Chemical Reactor Technology For Environmentally Safe Reactors and Products

Chemical Reactor Technology
for Environmentally Safe Reactors and Products

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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+BUSINES
SMEDIA, B.V
Proceedings of the NATO Advanced Study Institute on
Chemical Reactor Technology for Environmentally Safe Reactors and Products
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 a n 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. D o g u , A . R a v e l l a .
p. cm. — (NAT O A S 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 index .
ISBN 978-94-010-5219-1 ISBN 978-94-011-2747-9 (eBook)
DOI 10.1007/978-94-011-2747-9
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 aspects . I . DeL 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 .
T P 1 5 7 . C 4 18 1 9 9 2
660'.283—dc2 0 92-3659 1
ISBN 978-94-010-5219-1
Printed on acid-free paper
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© 1992Springer-Science+Business Media Dordrecht
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No part of the material protected by this copyright notice may be reproduced or
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permission from the copyright owner.
Table of Contents
Hugo I. de Lasa
Preface ix
I. Fuels of the Future and Changing Fuel Needs
A. Ravella
How Should Environmentally Benign Gasolines be Formulated? 1
G.L. Haning, H. Shannon
Oxygenates as Gasoline Blending Components 7
D. King
Engineering of Fluidized Catalytic Crackers 17
A. W. Peters, W-C Cheng, T. G. Roberie

Scientific Aspects of Novel Catalysts for FCC 51
H. de Lasa, D. Kraemer
Novel Techniques for FCC Catalyst Selection and 71
Kinetic Modelling
A. Pekediz, D. W. Kraemer, J. Chabot, H.!. de Lasa

Mixing Patterns in a Novel Riser Simulator 133
P.H. Schipper, A. V. Sapre, Q.N. Le

Chemical Aspects of Clean Fuels Production 147
II. Alternative Sources
J.e. w.
Kuo
Evaluation of Direct Methane Conversion Processes 183
vi
M.M. G. Senden, S. T. Sie, M.F.M. Post, J. Ansorge

Engineering Aspects of the Conversion of Natural Gas 227
Into Middle Distillates
J. Rostrup-Nielsen, I. Dybkjaer, L.J. Christiansen

Steam Reforming Opportunities and Limits of the Technology 249
M. Baerns
Oxidative Coupling of Methane for the Utilization of 283
Natural Gas
O. Altin, I. anal, T. Dogu, J.B. Butt

Dysprosium Oxide for Oxidative Coupling of Methane 317
F. Berruti, L.A. Behie

Ultrapyrolysis of Heavy Oils: Reaction Kinetics and 325
Reactor Technology
M.P. Dudukovic, N. Devanathan

Bubble Column Reactors: Some Recent Developments 353
F. Berruti, R. Wong
Strategies for Low Emissions From Circulating 379
Fluidized Bed Boilers
G.F. Froment
Kinetic Modelling of Complex Processes. Thermal Cracking 409
and Catalytic Hydrocracking
P. Trambouze
Engineering of Hydrotreating Processes 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
vii
C. Brereton, J.R. Grace, C.J. Lim, J. Zhu

Engineering Aspects of Recirculating Fluidised Bed Combustion 507
B.P.A. Grandjean, J. Chaouki
Application of a Monte Carlo Method to the Solid Flow Pattern 537
Visualization in CFB
J.P. Leclerc, D. Schweich

Modeling Catalytic Monoliths for Automobile Emission Control 547
E. Pelizzetti, C. Minero, E. Pramauro
Photocatalytic Processes for Destruction of Organic Water 577
Contaminants
I. Poulios, A. Avranas
Heterogeneous Photocatalytic Degradation of the Cationic 609
Surfactants Cetyldimethylbenzylammonium Chloride
and Cetylpyridinium Chloride
J.J. Lerou, L.E. Manzer

Progress in the Development of Chlorofluorcarbon 617
(CFC) Alternatives
Index 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

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 3A7.
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,
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 Decines-
Carpieu Cedex France
G. Olmez, Gazi University, Faculty of Engineering and Architecture, Chemical
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
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,
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.
HOW SHOULD ENVIRONMENTALLY BENIGN GASOLINES BE FORMULATED?
A.RAVELLA
Imperial Oil Ltd. - Products Division - Research Department
P. O. Box 3022
Sarnia, Ontario, N7T 7M1, Canada.
ABSTRACT. This contribution, presented as an introduction to a Panel Discussion of the NATO-Asi

meeting, highlights some of the most important subjects concerning gasoline formulation. It is by no means
exhaustive, as it is intended to just briefly introduce a few key points of interest such as: product quality
and its impact on emissions (volatility, oxygenates), additives, need for processing changes and alternative
fuels.
1. Introduction
Environmental considerations have become by far the most substantial drive in product
reformulation for transportation fuels. The late 80s and early 90s have shown an ever-increasing
trend in public awareness and concern over environmental issues. Governments and regulatory
agencies allover the world have by now been sensitized to these issues and are taking legislative
steps that affect rather profoundly the refining industry. Regulations, aimed at reducing the
impact of transportation fuels on the ecosystem and especially on human health, are being
promulgated throughout the Western Countries almost on a continuous basis.
Meeting the challenge posed by these regulations will require a great deal of the two
most-precious resources, time and money. There is no doubt that most of the requirements
technically could be met, the real question is to what extent our economies could afford to do it
(Tallett and Dunbar, 1990). For example, pure Hydrogen would be an ideal fuel due to its
perfectly clean combustion reaction. As we all know, a Hydrogen-powered transportation fleet
is all but unthinkable: cars are not presently equipped to store and burn it, the distribution
facilities do not exist. Not to mention that the energy requirement to produce the massive
amounts needed for global transportation, would probably outbalance several times the benefits
acquired by using Hydrogen.
The end result? Maintaining transportation fuels quality in the 1990s is quickly becoming a
delicate balancing act between the various regulating agencies and the economic realities of the
petroleum refining industry (Unzelman, 1990).
2. Product Quality and its impact on emissions
Correlation of gasoline physical properties and their impact on human health, air quality and the
environment, is the issue of greatest relevance for the definition of proper quality standards which
could really affect the end result of the legislation. Unfortunately, in spite of the great deal of
H.I. de Lasa et al. (eds.). Chemical Reactor Technology for Environmentally Safe Reactors and Products. 1-6.
© 1993 Kluwer Academic Publis/;,·n.
2
work in this area, it is still difficult to establish, beyond doubt, relationships of cause and effect
between all the variables.
Smylie et al., (1991), reviewed the impact on air quality of gasoline reformulation efforts.
These gasolines would usually differ from "conventional" fuels in at least three features: lower
volatility, presence of an oxygenate and lower aromatics. Other quality considerations, such as
toxic or air-toxic content, (e.g. lead, benzene, etc.) also come into play for a variety of other
effects.
2.1. VOLATILITY
Gasoline volatility is usually expressed in terms of Reid Vapor Pressure (RVP) , which is the
fuel's vapor pressure at 37.7 °C (100 OF). Smylie et al., (1991) presented very interesting data
showing that reductions in RVP determine corresponding reductions in evaporative and running
losses, but have little or no effect on exhaust and refuelling losses. Also, RVP reductions below
8 psi seem to have very little incremental effect on overall emissions. The impact of reduced
volatility on emissions and air quality can be better understood from the indices of atmospheric
reactivity of various blending components. Some of these data, presented by Unzelman, (1990)
and Smylie et al., (1991), are reported in Table 1.
Probably the most visible impact of volatility legislation on refinery operations has been to find
and maintain a butane balance in the refinery. Conversely, the challenge from a product quality
standpoint, is to maintain cold-start capabilities of the fuel at the lower RVP (NPRA, 1990).
2.1. OXYGENATES
The use of oxygenates, alcohols and ethers, in reformulated gasoline, is due to a combination of
good burning characteristics (high octane number), low vapor pressure, and lower atmospheric
reactivity than aromatics. The advantage of ethers over alcohols is their lower blending RVP.
From an air quality standpoint, oxygenates control CO and unburned hydrocarbons (HC)
emissions, tailpipe emissions. Ethers and alcohols are also well compatible with fuels systems
and can be handled fairly easily in the present distribution facilities.
Piel, (1989), presented data showing that the optimum oxygen content for emissions control is
about 2 wt% oxygen in the fuel. This reduction is mainly obtained by backing-out aromatics,
which are deemed to be strong contributors to ozone pollution. High aromatic contents are also
the cause of NOx emissions, because of their high combustion temperature due to their Carbon
content. Heats of combustion of MTBE, ETBE and TAME are about 109, 117 and 112
BTU/gal, respectively, versus a typical value of 125 BTU/gal for blended gasoline.
Table 2 reports octane values for various gasoline components, including oxygenates.
3. Additives
A wide variety of additives is available to refiners to improve gasoline quality, including octane
number. Although lead has been banned in most western Countries, other octane-enhancers like
MMT (Methyl-Cyclopentadienyl Manganese Tri-carbonyl) are widely used. Gibbs, (1989),
presents a review of the various types of additives currently employed. Oxidation inhibitors and
metal deactivators are normally added in the refinery or processing plant to prevent oxidation and
gum formation. Dyes for product identification and antiknock compounds can be added prior
3
Table 1. Reactivity and Vapor Pressure of Gasoline Blending

