of the NATO-ASI, Professor G. DogtI, Gazi University and Dr. A. Ravella, Imperial Oil Ltd., Canada, who contributed considerably to the success of the NATO-AS!. Furthermore, I would also like to express my sincere thanks to the Members of the Scientific Advisory Committee; Professor F. Berruti, Professor J. Grace, and Dr. A. Sapre who helped in the difficult task of selecting the topics and lecturers.

My special thanks must also be addressed to the Local Organizing Committee, graduate students of the University of Western Ontario, and Mr. S. Afara, Mr. A. Pekediz and Ms. J. Chabot from CREC-UWO, who contributed with remarkable enthusiasm to make our meeting successful.

My special appreciation to Dr. Ravella and Professor Dogu for their contribution in the process of reviewing all papers included in this book. My gratitude to Mr. Afara and Mrs. P. Young from CREC-UWO for their most valuable help in bringing all of the manuscripts to the high level of presentation required.

I would also like to express my sincere gratitude to the NATO Scientific Affairs Division who supported financially the NATO-ASO conference. As well, I would also like to gratefully acknowledge the financial contribution of the Natural Science and Engineering Research Council of Canada.

Finally, my deepest gratitude to my wife Graciela and my children who provided the understanding, cooperation and inspiration needed for the success of this event.

Hugo de Lasa

London, Ontario, Canada

List of Lecturers

M. Baerns, Ruhr-Universitat Bochum, 4630 Bochum 1, Universitat str 150, Germany.

F. Berruti, University of Calgary, Department of Chemical & Petroleum Eng., 2500 University Drive N.W., Calgary, Alberta, T2N IN4.

C. Brereton, University of British Columbia, Department of Chemical Engineering, Faculty of Engineering Science, 2216 Main Mall, Vancouver, BC, V6T lW5.

L. Christiansen, Haldor Topsoe A/S, Nymoellevej 55, 2800 Lyngby, Denmark.

H.I. de Lasa, The University of Western Ontario Faculty of Engineering Science, London, Ontario, N6A 5B9.

G. Dogu, Gazi University, Department of Chemical Eng., Faculty of Eng. and Arch., Maltepe, Ankara 06570, Turkey.

M.P. Dudukovic, Washington University in St. Louis, Chemical Engineering Department, Campus Box 1198, St. Louis, Mo 63130.

G.F. Froment, Laboratorium Voor Petrochemische Technick, Rijkuniversiteit, Krijgslaam 271, 9000 Gent, Belgium.

D. King, Chevron Research Co., P.O.Box 1627, Richmond CA, USA.

J. Kuo, Mobil Research and Development Corporation, Research Department, Paulsboro, New Jersey 08066.

J.P. Leclerc, ENSIC, Laboratoire de Sciences du Genie Chimique, 1 rue Grandville, 54042 Nancy, France.

M. Morbidelli, Universita di Cagliari, Dipartimento di Ingegneria Chimica e MateriaIi, Cagliari, Italy.

E. Pelizzetti, Universita di Parma, Instituto di Chimica Fisica Applicata, 43100 Parma, Italy.

A. Peters, W.R. Grace & Company, Davison Chemical Division, 7379 Route 32, Columbia, MD 21044.

P.H. Schipper, Mobil Research and Development Corporation, Paulsboro Research Laboratory, Paulsboro, New Jersey, 08066-0480.

M.M. Senden, Koninklijke/Shell Laboratorium (Shell Research B.V.), P.O.Box 3003, 1003 AA Amsterdam, The Netherlands.

P. Trambouze, Institut Fran~ais du Petrole, Centre D'Etudes et de Developpement Industriels, CEDI, P.O.B. 3, 69390 Vernaison, France.

xiii

List of Participants

S. Afara, The University of Western Ontario, Faculty of Eng. Science, London, Ontario, N6A 5B9.

P.J. Allen, Atomic Energy of Canada, CANDU 3, 2251 Speakman Drive, Mississauga, Ont. L5K lB2.

O. Altin, Middle East Technical University, Department of Chemical Engineering, Ankara Turkey.

I. Ar, Gazi University, Faculty of Engineering and Architecture, Chemical Engineering Department, Maltepe, Ankara 06570, Turkey.

J. Arandes, Universidad del Pars Vasco, Departamento de Ingenieria Quimica, Apartado 644, E-48080 Bilbao, Spain.

A. Avranas, Aristotle University, Laboratory of Physical Chemistry, Department of Chemistry, 54006, Thessalonoki, Greece.