Components.
COMPOUND Atmospheric Reactivity (2) Blending RVP (3)

reactivity (I) Illii
Propene 6.6
n-butane 2.7 0.5 60
Isopentane 3.6 21
n-pentane 5.0 16
Isohexane 5.0 7
n-hexane 5.6 5
Octane 0.8
Benzene 1.3 0.1 3
Toluene 6.4 1.3 0.5
m-xylene 23.0 6.2 0.3
Trimethyl-benzene 10.4
Butene-l 30.0 65
Butene-2 65.0 50
Pentenc-l 30.0 16
2-methyl,2-butene 85.0 15
2-methyl, I-butene 70.0 19
Methanol 1.0 60
Ethanol 3.4 18
MTBE 2.6 9
ETBE 8.1 3-5
TAME 7.9 1-2
(l)Gas-phase reaction rate with the hydroxyl radical (Unzelman, 1990)

(2)Reactivity, g Ozone/g emitted (Smylie et aI., 1991)
(3)(Unzelman, 1990)
Table 2. Octane Rating of Aromatics and Oxygenates.
Compound RON MON (RON + MONl/2
Benzene 106 88 97
Toluene 114 93 103.5
p-Xy1ene 120 98 109
m-Xylene 120 99 109.5
o-Xylene 105 87 96
Ethylbenzene 114 91 102.5
C9 Aromatics 117 98 107.5
C 10 Aromatics 110 92 101
Methanol 133 99 116
Ethanol 130 96 113
MTBE 118 100 109
ETBE 118 102 110
TAME 111 98 104.5
4
to storage in tankage. Corrosion inhibitors may be required if the products are shipped via
pipeline. Carburetor or injection system detergents and deposit-control agents are normally
blended before final delivery.
4. Need for Processing changes
Environmentally driven fuel quality modifications, particularly in the gasoline pool, will require
refiners to play more of the 'Blending Game' (Kingsbury and Vadori, 1990) but also to modify
existing production facilities as well as install new processes.
A recent paper by Wilson et al. (1991) reviews feasible processing options available to improve
the environmental quality of gasoline and distillate fuels. Dosher (1990), forecasts large
construction efforts as the result of pending regulations, but little or no overcapacity as a result
of this growth.
The growing demand for higher and better performance from existing equipment is stimulating
the catalyst vendors, that are marketing new generations of cracking, hydrotreating and reforming
catalysts. Catalyst developments go hand in hand with new processing strategies, which may
require installing grassroot facilities. The strategy of choice has to fit the plant and its location.
Obviously, a common solution to the problem of balancing the gasoline pool is not available, and
most refiners are hard pressed to find the one that suits their case the best.
Some examples of these considerations, taken from the most recent contributions in this topic,
can be found papers by Akzo (e.g. Humphries et a\., 1991; Desai and Haseltine, \989), UOP
(Weiszmann et al., 1986) and BP (pritchard, 1987). Yatsu and Keyworth, (\990), of Akzo,
provide a good example of the work that is going on in the matter of property prediction from
analytical tests.
5. Alternative Fuels
Although a bit aside from the main element of the present discussion, alternative fuels are worth
mentioning because they frequently reappear in the plans for environmentally friendly fuels as
potentially viable options. Methanol is losing ground, in these days, because of its toxicity and
volatility. Electricity, natural gas and hydrogen are however still being considered by
environmental groups because of their advertised low pollution effects. De Luchi et aI., (1989),
present very interesting data on the greenhouse effect impact of these alternatives, and the
interesting conclusion is that some of these apparently innocuous sources of energy would actually
be worse than the present fuels, due to the level of pollution involved in their production.
A detailed description of alternative fuels and their environmental impact is given by Ecklund
and Mills, (1989) and Mills and Ecklund, (1989).
A pro-Methanol stand is taken by Gray and Alson, (1989). They base their findings on
automotive emissions and their impact on the environment, specifically air. This is in conflict
with the findings of De Luchi et a\., (1989), apparently because the production process was not
very well accounted for as a source of pollution. De Luchi et a\., (1989) showed that the overall
effect of production and combustion for automotive purposes of methanol from coal would
actually almost double the emissions of greenhouse gases, while at best the use of methanol
produced from natural gas could reduce emissions by 3 %. They concluded, after studying
several types of alternative fuels, that the only way to accomplish substantial long-term reductions
in CO2-equivalent emissions from the transportation sector is greatly increased efficiency.
5
6. Conclusions
The present discussion has barely touched upon some of the issues the refining and distribution
industry is facing. The only certainty seems to be the fact that substantial changes are facing the
way fuels are being manufactured, delivered and sold. If this situation puts refiners in the
difficult position of having to cope with this rapid rate of change, it can be said that at least it
provides a strong reason for research, development and commercial improvement. The example
of the several catalyst developments in recent years, driven by environmental regulations, proves
that the need for different technology served as a springboard for development.
The regulations being imposed on product quality are based, or should be, on the available
scientific information concerning the environmental impact of pollution and health effects.
Sometimes this knowledge is not as profound as it should be, in order to fully understand causes
and effects of the compounds that are being legislated. The refining industry can really playa
dual role in improving air quality: by meeting the product quality specifications set by the
regulating agencies, but also by collaborating with the regulating agencies in setting those
standards. This collaboration is the only way to ensure that the agreed-upon standards are set
at target levels which can realistically be met.
Because of the relatively small and controversial database of scientific information on the
environmental impact of hydrocarbon compounds, the present contribution probably addressess
the question of 'How environmentally friendly gasoline is going to be formulated', meaning
'What can refineries realistically do in the near future?' rather than 'how should it be
formulated?'
Acknowledgements
Dr. B. Umesh Achia of Imperial Oil Ltd., Product Division - Research Department -provided
much appreciated information and guidance.
REFERENCES
De Luchi, M.A., Johnston, R.A., and Sperling, D., (1989), 'Transportation Fuels and the
Greenhouse Effect', from Transportation Research Record, (1989). Also, Research Report
UER-182, University Energy Research Group, University of California, Berkeley, December
1987.
Desai, P.H., and Haseltine, R.P., (1989), 'Advanced FCC Catalyst Formulations Can Be Used
to Boost Octane Number of Gasoline', Oil & Gas J., October 23, 1989,68-76.
Dosher, J.R., 'Outlook for the U.S. Refining Industry', (1990), Paper AM-90-06, presented at
the 1990 NPRA Annual Meeting, March 25-27, 1990, Convention Center, San Antonio, Texas.
Ecklund, E.E., and Mills, G.A., 'Alternative Fuels: Progress and Prospect - Part 1', (1989),
CHEMTEC, September 1989,549-556
Gibbs, L.M., 'Additives Boost Gasoline Quality', (1989), Oil & Gas 1., April 24, 1989,60-63.
Gray, C.L., and Alson, J.A., (1989), 'The Case for Methanol', Scientific American, November
1989, 108-114.
Humphries, A., Yanik, S.J., Gerritsen, L.A., O'Connor, P.O., Desai. P.R., (1991), 'Catalyst
Helps Reformulation', Hydrocarbon Processing, April 1991,69-72.
6
Mills, G.A., and Ecklund, E.E., 'Alternative Fuels: Progress and Prospect - Part 2', (1989),
CHEMTEC, October 1989, 626-631.
National Petroleum Refiners Association (NPRA) Annual Meeting, (1989), Question and Answer
period, , 1900s Fuel Specifications will require process changes', in Oil and Gas J., February
26, 1990, 83-87.
Pritchard, (1987), 'Novel Catalyst Widens Octane Opportunities', Paper AM-87-48, presented
at the 1987 NPRA Annual Meeting, March 29-31, 1987, Convention Center, San Antonio,
Texas.
Smylie, M., Chinkin, L.R., and Whitten, G .Z., 'Assessing the Effects of Reformulated Gasoline
on Air Quality' (1991), Paper AM-91-21, presented at the 1991 NPRA Annual Meeting,
March 17-19, 1991, Convention Center, San Antonio, Texas.
Kingsbury, E., and Vadori, L., 'The Refinery of the Future', paper presented at the seminar on
'Transportation Fuels and the Environmental Challenges', Toronto, Prince Hotel, November
8, 1990.
Tallet, M.R., and Dunbar, D.N., 'Impact of Green Gasoline', (1990), Petroleum Economist,
April 1990, 126-128.
Unzelman, G .H., 'Reformulated Gasolines Will Challenge Product-Quality Maintenance' ,(1990),
Oil & Gas J., April 9, 1990, 43-48.
Unzelman, G.H., 'Options to Meet 1990s Fuels Composition Rules Limited', (1990), Oil & Gas
J., April 23, 1990,91-93.
Weiszmann, J.A., D'Auria, J.H., McWilliams, F.G. and Hibbs, F.M., (1986), 'Pick your Option
for Higher Octane', Hydrocarbon Processing, June 1986, 41-45.
Wilson, J.W., Keyworth, D.A., and Gilman, R., 'Catalyst and Processing Options for Cleaner
Gasoline' (1991), Paper AM-91-33, presented at the 1991 NPRA Annual Meeting, March
17-19, 1991, Convention Center, San Antonio, Texas.
Yatsu, C.A., and Keyworth, D.A., (1990), 'Modified MAT and GC Help Predict FCC Gasoline
Quality', Oil & Gas J., March 26, 1990,64-70.
OXYGENATES AS GASOLINE BLENDING COMPONENTS
G.L. HARTING, HUGH SHANNON