M.J. Azkoiti, Universidad del Pars Vasco, Departamento de Ingenieria Quimica, Apartado 644, E-48080 Bilbao, Spain.

Mr. Balbasi, Gazi University, Faculty of Engineering and Architecture, Chemical Engineering Department, Maltepe, Ankara 06570, Turkey.

S. Bald, Middle East Technical University, Chemical Engineering Department, 06531 Ankara, Turkey.

C.M.G. Baptista, S.A. Engenharia Quimica - FCTUC, Largo Marques de Pombal, 3000 Coimbra, Portugal.

M.A. Bergougnou, The University of Western Ontario, Faculty of Eng. Science, London, Ontario, N6A 5B9.

A. Blasetti, Universidad de La Patagonia, Facultad de Ingenieria, Comodoro Rivadavia, Argentina.

J. Chabot, The University of Western Ontario, Faculty of Eng. Science, London, Ontario, N6A 5B9.

J. Chaouki, Ecole Poly technique, Chern. Eng. Dept., Case Postale 6079, Succursale A, Quebec, H3C 3A 7.

J. Christie, General Motors of Canada Limited, 1908 Colonel Sam Drive, Oshawa, Ont. LIH 8P7.

L.M.S. Da Silva, Universidade do Porto, Departamento de Engenharia Quimica, Faculdade de Engenharia, Rua dos, Bragas, 4099 Porto Codex, Portugal.

M. del Pozo, Total Petroleum, Centre de Recherches Total France, BP 27, 76700 Harfleur, France.

xv

xvi

S. de Santiago, Instituto Mexicano del Petrol eo , Gerencia Sistemas y Simulacion, 1, Lazaro Cardenas 152, Mexico 07730, Mexico.

T. Dogu, Middle East Technical University, Department of Chemical Engineering, Ankara, Turkey.

G. Donati, Enichem, Instituto Guido Donegani, Via Maritimo 26, 20097 San Donato, Milano, Italy.

P.E. Ege, Institute of Technology, Dept. of Chemistry and Chemical Engineering, Laboratory of Chemical Engineering, NTH-Norwegian, 7034 Trondheim Norway.

H. Farag, The University of Western Ontario, Faculty of Eng. Science, London, Ontario, N6A 5B9.

J.L. Figueiredo, Universidade do Porto, Departamento de Engenharia Quimica, Faculdade de Engenharia, 4099 Porto-Portugal.

P. Galtier, Institut Fran~ais du Petrole, Centre D'Etudes et de Developpement Industriels, CEDI, P.O.B. 3, 69390 Vernaison, France.

A. Gervais, ENSIC, 1 rue de grandville, 54042 Nancy Cedex, France.

G. Harting, Exxon Product Research Division, Linden N.J., USA.

J.A.G. Justino, Instituto Superior Tecnico, Centro de Quimica Estrurural, Complexo Interdisciplinar, 1096 Lisboa - Codex, Portugal.

A. Jutan, The University of Western Ontario, Faculty of Eng. Science, London, Ontario, N6A 5B9.

K. Kinnari, STATOIL, Staff Engineer, P.O.Box 300, Stavanger, Norway.

T. Kopac, H.U.Z.M.F. Mak. Muh. Bol., 67100 Zonguldak, Turkey.

N. Kosaric, The University of Western Ontario, Faculty of Eng. Science, London, Ontario, N6A 5B9.

D. Kraemer, Imperial Oil Research, P.O.Box 3022, Sarnia, Ontario, N7T 7Ml.

Q.N. Le, Mobil Research and Development Corporation, Paulsboro Research Laboratory, Paulsboro, New Jersey, 08066-0480.

J.M. Ie Blevec, Atochem, Centre Technique de Lyon, Chemin de la Lone, B.P. 32, 69310 Pierre-Benite, France.

T. Ie Prince, ELF Petroleum, LACQ, Pyrennes-Atlantiques, Boite Postale 34, 64170 ARTIX, France.

J.J. Lerou, DuPont, Central Research and Development, Experimental Station 262/331, P.O.Box 80262, Wilmington, Delaware 19880-0262.

M. Lysberg, Norwegian Institute of Technology, SINTEF Applied Chemistry, N-7034 Trondheim, Norway.

A. Martin, Memorial University, Dept. of Biochemistry, St. John's Newfoundland, AlB 3X9.

xvii

O. Marroquin, Instituto Mexicano del Petroleo, Direccion Investigacion Aplicada, Processes. Eje Central Lazaro Cardents 152, Mexico 07730

I. Mazzarino, Politecnico di Torino, Dip. Scienza dei Mat e Ing. Chimica, C. Duca Degliabruzzi 24, 10129 Torino, Italy.

B. Nelson, The University of Western Ontario, Faculty of Eng. Science, London, Ontario, N6A 5B9.

O. Nore, Rhone Poulenc, Centre de Decines, 24 Av. Jean-Jaures BP 166, 69151 Decines­Carpieu Cedex France

G. Olmez, Gazi University, Faculty of Engineering and Architecture, Chemical Engineering Department, Maltepe, Ankara 06570, Turkey.

G. Ozkhan, Gazi University, Faculty of Engineering and Architecture, Chemical Engineering Department, Maitepe, Ankara 06570, Turkey.

A. Pekediz, Gazi University, Faculty of Engineering and Architecture, Chemical Engineering Department, Maltepe, Ankara 06570, Turkey.

A. Ravella, Imperial Oil Research, P.O.Box 3022, Sarnia, Ontario, N7T 7Ml.

D. Rojas, Instituto Venezolano del Petrol eo (INTEVEP), Santa Rosa, Los Teques, Venezuela.

Y. Roques, Institut Fran~ais du Petrole, Centre D'Etudes et de Developpement Industriels, CEDI, P.O.B. 3, 69390 Vernaison, France.

A. Sapre, Mobil Research and Development Corporation, Engineering Department, Pennington, NJ, 08534-0188.

U. Sedran, INCAPE, Instituto de Catalisis y Petroquimica, Santa Fe, Argentina

C. Serpa, Instituto Venezolano del Petrol eo (INTEVEP), Santa Rosa, Los Teques, Venezuela.

H. Shannon, Exxon Product Research Division, Linden N.J., USA.

J. Shen, Instituto of Chemical Metallurgy, Academia Sinica, Beijing, China.

F. Simard, Chevron Research Co., P.O.Box 1627, Richmond CA, USA.

R. Soares, Universidade do Porto, Departamento de Engenharia Quimica, Faculdade de Engenharia, Rua dos Bragas, 4099 Porto Codex, Portugal.

A. Soria Lopez, Universidad Autonoma Metropolitana, Chemical Eng. Department, Mexico

J. Turner, Washington University in St. Louis, Chemical Engineering Department, Campus Box 1198, St. Louis, Mo 63130.

J. Valladares, The University of Western Ontario, Faculty of Eng. Science, London, Ontario, N6A 5B9.

M. Verwaerde, Institut Fran~ais du Petrole, Centre D'Etudes et de Developpement Industriels, CEDI, P.O.B. 3, 69390 Vernaison, France

R. Weimer, Air Products & Chemicals Inc., 7201 Hamilton Blvd., Allentown, PA 18195

Q.N. Zhou, The University of Western Ontario, Faculty of Eng. Science, London, Ontario, N6A 5B9.

xviii

Organizing Advisory Committee

Professor F. Berruti University of Calgary, Canada

Professor J. Grace University of British Columbia, Canada

Dr. A. Sapre Mobil Research and Development Corporation, USA

Local Committee

s. Afara, The University of Western Ontario, FacuIty of Eng. Science, London, Ontario, N6A 5B9.

A. Blasetti, Universidad de La Patagonia, Facultad de Ingenieria, Comodoro Rivadavia, Argentina.

J. Chabot, The University of Western Ontario, FacuIty of Eng. Science, London, Ontario, N6A 5B9.

H. Farag, The University of Western Ontario, FacuIty of Eng. Science, London, Ontario, N6A 5B9.

B. Nelson, The University of Western Ontario, Faculty of Eng. Science, London, Ontario, N6A 5B9.

A. Pekediz, Gazi University, Faculty of Engineering and Architecture, Chemical Engineering Department, MaItepe, Ankara 06570, Turkey.

J. Valladares, The University of Western Ontario, FacuIty of Eng. Science, London, Ontario, N6A 5B9.

Q.N. Zhou, The University of Western Ontario, Faculty of Eng. Science, London, Ontario, N6A 5B9.