Exxon Research and Engineering Company
P.O. Box 51
Linden, NJ 07036
ABSTRACT. Oxygenate fuel components are currently receiving renewed attention given their importance
as a potential solution for the manufacture of fuels that lower automotive emissions. This paper addresses
various relevant issues concerning this topic as follows: oxygenates for fuel blending, emission impact of
oxygenates and oxygenate manufacture.
1. Introduction
While the use of oxygenated compounds as fuel components has long been considered, interest
in this concept was accelerated by the energy shortages experienced in the mid-1970's. The
heavy reliance by many countries on imported petroleum crude oil and the vulnerability of its
supply engendered the exploration of alternative sources for transportation fuel. Coincident with
these shortages, the significant rise in crude oil prices (and the corresponding price of petroleum
fuel made from crude) caused severe balance of payment disruptions for many countries, again
prompting the search for alternative fuel components, including oxygenates.
In the early 1980's, as demand for unleaded gasoline grew, oxygenated fuel components
received renewed attention. Their combustion properties, as will be shown later, allow them to
suppress the undesirable phenomenon known as engine knock. Lead-containing additives had
traditionally played this role, and, with their use being restricted or eliminated by regulation or
law, the use of oxygenates as gasoline blend components grew.
More recently oxygenated fuel components have been found to have a beneficial effect on air
quality. As public interest in environmental issues has grown, legislators and regulators are
seeking various routes to improve air qUality. As will be shown later, oxygenates could playa
role in lowering automotive emissions.
2. Oxygenates for Fuel Blending
Two classes of oxygenates are of primary interest as fuel blending components, alcohols and
ethers. The alcohols include methanol, ethanol, tertiary butyl alcohol, and blends such as a 50150
mixture of methanol and tertiary butyl alcohol. Methyl tertiary butyl ether (MTBE) is the most
widely used ether, although recently ethyl tertiary butyl ether (ETBE) and tertiary amyl methyl
either (TAME) are being increasingly considered.
Many factors must be weighed by a fuel supplier as he tries to decide which, if any, oxygenate
should be used in blending his gasoline product. These include the impact oxygenates have on
7
H.I. de Lasa et al. (eds.), Chemical Reactor Technology for Environmentally Safe Reactors and Products, 7-15.
© 1993 Kluwer Academic Publishers.
8
other parameters of fuel performance, environmental credits associated with the use of
oxygenates, regulatory requirements associated with these credits, and availability and cost. This
paper will review the first three of these seen in Figure 1. Here Reid Vapor Pressure is plotted
vs. oxygenate concentration for several alcohols and MTBE. Methanol, which pure had a vapor
pressure far lower than that of gasoline, causes a significant increase in vapor pressure when
blended into gasoline (over 3 psi). This is due to the fact that neat methanol is strongly hydrogen
bonded which suppresses its volatility, but in low concentrations in a non-polar medium such as
gasoline, these hydrogen bonds are broken. Methanol in the blend thus behaves more as one
would expect for a lower molecular weight liquid and is highly volatile. This effect is partially
mitigated by using methanol as a 50150 mixture with tertiary butyl alcohol, but its effect on Reid
Vapor Pressure is still large.
13r------.-------,-------,-------,------,
12
.,--
Methanol _ _
e _ _ e---';';e
.
Q."
>
0::_ 11
-g!.
II
in
10 o~ Ethanol
- - 0_ _ 0
.-'--<>-----_.------..III. ____
.----11. ... - ........ 6 ... __ <6• • ___ ..6
TBA
MTBe --"I
80L-----~5-------1LO-------1L5-------~L-----~
Volume "10 Oxygenate In Indolene
Data Source: (API, 1988).
Figure 1. Effect of Oxygenates on Blend Vapor Pressure
Ethanol behaves similarly but to a lesser degree. In spite of its low vapor pressure neat,
ethanol also boosts volatility by about 1 psi when used in the 5 to 15 % range. Tertiary butyl
alcohol, being of higher molecular weight, has little effect on RVP.
Ethers, such as MTBE, have neat vapor pressures only slightly below that of gasoline.
However, they are not as heavily hydrogen bonded as are the alcohols, hence have little impact
on blend vapor pressures.
Another important property of a fuel component is its octane value. Octane is an empirical
measure of the ability of a fuel to resist engine knock. It is measured in an engine, using one
of two sets of operating conditions, and is compared on a relative scale to the performance of
9
n-heptane (0 octane) and 2,2,4 trimethylpentane or isooctane (100 octane). One of the two
conditions for the engine yields the Research Octane Number (RON) and the other gives the
Motor Octane Number (MON). In the U.S., one also considers the arithmetic average of these
two values, known as (R + M)/2, which is the octane value posted at service stations.
Table 2 lists the octane values of various oxygenates as measured by their ability to contribute
octane when blended with gasoline. It can be seen that all of these oxygenates have high octane
values, higher than the 91-94 (R + M)/2 found even in premium grade gasolines. While methanol
has the highest blending octane value, it is most often used in conjunction with t-butyl alcohol,
and this results in a sightly lower, but still impressive, octane value. It was these high octane
values which stimulated interest in oxygenates as unleaded gasoline blend components in the early
1980's.
Table 2. Oxygenate Octane Values
(R+M)/2
Gasoline (premium Unleaded) 91-94

Methanol 116
Ethanol 113
t-Butyl Alcohol 100
Methanol + TBA 107
MTBE 110
ETBE 111
TAME 105
Data Sources: API, 19~8 and Piel,W.J., lY8Y.
Water tolerance is another important parameter to be measured for gasoline/oxygenate blends.

Water is present in most fuel distribution systems to varying degrees, accumulating in terminal
tanks and in the underground storage tanks at service stations. This water is normally harmless,
settling to the bottom of the tanks where it is periodically drawn off and properly disposed of.
Gasoline-alcohol blends have been found to experience phase separation when they come in
contact with relatively low concentrations of water. This is because hydrogen bonds are formed
between the water and alcohol molecules, and this polar mixture is no longer soluble in gasoline,
which leads to phase separation. Thus, a hydrocarbon-rich upper phase is formed, with the lower
phase consisting primarily of water, alcohol, and small amounts of aromatic hydrocarbons.
In Figure 2, the amount of water, in parts per million, necessary to cause phase separation is
plotted vs. temperature. Methanol again shows its highly polar character separating at less than
1000 ppm water. This effect is partially mitigated by admixing the methanol with t-butyl alcohol.
Ethanol also demonstrates phase separation in the 4,000 to 5,000 ppm range.
Ethers such as MTBE have little affinity for water and do not separate under these conditions.
This reduced affinity for water is illustrated by the fact that MTBE is less than 5% soluble in
water whereas low molecular weight alcohols are 100% soluble.
Oxygenates can also affect elastomers which are commonly found in the seals, lines, and other
parts of vehicle fuel systems. Table 3 shows the swelling performance of gasoline and 10%
blends of oxygenates in gasoline with a variety of elastomeric compounds. One would like to
see the gasoline/oxygenate blend have the same swelling performance as gasoline alone, so that
when fuel is switched from gasoline to a blend, the elastomer neither shrinks (causing leakage,
embrittlement, etc.) nor swells (causing weakening, etc.). It can be seen that the use of MTBE
meets these criteria, but alcohols, especially methanol, contribute to different swelling
IO
performance (e.g., with polyester urethane and ethylene-propylene-diene polymer). This can be
overcome, especially for ethanol, by specially selecting elastomers for use in a car which are
equally compatible with gasoline and alcohol, but it could still be a problem with older cars that
were not designed to be alcohol compatible.
sooo
2.75 Volume % Methanol

2.75 Volume % Gasolln~rade
~
~$'OVOIIJry",
" Afe/h1J1)0i'"
• 37 Volume % Aromatics Base Fuel
+70 +32 +20 0 ·20
Temperature, 'F
Figure 2. Water Tolerance of Gasoline-Alcohol Blends
Table 3. Elastomer Swelling Due to Oxygenates.
Volume Swell, %
Elastomer Gasoline Methanol(l) Ethanol(l) MTBE(I)
Fluorocarbon 0 27 3 2
Polyester Urethane 11 42 37 13
Flurosilicone 14 21 18 --
Butadiene-acrylonitrile 34 53 51 34
Polyacrylate 44 112 136 --
Chlorosulfonated Polyethylene 49 41 56 48
Ethylene-propylene-diene polymer 137 109 124 138
Natural Rubber 169 143 176 --
(1) Tested as 10% blends With gasolme
11
3. Emission Impact Of Oxygenates
Automotive equipment emits many chemical species which directly or indirectly can impact on
air quality. These emissions are directly evaporated from the fuel as it is loaded onto a vehicle,
as it experiences diurnal temperature cycles in the fuel tank of the vehicle, and as it is heated due
to operation of the vehicle. Other emissions enter the atmosphere via the tailpipe after the fuel
has been combusted in the engine. These latter emissions may be further modified by passing
them over a catalytic converter which is specifically designed to oxidize unburned hydrocarbons
and carbon monoxide and to reduce nitrogen oxides.
The three types of emissions from automotive sources that are of primary concern are unburned
hydrocarbons (from either evaporation or the tailpipe), carbon monoxide (CO) and nitrogen
oxides (NOJ. The latter two are tailpipe emissions only. Most hydrocarbons and NOx are not
of concern directly, but they do react with oxygen in the atmosphere under intense sunlight to
form ozone, the basic ingredient of urban smog. CO is, of course, directly harmful to human
health and is of direct concern.
Evaporative emissions are a function of fuel volatility. Recently, a model for estimating the
impact of various factors on evaporative emissions was published (Kishan,S., 1988). In this
model, Reid vapor Pressure is one of the determinants of emissions via an exponential term,
ea *(RAP-9.0). Using this model, the use of oxygenates which increase Reid Vapor Pressure, such
as alcohols, would be expected to increase evaporative emissions, whereas the ethers which do
not significantly affect RVP would not.
With regard to tailpipe emissions, it has been speculated that oxygenates could lower the levels
of emitted unburned hydrocarbons and CO. In effect, the oxygen content of the oxygenated
blend component could cause the combustion event to occur at a slightly higher air-to-fuel ratio
resulting in more complete hydrocarbon burning. These leaner conditions would thus lead to
lower burning hydrocarbon and CO emissions. However, moving the engine's operation to the
lean side of stoichiometric could also increase the production of NO.. as illustrated in Figure 3.
Emissions
-~T
Nitrogen O,ide.
Lean
0ec"'~f-8~
..-----MIx1ure Strength--- Inc,';sse
Figure 3. Effect Of Air/Fuel Ratio On Emissions.

12
Some data has been recently generated on the actual effect of oxygenates on tailpipe emissions
as part of a cooperative program between the petroleum and automotive industries (AQIRP,
1990). In this program, the effect of the inclusion of 15% MTBE was measured along with an
assessment of the impact of other fuel composition variables. In Table 4, the MTBE results are
shown for the two test fleets employed. One of these fleets consisted of 10 different 1989 vehicle
models and the other 7 models of 1983 to 1985 vintage.
Table 4. MTBE Effect On Tailpipe Emissions.
Emissions Effect. %(1)
l
He CO NOx
Current Fleet -5.1 -11.2 Not Significant

Older Fleet -7.3 -13.0 Not Significant
( ) Chan ge in moving from u to 15% MTBE; measur ed
under Federal Test Procedure conditions, e.g., 75°F.
Data Source: (AQIRP, 1990).
In both fleets the inclusion of 15% MTBE lowered hydrocarbon and CO tailpipe emissions vs.
a 0% MTBE base case. The NO, emissions were not different to a statistically significant degree
except in fuels with low aromatics contents in the current fleet. This suggests that the model
above is reasonable, and the NO, effect, if present, was too small to be statistically discernible
in a test program of this size. Further tests are underway to evaluate the effects attributable to
ethanol and ETBE as blending components.
A similar program measured the effect of fuel oxygen content on CO emissions at low
temperature (Most,W.J., 1989). Since CO is the result of incomplete combustion and does not
require intense sunlight to be a concern, CO emissions are most often an air quality problem
during the cold winter months. In this testing, 12 1983 to 1988 model year cars were tested (half
of them having the advanced adoptive learning engine control systems), and 4 1979 to 1980
model year cars were also included.
The base fuel used was a 13 psi (90 k Pa) wintergrade gasoline. It was either blended with
11 % MTBE (2.0% oxygen) or 10% ethanol (3.9% oxygen) to test the effect of oxygenates. The
results obtained at 35°F (1.7°C) and at an altitude of 5,000 feet (1,700 meters) are shown in
Figure 4. These conditions created the maximum level of CO emissions in the test program.
<0 ~---~----~,-----~----
35 FISK FT
~OdoIY."
~ 30 """""'---~-----_-..l
{ 20 __ ~ ________ -I_
! 1983· 8'9 Modol Year w/o Adapllve Learning
810
1~· 89 Mooel Year with Adaptive learn.~lng,--_ _ _~
Oxygen COOlent, "
Data Source: (Most,W.J., 1989).
Figure 4. CO Emissions vs. Fuel Oxygen.

13
It can be seen that the inclusion of oxygenates does decrease CO emissions, but only in older
cars. For the 1983 to 1988 models, there is little area effect on CO emissions when tested under
these conditions.
Superimposed on these measured emissions effects are regulatory or legislative requirements
which may mandate the use of oxygenates in motor gasoline. Probably the most pervasive of
these requirements are embodied in the Clean air Act Amendments passed into law in the U.S.
in late 1990. These amendments will require the use of oxygenates in fuel to the extent of
providing a minimum oxygen content in the fuel of 2.0% when that fuel is sold in the summer
months in areas of the country with the worst ambient ozone problems. It also requires the use
of gasoline containing a minimum of2.7% oxygen in the winter months in areas having ambient
CO emissions problems. The type of oxygenate to be employed is not specified.
4. Oxygenate Manufacture
Clearly, with the use of oxygenates spreading as a means of combatting air pollution, the supply
of additional volumes of these components has assumed added importance. Most of the interest
in added oxygenate capacity seems to be centered on ethanol and the various ethers.
Ethanol is primarily produced by the fermentation of agricultural starches or sugars. The
simplified flow chart for ethanol manufacture is shown in Figure 5. If starting from grain or
another natural starch, the product must first be milled, and converted by enzymes into sugars.
These converted sugars, or alternatively natural sugars, are then fermented to yield ethanol. The
ethanol is then separated by distillation and dried before blending with a fuel. The water
tolerance characteristics of ethanol noted above generally limit its use to terminal blending just
before trans-shipment to a service station.
Figure 5. Ethanol Production Process - Simplified Diagram
The ethers are manufactured by combining iso-olefins with alcohols. If the iso-olefin is iso-
butylene and the alcohol is methanol, the resultant ether is methyl tertiary butyl ether (MTBE).
If the olefin is iso-amylene, one makes tertiary amyl methyl ether (TAME), and switching the
alcohol to ethanol yields ethyl tertiary butyl ether (ETBE).
14
CH2 CH3
"
I
CH3C-CH3 + CH30H .... CH3-C-O-CH3
I
CH3
Iso-Butylene Methanol MTBE
CH3
I
CH3-C=CHCH3 + CH30H .... CH3C-CH2CH3
I I
CH3 CH3
Iso-Amylene Methanol TAME
CH2 CH3
II I
CH3C-CH3 + CH3CH20H .... CH3-C-O-CH2CH3
I
CH3
Iso-Butylene Ethanol ElBE
One of the major factors limiting production of these fuel grade ethers is the availability of
iso-olefins. Therefore, in many cases, the isomerization and hydrogenation of alkenes, such as
butane, to form iso-butylene is conducted in order to generate the needed olefin.
N-Butane Iso-Butane Iso-Butylene
The overall process is outlined in Figure 6. The isomerization technology employs a fixed bed
noble metal catalyst operating at a temperature 200°C and a pressure of 450 psi (3,100 k Pa).
The iso-paraffins are then separated from their saturated analogs by distillation, and they are then
converted to the corresponding iso-olefin. This is normally done over a fixed bed catalyst at
temperatures of about 600°C anywhere from a mild vacuum to slightly above atmospheric
pressure. The iso-olefin/alcohol reaction then takes place over a strongly acidic cationic exchange
resin, typically at 100 to 150 psig (690 to 1,035 k Pa) and 50 to 80'C. The ethers, being more
water tolerant, are generally blended into gasoline before shipment from the refinery.
For all of the above processes, opportunities to improve conventional manufacturing technology
exist. Routes to lower energy cost in ethanol production and to increase the conversion efficiency
of alkane isomerization and dehydrogenation are two examples of key process technology needs.
15
,:..;.;..-=..;:..::c-+j Oehydr~nallon 1--'-'-"" r--_+_MTBE

Unit
5.0 KBISO
Methanol
IC/nC. 1.7 KBISD
8.3 KBISO
nCo FHd Butane

5.0 KBISO Isomerization
Figure 6. MTBE Produced From Normal Butane.
5. Conclusions
Oxygenates, driven primarily by environmental concerns, are being increasingly used as fuel
components. They have been shown to have beneficial effects on tailpipe hydrocarbon and CO
emissions, probably related to their ability to promote leaner and better combustion in some
portions of the driving cycle. Both alcohols and ethers are being considered for this application.
The choice between the various oxygenates is being influenced by cost, availability, and their
impact on fuel properties. All have high octane, but alcohols (especially methanol) can have an
effect on volatility, water tolerance, and elastomer compatibility.
As demand for oxygenates increases, new supply capability will have to be build. This is
creating opportunities for new, more efficient manufacturing process technology.
References
API (American Petroleum Institute), "Alcohols and Ethers - A Technical Assessment of Their
Application as Fuels and Fuel Components," API Publication 4261, 2nd Edition, July 1988.
AQIRP (Air Quality Improvement Research Program) Technical Bulletin No.1, "Initial Mass
Exhaust Emissions Results from Reformulated Gasolines," December 1990.
Kishan,S., DeFries,T.H., and Klausmeier,RF., SAE Technical Paper 881593, "Description of
a Motor Vehicle Evaporative Emissions Model - EVAP 2.0," October 1988.
Most,W.J., SAE Technical Paper 892091, "Coordinating Research Council Study of Winter
Exhaust Emissions with Gasoline/Oxygenate Blends," September 1989.
Piel,W.J., National Conference on Motor Fuels and Air Quality, "The Role of Ethers in Low
Emission Gasoline," October 3-5, 1989.
ENGINEERING OF FLUIDIZED CAT AL YTIC CRACKERS.
DESMOND KING
Chevron Research and Technology Company
100 Chevron Way
Richmond, CA 94802-0627
USA
Abstract
This paper reviews the importance of Fluidized Catalytic Cracking (FCC) in the refining of crude
oil to transportation fuels. The FCC's role in converting vacuum gas oils (VGO) to meet the
world's shrinking demand for fuel oil but increasing demand for gasoline and mid-distillates is
discussed. The basic FCC hardware and yields are introduced followed by specific process design
and fluidization considerations. The demands on the FCC posed by gasoline reformulation are
reviewed and the emerging technology to meet those dcmands highlighted. The development of
FCC technology to crack heavy (resid) feeds to further reduce refinery fuel oil yields is outlined.
1. Introduction
Fluidized Catalytic Cracking (FCC) owes its origins to the 1915 discovery by A. M. McAfee of
Gulf Refining Co. (now part of Chevron) that a Friedel Craft aluminium chloride catalyst could
catalytically crack heavy oil. Since those early days, the vehicle for catalytic cracking has evolved
from fixed beds to moving beds to fluidized beds.
The first commercial application of truly fluidized catalytic cracking was in 1942 at the Standard Oil
Co. of New Jersey's Baton Rouge, LA. refinery. The vaporized oil was cracked in a dense, fluidizcd
bed of catalyst ("bed cracking"). Details of that Model I FCC are given by A vidan et al. (1989).
Various hardware improvements were made to bed crackers over the ensuing 30 years, but the advent
of Davison's synthetic Y zeolites signalled the demise of bed crackers as state-of-art.
The new zeolites were so much more active that they not only produced better yields but also required
only a few seconds of contact with the oil to achieve those yields. The 2 or 3 minutes of residence
time designed into bed cracker reactors (to accommodate the old amorphous silica-alumina catalysts)
rendered them largely unsuitable for the new zeolites.
Since the early 1970's bed crackers have been steadily updated to achieve residence times in the 2
second range by revamping to riser cracking. In riser cracking, contact time is kept to a minimum
by forcing the oil vapors to flow cocurrently with catalyst at high velocity in a riser pipe. New
FCC designs have incorporated riser reactors as standard for nearly 20 years.
17
H.I. de Lasa et af. (eds.), Chemical Reactor Technology for Environmentally Safe Reactors and Products. 17-50.
18
Today there are over 250 operational Fees in the world; about half are in the U.S. Many oil
companies have designed their own Fees (e.g., Exxon, Shell, Texaco, Total, Gulf), but the
majority of units over the last 50 years have been designed by two technology suppliers; UOP and
Kellogg. A third supplier (Stone & Webster) successfully entered the arena ten years ago.
2. The Importance of FeC
In a simple topping/reforming refinery (Figure I) crude is distilled in an atmospheric distillation

column and any material boiling above about 700°F is rejected as low value fuel oil. If that
refinery were upgraded to a cracking refinery (Figure 2), the atmospheric column bottoms would
be further distilled under vacuum to produce fuel oil and a vacuum gas oil (material boiling
between 700 and lOOO°F).
Process Gas
Butanes and Lighter (Ci) Propane LPG

Butane LPG
Butane
Naphtha }
MTBE Gasoline
C S-400'F
Reformate •
Naphtha L---r.=~
Atm. L-:C~~~~T;e~~~~~~
Crude Crude
Feed Disl.
Gas Oil 400-700'F Max.

or Pour Pt O°F, (-18'C)
- - - - -__ Gas Oil
Cutter
Fuel Oil
Figure 1. Topping/Reforming Refinery
.-_Bu_'_an_e_s_an_d_L..."IQ,-h_,e_r_ _ _ _ _ _ _ _ _ _ _ _ _ _~:~~c~~~ Gas
I------------~Gasoline
I------------~ Gas Oil
Gasoline
l=;==~=='-- Mid-Distillate
Vacuum Residuum
~--:B:-:P:->"'1CCOO:-::O-:-:0F:---------..-L---- Fuel Oil
Figure 2. Vacuum Gas Oil Cracking Refinery

19
The vacuum gas oil (VGO) is cracked in the FCC to produce largely gasoline and mid-distillates.
Propylenes, butylenes and isobutane produced in the FCC are combined in the alkylation plant to
produce still more gasoline. A hydrotreater is shown ahead of the FCC in Figure 2, this option
both increases the crackability of the VGO and reduces SO, and NO, emissions when the VGO is
cracked in the FCC.
Upgrading to a cracking refinery reduces the amount of low value fuel oil that a refinery yields
(Figure 3). For Arabian Light Crude, heavy product (fuel oil) is reduced from 47% of refinery
products to 27% by the addition of the FCC and ancillary equipment. The refinery product slate is
now roughly in balance with Western European demands. The refinery is still long on fuel oil by
U.S. product demands so further upgrading of the 1000°F+ residuum may be necessary (e.g., in a
resid FCC or a coker).
c:::::::J Light Products ~ Heavy Products

100
80
53% 73% 92% 88% 79%
60
E
'~"
'"
Il.
40
20
0
Topping/
Reforming Refinery
~~-Arabian Light Crude ~~- ~ 1987 Consumption-
Figure 3. Refinery Product Yields and Product Demand
The importance of the FCC to increase refinery gasoline and mid-distillate yields at the expense of
fuel oil becomes more apparent in the light of world trends in product demands. Denny et al. (1990)
report that fuel oil consumption plummeted in the 1980's even though crude oil consumption
remained relatively steady. Most of the drop occurred in Western Europe, Japan, and other Pacific
Rim countrics (U.S. consumption was already low) due to increased demands for lighter products,
alternative fuels and concerns over emissions from burning fuel oils. As fuel oil consumption has
dropped, worldwide gasoline and mid-distillate consumption has increased. Much of the increased
demand has been in Pacific Rim countries.
To meet these changes in world product demands, FCC capacity has now increased to process 22% of
world crude production. Avidan et al. (1989) (Figure 4) report that in the U.S. about 35% of all crude
is processed in an FCC (FCC capacity of about 5,250 KBbIJD) and in the rest of the world market
economies about 10% of crude processed goes to FCCs (FCC capacity of about 4,500 KBbIJD).
Worldwide, roughly a third of all gasoline produced comes from FCC and ancillary units (alkylation).
20
40
#.
;;:. 30
'u
"g- 1
USA
U
m
-g
0
'0
~
~
II>
'~ Rest of World
::J
U
U
u.
1960 1970 1980 1990

Year
Figure 4. FCC Capacity as a Percent of Crude Run - Avidan et at. (1989)
3. Basic FCC Hardware and Yields
The basic FCC hardware can be divided into three; the reactor-regenerator, product recovery and
regenerator flue gas cleanup (Figure 5). This article will concentrate on reactor-regenerator
engineering, but a cursory mention of the other two elements is included below.
~
a;
c
Feed m
Cl
m
II:
Recycle
Figure S. Block Diagram of a Fluid Catalytic Cracker
The product recovery section distills the reactor products into various fractions. The main
fractionator is often designed to recover a heavy gasoline cut, mid-distillate cut(s), and reject fuel
21
oil material as a bottoms product. The main fractionator overhead vapor is partially condensed to
give a light gasoline liquid stream and a vapor phase "wet gas" stream (mostly C4 and lighter). Both
overhead streams are compressed and fed to a gas recovery unit (GRU). The wet gas is compressed
via a wet gas compressor. In many FCCs. reactor conversion has to be suppressed in order to keep
yields of C 4 and lighter material within the capacity of the existing wet gas compressor. The GRU (a
series of columns including at least a deethaniser and debutaniscr) debutanises the light gasoline to
meet RVP (Reid vapor pressure) specifications, produces C 3 rich and C4 rich streams for further
processing (e.g., alkylation) and a C 2- stream for refinery fuel gas use (ethylene may be extracted for
chemicals before the stream makes it to fuel gas).
The flue gas leaving the regenerator is cooled in flue gas coolers and cleaned of particulates in an
electrostatic precipitator and any carbon monoxide in the flue gas is combusted to carbon dioxide in a
CO boiler. With higher pressure regenerators (e.g., operating above 30 psig) it is often economic to
include a power recovery turbine ahead of the precipitator. A multi-clone particle separator is placed
in front of the turbine to protect its blades from particle impaction. As SO, and NO, emission limits
become more severe, the flue gas train can be upgraded to include SOx scrubbing and selective
catalytic reduction (SCR) for NO, control.
A generic side-by-side FCC is shown in Figure 6 taken from Hemler (1989). Hot regenerated catalyst
(typically 1200 to I 300°F) t10ws out of the regenerator and down the regenerated catalyst standpipe to
meet the feed at the bottom of the riser reactor. The incoming liquid feed is vaporized by the hot
catalyst and the vapor then lifts the catalyst up the riser pipe. The feed vapor is steadily cracked by the
catalyst as they travel together. By the end of the riser there is about a three fold molar expansion as
the approximately 300 molecular weight feed is cracked down to 100 molecular weight product.
Typical riser outlet temperatures are in the 925 to 1025°F range (riser outlet temperaturcs are typically
200 to 300°F cooler than regenerator temperatures due to the vaporization of the feed and the fact that
cracking is endothermic). At the end of the riser, catalyst and vapor products are separated by a
simple riser turndown (or other type of ballistic separator). Residual catalyst carried by the products is
removed in one stage of cyclones (two stages in older units as shown in Figure 6) before the mix of
reaction products (reaction mix) passes to the main fractionator.
After the ballistic separator the catalyst (now spent) falls down to the stripper where it flows counter-
current to rising steam in a dense, baffled fluidized bed. The steam purges hydrocarbons entrained by
the falling spent catalyst and desorbs some of the residual hydrocarbons on the catalyst. The spent
catalyst t10ws to the regenerator via a spent catalyst standpipe.
Once in the regenerator, air is supplied from an air blower through an air grid to bum off thc residual
hydrocarbon left on the catalyst (called "coke") to render the catalyst regenerated. The heat of
combustion raises the catalyst temperature back up to the 1200 to 1300°F range. An FCC often has to
limit coke make to keep within the capacity of its existing air blower (since coke is a by-product of
conversion, this often means limiting conversion too). The t1ue gas from the dense bed of
regenerating catalyst exits the regenerator vessel via two stages of cyclones. The collected catalyst is
returned to the regenerator bed via cyclone diplegs.
Control of the FCC is achieved by the two slide valves. The regenerated catalyst standpipe slide valve
controls the riser reactor outlet temperature by controlling the t10w of hot regenerated catalyst
supplied to the riser. The spent catalyst standpipe slide valve controls stripper level by adjusting the
efflux of catalyst from the stripper.
22
Product to
Reaction Separation
Products
Upper Cyclones Dlsengager
Cyclones Riser 90° Turn Riser Cyclones
Regenerator
Riser Reactor
Stripping Stripper
Steam
Two-Stage Regenerator
Regenerator
It.... _ Spent Catalyst Cyclones
Standpipe Spent Catalyst
Standpipe
_ Spent Catalyst
Slide Valve
Riser Reactor
Spent Catalyst
Feed Injection Plug Valve
Regenerated Catalyst Riser Expansion
-- Slide Valve JOint
lateral Regenerated
t
Catalyst
~:~a~~:~aled Plug Valve
Standpipe Feed
Figure 6. Side· by-Side FCC Unit Figure 7. Kellogg Orthot1ow F

Hemler (1989) Whittington and Niccum
(To be Published)
Reactor Vapor
Regenerator
Flue Gas Reacior
Riser Reactor
Regenerator
Spent Catalyst
Stripper
COmb~~!~~ ---+---i
Combustor
Spent Catalyst
Standpipe
Catalyst
Cooler \tJY+--~:f~;:;~:adndPiPe
(Future)
Cooled 1:1-+J1k'rioS-- ~:~~~;~~~~~~dPiPe

Catalyst -
Standpipe
(Future)
~ Charge Stock
Lift Gas
Figure 8. UOP High Efficiency - FCC Reactor-Regenerator Assembly

Hemler (1989)
23
General criteria for sizing FCC hardware are included in Table 1. Many other more modern VGO
FCC designs are available. Kellogg's "Orthoflow F" design is given in Figure 7 [(adapted from
Whittington and Niccum (to be published)]. UOP's "High Efficiency" design is shown in Figure
8 from Hemler (1989). Both designs build upon the basic hardware previously described for the
generic side-by-side FCC.
The Kellogg design stacks the reactor above the regenerator in the same structure to reduce
construction costs. The UOP "high efficiency" design incorporates a high velocity combustor
style regenerator to achieve reduced catalyst inventories without any degradation in catalyst
regeneration. Both the Kellogg and UOP designs can be upgraded to process resid. Further
discussion about resid units is deferred to the resid cracking section of this article.
Table 1. Guidelines for Sizing FCC Hardware
Standpipes
Minimum Catalyst Flux: 100 Lb/S Ft2
Maximum Catalyst Flux: 300 Lb/S Ft2
Typical Flux: 150 to 250 Lb/S Ft2
Orient Standpipes Vertically or No More than 35° to Vertical
Aeration: 20 to 25 SCF per Ton of Catalyst per 100 Ft Vertical Drop
Aeration May Not Be Required for Short Standpipes and Other Special
Circumstances
Regenerator Catalyst Hoppers

• Mouth Area at Least Four Times Standpipe Area
• Hopper Cone Half Angle 20 to 30°
Controlling Catalyst Slide Valves

• 2 psi Minimum for Control
• 15 psi Maximum for Wear
• 25% to 75% Open for Control
• Design for About 7 psi and 50% Open
• Slide Valve Port Area About 0.25 to 0.45 of Standpipe Area
Riser
Minimum Velocity for Vertical Spent Catalyst Risers: 8 to 10 Ft/S
Minimum Velocity for Vertical Feed Risers: 15 to 20 Ft/S (At Bottom)
Maximum Riser Velocity: 90 Ft/S (For Wear)
Typical Feed Riser Exit Velocity: 50 to 70 Ft/S
Feed Riser Residence Time: 1.8 to 2.4 Seconds (Based on Outlet Moless)
Feed Riser LID: At Least 20 Preferred
• Feed Riser Turndowns: 80% to 90% Separation Efficiency
Reactor Vessels
• Maximum Operating Velocity: 3.5 Ft/S (with Efficient Cyclones)
• Typical Operating Velocities: 2.0 to 3.0 Ft/S
• Disengaging Height (Riser Turndown to Cyclone Inlet): 15 Ft Minimum
24
Strippers
Typical Steam Rates: 2 to 4 Lb of Steam per 1000 Lb of Catalyst
Typical Operating Velocities: 0.5 to 1.0 Ft/S
Typical Catalyst Residence Time: 60 to 90 Seconds
Typical Catalyst Flux: 400 to 900 Lb/Min. Ft2
Maximum Catalyst Flux: 1200 Lb/Min. Ft2
Stripper LJD at Least 1
Unbaffled Strippers Not Recommended if Stripping Steam Efficiency
a Concern
Regenerator Vessels
Maximum Operating Velocity: 3.3 Ft/S
Typical Operating Velocity: 2 to 3 Ft/S
3.5 to 5.5 Ft/S (UOP High Efficiency)
Catalyst Resident Time: 5 to 10 Minutes (1 Stage Regenerator)
One Minute (UOP High Efficiency)
3 to 5 Minutes (Each Stage in 2 Stage Design)
• Bed LID: 0.3 to 0.7 in Conventional Designs
Disengaging Height: 18 to 20 Ft (Bed Surface to Cyclone Inlet in
Conventional Design)
Grid Pressure Drop: Typically 1-2 psi, at Least 30% of Bed Head
Minimum Grid Pressure Drop: 0.7 to 0.8 psi
Cyclones
Reactor 1 Stage Design: Typical Collection Efficiency: 99.995%
Typical Pressure Drop: 0.5 to 0.7 psi
Inlet Catalyst Loading About 0.25 Lb/Cubic Ft
Regenerator 2 Stage Design: Typical Overall Collection Efficiency: 99.998%
Typical Pressure Drop: I psi
Inlet Catalyst Loading About 0.5 Lb/Cubic Ft
Once an FCC is operational, there are four main ways to adjust the yield slate for a given feed;
I) CAT/OIL RATIO (the pounds of regenerated catalyst supplied to the riser per pound of feed
oil) - the higher the cat/oil the higher the conversion. Murphy and Cheng (1984) report in Table
2 that a 1.3 increase in cat/oil raised conversion by 5 Wt % of fresh feed (FF) - i.e., 5 Wt %
more of the feed was converted to gasoline or lighter products.
At a given reactor outlet temperature, lowering the temperature of the feed oil increases cat/oil
(the regenerated catalyst slide valve opens up to supply more hot catalyst to the riser to make up
for the reduction in enthalpy of the feed).
2) REACTOR OUTLET TEMPERATURE - the higher the value, the higher the conversion.
Table 2 shows a 5 Wt % FF conversion gain for a 43°F increase in riser outlet temperature.
3) RECYCLE OF FRACTIONATOR BOTTOMS - to give the reactor a second chance to

convert this fuel oil type material (recycling is rarely economic unless a unit has spare air blower
and wet gas compressor capacity).
25
Table 2. Average Effect of Variables in Fluid Catalytic Cracking

Murphy and Cheng (1984)
Riser Regen. Carbon on Hydrocarbon Feed Con

Outlet Bed Cat/Oil' Regen. Partial Carbon
Temp. Temp. Ratio/TF Activity Catalyst Pressure ResIdue I
Change In Vanablcs
Riser Outlet Temp., of 43
Regenerator Bed Temp., of 80
Catalyst-to-Oil Ratio, Wt/Wt (TF) 1.3
Catalyst Mlcroactivity (MAT) 4
Carbon on Regenerated Catalyst, Wt % -0.13
Hydrocarbon Partial Pressure at Feed 8.5
Injection Point, pSIa
Feed Conradson Carbon ResIdue, Wt % 1.0
Differential ConVerSlOI1, Wt % FF 5.0 2.0 5.0 5.0 5.0 2.0 -0.32

DIfferential Yields, Wt o/,') FF
Debutamzed Gasohne 0.51 0.70 2.29 3.20 2.86 0.52 -0.89
Butane-Butylcne 2.35 0.55 1.17 1.06 1.10 0.35
Isobutane 0.13 0.05 0.63 0.60 0.61 0.46
n-8utanc 0.14 0.05 0.16 0.15 0.16 0.17
1<"
Butylenes 2.08 0.45 0.38 0.31 0.33 -0.28
Propane-Propylene 1.18 0.27 0.36 0.43 0.53 0.26
Propane 0.16 0.02 0.09 0.08 0.13 0.27
Propylene 1.02 0.25 0.27 0.35 0.40 -0.01
Light Cat. Gas Oil -2.23 -0.80 -2.23 -1.97 -2.23 -0.80 0.17
Fractlonator Bottoms -2.77 -1.20 -2.77 -3.03 -2.77 -1.20 0.15
C,+ LIghter 0.67 0.43 0.34 -0.06 -0.16 0.08 0.03
Hydrogen 0.01 0.0 0.01 -0.01 -0.02 -0.01
Methane 0.23 0.20 0.13 -0.05 -0.15 -0.01
Ethane 0.19 0.13 0.13 0.0 0.02 0.08
Ethylene 0.24 0.10 0.07 0.0 -0.01 0.02
Coke 0.29 0.05 0.84 0.37 0.67 0.79 1.01
Differential Octane Ratings
Research Clear 1.6 1.1 0.3 0.0 -1.2 -1.2 0.04
Motor Clear 1.8 0.9 0.9 0.4 0.1 -0.9 -0.02
'The Effect IS EstImated Based Upon the FolloWIng Feedstock Blend:

Gas Oil 29' AP1 725'F V ABP 0.05 Wt % Con C 0.8 ppm NI + V
Residue 10' API 1075°F V ABP 17.0 Wt % Con C 58.0 wppm Ni + V
The Increase of Con Carbon IS Obtained in Increasing the Composition of Residue in the Gas OiljResldue Blend
2At Constant Catalyst Residence Time (Based on Total Feed)

Note: Table vaJid if one variable changes by itself, others stay constant. More typically duc to FCC heat balance,
several variables change at once; add effects from table III that case.
4) CHANGING CAT AL YST - Changing from one catalyst to another can optimize yields
within the operational constraints of a given unit. Whereas the previous three operational changes
can occur in a matter of hours, fully changing out catalyst while an FCC is operational can take
a matter of months, Examples of the yield changes for various catalyst types is given by
Young et aL (1991),
Lomas et aL (1990) demonstrate how an FCC can be switched from mid-distillate (diesel type
material) mode to gasoline mode (Table 3) with a Middle Eastern VGO. Reactor temperature
and cat/oil are both increased (e.g., 930 to 980°F for reactor temperature and 4.5 to 7.5 for cat/
oil). Recycle of HCO (i,e" fractionator bottoms) is reduced. Catalyst type is changed in their
example from a rare earth Y zeolite (Re Y) to a chemically stabilized and dealuminated
Y zeolite (CSDY).
26
Table 3. Example of FCC Operating Modes - Lomas et. al (1990)
Middle- Light
Distillate Gasoline Olefin
Mode Mode Mode
Operating Conditions
Reactor Temperature, °c 449-510 527-538 538-560
Reactor Temperature, of 930-950 980-1000 1000-1040
Residence Time <Base Base >Base
Catalyst/Oil Ratio <Base Base >Base
Recycle, CFR 1.4 Optional Optional
(HCO) (HDTLCO) (Hvy Naphtha)
Catalyst Formulation
Zeolite Type ReY CSDY* USY
Zeolite Level, Wt % 15 30 40
Rare Earth, Wt % 1-2 0.5-1.5 0
Zeolite/Matrix Ratio <Base Base >Basc
Product Yields
H,S,Wt% 0.7 1.0 1.0
C:-, Wt % 2.6 3.2 4.7
C;,LV% 6.9 10.7 16.1
C4 ,LV % 9.8 15.4 20.5
C,+ Gasoline, LV % 43.4 60.0 55.2
LCO,LV% 37.5 13.9 10.1
HCO,LV % 7.6 9.2 7.0
Coke, Wt% 4.9 5.0 6.4
Product Properties
LPG, VollVol:
C] Olefin/Saturate 3.4 3.2 3.6
C4 Olefin/Saturate 1.6 1.8 2.1
Gasoline
ASTM 90% Pt., °c 193 193 193
ASTM 90% Pt., OF 380 380 380
RON Clear 90.5 93.2 94.8
MON Clear 78.8 80A 82.1
Light Cycle Oil

ASTM 90% Pt., °C 350 316 316
ASTM 90% Pt., OF 670 600 600
Pour Pt., OF (50°C) 4.0 7.0 2.0
Viscosity cSt at 122°F (50°C) 3.7 3.1 3.2
Sulfur, Wt % 2.9 3.4 3.7
Cetane Index 34.3 24.3 20.6
Clarified Oil
Viscosity cSt at 210°F (lOO°C) 10.9 9.0 10.1
Sulfur, Wt % 5.1 6.0 6.R
*Chemically Stabilized and Dealuminated Y Zeolite

27
These changes reduce mid-distillate (light cycle oil, LCO) from a volume equivalent to 37.5 LV
% of fresh feed (FF) to 13.9 LV % FF. Some of the reduction is due to a lowering of the 90%
point of the LCO. Gasoline is at the same time increased from 43.4 LV % FF to 60 LV % FF.
The total volume of liquid products (C 3 through clarified oil) increases from 105.2 LV % FF to
109.2 LV % FF. The volume of the products from an FCC is always larger than the volume of the
feed due to the molar expansion that occurs during cracking.
4. Specific Design Considerations
4.1 FLUIDIZATION
As the name fluidized catalytic cracking suggests, fluidization is a key design consideration. All
gas-solid fluidization regimes known can be exhibited in an FCC. After mechanical failures,
fluidization problems are one of the main causes of unit upsets. The basic regimes of fluidization
are illustrated in Figure 9. To move from one regime to another the gas superficial velocity
through the bed must be changed (superficial velocity - U -is defined as the actual volume
flow of gas divided by bed cross-sectional area).
FCC catalyst becomcs fully fluidizcd at values of U approaching 0.005 Ft/S. Between 0.005 and
0.01 Ft/S, catalyst is fluidized without observable gas bubbles (particulate regime). As gas
superficial velocity is increased further, FCC moves into the bubbling regime (i.e., gas bubbles
moving through a bed of fluidized catalyst). In a small pipe (e.g., standpipes) the bubbles can get
so large as to approach the size of the pipe itself (slug flow regime).
AP~;~~~ate _---'u=-<:..:O"'.O':....:F-""/S=--....._ _-=.:..=..:c.==-:..::-=----...o=--=-=-c:..::..:.=.. ~

Ranges . ,':
In FCC .. , , ' ,
:.' : "
:.' : "
" " . " " .
Fixed Bed Particulate Bubbling Slug Flow Turbulent Fast Pneumatic

Regime Regime Regime Regime FlUidization Conveying
Aggregative Fluidization
Increasing U
Figure 9. Principal Flow Regimes for Upward Flow of Gas Through FCC CatJayst
Above 3.5 Ft/S bubbles become unstable and break down to jagged tongues of gas that dart to and
fro - the turbulent regime. Eventually by 6 Ft/S, clusters of solids are conveyed up the centre
and out of the bed while other clusters fall down at the wall (fast fluidization). Beyond about
6 Ft/S the large clusters break down to small clusters that are pneumatically conveyed out of the
pipe with only relatively minor slippage back downwards at the wall.
28
Table 4 lists the regimes in different parts of the FCC along with typical densities. The regime
achieved is a direct result of the typical operating velocities quoted in Table I. Of all the FCC
components, the standpipes can be the most fickle. Depending on the relative velocity of gas to
Oowing catalyst, standpipe densities can vary from 0 to 40 Lb/Fe if the standpipe is underaerated and
back down to 0 Lb/Fe again if there is overaeration. This explains why so many catalyst circulation
problems in FCCs cmanate from standpipe aeration problems.
Table 4. Fluidization - Regimes/Densities in the FCC
Typical Densities,
Regime Lb/Fe
StandpipesiU -Bends Slug Flow 0-20

(Overaerated)
Bubbling 20-35
Particulate 35-40
"Fixed" Bed 40-0
(Underaerated)
Reactor Riser Pneumatic Conveying 1-10
Spent Catalyst Riser Pneumatic Conveying 5-15
Regenerator Bed BubblingjTurbulent 30-35
Regenerator (High Efficiency) Turbulent/Fast 5-15
Reactor Stripper Bubbling 40-45
4.2 STANDPIPE DESIGN
Standpipes are typically sized to pass 100 to 300 Lb/S Ft2 of catalyst (Table 1). Standpipes are
preferably vertical, although angled standpipes are acceptable providing they are at least about 35
degrees to the vertical. Ideally angled standpipes should not be too long - Ross (1990) suggests that
angled standpipes should be no longer than 40 Ft. Tn general angled standpipes deaerate more easily
because aeration can rise to the top of the pipe.
Many standpipes need additional aeration to be added along their length to prevent the catalyst
deaerating. Typically adding 20 to 25 SCF of aeration per ton of catalyst circulation per 100 Ft
vertical drop will keep the standpipe aerated. The example in Figure 10 shows a hopper feeding
catalyst from a regenerator bed into a regenerated catalyst standpipe. Aeration taps are located every
6 to 7 Ft down the standpipe. the total aeration is (as a first approximation) distributed evenly to taps
A through F. At optimum aeration, standpipe densities should be in the 30 to 35 Lb/FtJ range. Some
standpipes (especially short ones, e.g., less than 40 Ft) can operate fully fluidized without aeration.
This is a function of hopper design (i.e., how much aeration the hopper allows the catalyst to drag into
the standpipe), unit pressure, and catalyst flow properties. Raterman (1985) has proposed an equation
(based on catalyst properties) to predict when FCC standpipe flow problems might occur.
29
Operating Range: 100-300 lb/S Ft 2 (W)

Aeration: 20-25 SCF per Ton Cat. Gire. per 100 Ft (Vertical Drop)
Head Buildup (Apparent Density): 30-35 Lb/Ft3 (Psp)
Total Head BUildup = H Pspl144 (in psi)
Note Some standpipes can operate without aerallon (depends on

Hopper design, umt pressure, catalyst propertIes, etc.).
Regenerator Bed
Regenerator Grid
Hopper or Underflow Well
Standpipe
Aeration Taps - - A
(Every 6-7 Ft)
o
Standpipe Inside
DIameter
Slide Valve ;::::.-;'I'TO Reactor

FCC Feed Riser
Figure 10. Example of a Straight Standpipe
Results reported by King et al. (1989) as part of a cold model study to solve a commercial
catalyst circulation problem are given in Figure 11. As aeration is increased in multiples of Q, (20
to 25 SCF per ton per 100 Ft) from zero, apparent standpipe density builds from 15 to 20 Lb/Ft3
at QIQc of 0.5 up to 30 to 35 Lb/Fe at QIQ c ' s in the 1 to 1.5 range. When underaerated, low
apparent densities result because partly fluidized catalyst does not transmit its full head. Under
these conditions catalyst flows in a stop start manner ("stick-slip") down the pipe. Above QIQc of
1.5. the standpipe became very unstable and head buildup dropped off dramatically as the
overaeration caused gas slugs to form in the pipe. The exact aeration values at which standpipe
instabilities begin is a function of the particular system.
Qc = Equivalent of 20·25 SCFITon/100 Ft
,&SlIdeValveI5%Open
40 • Slide Valve 12% Open
.
• Slide Valve 25% Open
~ 35
• •
f
~
30 •
~
8. 25
ii
"
lil
C
~
20 ... « :tsndPlpe Steady) I «.:::sd:: )
y
Unsteady
~
., 15 ...
o~~-----L----~----~~
o 0.5 1.0 1.5 2.0
StandpIpe AeratIon Rate, QIQc
Figure 11. Apparent Standpipe Density Versus Aeration Rate - King et al. (1989)
30
A key element of regenerated catalyst standpipe design is the design of the hopper that feeds
catalyst to the standpipe. The purpose of the hopper is to "debubble" the catalyst so it does not
pull large gas bubbles from the regenerator into the standpipe (thereby causing overaeration
problems). Figure 12 shows two typical hoppers along with typical hopper design criteria (to
ensure that the hopper supplies well aerated catalyst without big bubbles).
Rules of Thumb:
1. Hopper mouth area should be at Jeast four times

standpipe cross-sectional area.
2. Best design often cone or offset cone whose angle (e)

is at most 30° (20 0 is ideal).
3. Hopper aeration not necessarily required.
4. Head buildup in hoppers is typically 35-40 Lb/Ft3.
Figure 12. Standpipe Hoppers
A design for a standpipe slide valve to control catalyst flow is given in Figure 13 from Cabrera et
al. (1984). In its simplest manifestation, a slide valve is a flat metal plate (lined with erosion
resistant refractory) that traverses an orifice placed perpendicular to the catalyst flow. Design
rules of thumb for catalyst slide valves are given in Table 1. The pressure drop available to be
taken across a slide valve is set by unit pressure balance. For example in Figure 6 the pressure
drop across the regenerated catalyst slide valve (RCSV) is given by:
RCSV Pressure Drop Regenerator Pressure

+ Head Buildup across Regenerator Bed
+ Head Buildup down Regenerator Standpipe
- Feed Riser Head and Pressure Losses
- Reactor Pressure
Head buildup down the standpipe is normally the biggest head buildup term. If the standpipe is
encountering operational difficulties (typically resulting in low densities) little or no pressure drop
might be available to be taken across the valve - i.e., the valve no longer controls the solids flow.
Hexmesh
Refractory
Conventional Hydraulic
Actuating Cylinder
~
Valve Stem Packmg
Purge Pomt Valve Disk
Figure 13. Catalyst Slide Valve - Cabrera et aI. (1984)

31
4.3 FEED RISER DESIGN
Risers are used primarily in FCCs to effect the conversion of the feed oil. They are also used in
some older FCC designs (e.g., ESSO Model IV, Kellogg Model III) to air lift spent catalyst up
into the regenerator.
The minimum velocities for risers are listed in Table I. For a feed riser the lowest velocity is
normally encountered at the bottom where the oil is first vaporized. In a vertical feed riser (e.g.,
Figure 6) it is important that the diameter of the riser at the feed injection point is sized to give at
least 15 to 20 FtlS (based on 100% vaporization of the feed). The riser diameter may be
increased further up the riser as velocity picks up due to molar expansion. The bottom, narrow
part of the riser is often referred to as the acceleration zone. Riser exit velocities arc generally in
the 60 FtlS range. Riser velocities rarely exceed the limits of erosion resistant lining (90 Ft/S).
The trend in feed nozzles over the last few years has been to retrofit simple feed nozzles (often
just straight pipes) with ones that atomize the feed (usually by a combination of mechanical
design, steam and pressure drop). All the major technology suppliers (Kellogg, Stone and
Webster, UOP) now offer atomizing nozzle designs.
Stone and Webster's design based on Dean et al. (1982) is shown in Figure 14. These nozzles
currently feed a total of 700 KBbl/D of FCC feed in 23 units. The steam [Ross (1990) quotes 2.5
to 3 Wt % of feed for VGO and 5 Wt % for res ids 1and oil are mixed in a chamber outside the
riser. The high pressure drop (about 50 psi for VGO, 100 psi for resid) smashes the oil to droplets
(reported to be about the same diameter as the FCC catalyst) and supplemental steam assists the
mist into the riser. Due to the high nozzle exit velocities, the nozzles point upward and are
normally arranged as opposing pairs (if the nozzles enter through the riser side wall) to prevent
eroding a hole in the riser wall.
Figure 14. Stone and Webster Feed Nozzles - Dean et a!. (1982)
32
Improved catalyst/oil mixing achieved by good atomizing nozzles results in less thermal cracking
and yields that are more selective to gasoline. The presence of the large quantities of diluent in
the riser (the steam) reduces hydrocarbon partial pressure and hence reduces coke make (see
Table 2).
At thc termination of the riser it is important to have quick separation of reaction mix from spent
catalyst. After the riser, the reaction mix can remain in the reactor vessel for over 20 seconds
before it enters the reactor cyclones and is separated from the spent catalyst. Typically, catalyst
densities between riser outlet and cyclone inlet average only 1 to 3 Lb/Ft3 • During that 20+
seconds additional conversion can occur, but since the catalyst is spent the conversion is thermal
in nature and not selective to gasoline. Ross (1990) reports commercial information (Figure 15)
for a simple riser turndown that shows a 4 LV % FF conversion gain between riser outlet and
cyclone inlet. Even though conversion increased, gasoline yield went down.
A B C
Riser Cylone Stripper
Outlet Outlet Outlet
Conversion, Vol % 74 78 84
C2" 1.6 2.8 17.3
C3 =' 4.7 5.5 2.1
C4 =' 6.6 7.2 1.2
(C 3 + C4)% Olefin 71.7 64.5 11.1
Gasoline' 56.5 55.5 36.7
LCO' 17.3 14.8 10.0
~C HCO' 8.7 7.2 6.1
• Wt % (Coke Free)
Figure 15. Post Riser Cracking - Commercial Data from Ross (1990)
A number of standard riser separator designs are available. Simple separators are very suitable for
VGO cracking at moderate severity. They typically allow only 20% to 10% (or less) of the catalyst
circulation up the riser to be entrained to the cyclones. More efficient and intricate devices are
required for high temperature operation as the thermal cracking after the riser is exacerbated under
these circumstances. This will be discussed later under reformulated gasoline.
Riser pressure drop and densities can be calculated by a number of different methods e.g., Jazayeri
(1991). Typically feed risers have an average density of 5 Lb/Ft'; 10 Lb/Ft 3 at the bottom, 1 Lb/Ft3 at
the top. Including entrance and exit (separator) effects, riser pressure drop is usually in the 4 psi range.
For optimum conversion, riser residence times are designed to be about 1.8 to 2.4 seconds based on
outlet moles (i.e., the volume of the riser divided by the volume of hydrocarbon and steam exiting the
riser). Most state-of-art risers are 100+ Ft long with an LID ratio of over 20.
33
Reactors are now little more than holding vessels for the reactor cyclones. With efficient riser
separators, reactor velocities of up to 3.5 Ft/S are not uncommon. A new reactor would be sized
for about 2.5 Ft/S. Cyclone inlets are normally placed at least 15 Ft above simple riser turndowns
to allow for any catalyst disengagement that might take place.
4.4 STRIPPER DESIGN
Strippers are designed to purge the hydrocarbons entrained with the downfalling spent catalyst
and desorb some of the heavier hydrocarbons from the catalyst itself.
Steam is introduced at the bottom of the stripper through a pipe grid and it mostly rises up counter
current to the downwardly flowing dense stripper bed. Most strippers have baffles in order to
achicve the most efficient use of steam. Normal steam rates are 2 to 4 Lb of steam per 1000 Lb of
catalyst. Steam superficial velocities in the stripper are normally 0.5 to 1.0 Ft/S.
According to Ross (1990), strippers are sized for a catalyst flux in the 400 to 900 Lb/Min. Ft2
range. A typical maximum operating condition is 1200 Lb/Min. Fe - if the catalyst flows down
too quickly it drags the steam down with it, limiting the steam's effectiveness to purge
hydrocarbons. Most strippers have a catalyst rcsidcnce time of 1 to 2 minutes and an LID of at
least 1. The density of the stripper bed can be calculated using King's (1989) equation (Table 5).
Table 5. King's (1989) Equation to Predict Bed Density
Applies to Strippers, Conventional Regenerators and Bottom Part of

High Efficiency Regenerators
SI Units
Bed Density (in kg/m3) = ABD/[0.6(U+2)]

ABD = Catalyst Bulk Density (kg/m3)
U = Bed Operating Superficial Velocity (m/s)
British Units
Bed Density (in LblFt 3) = 3.3 ABD/[0.6(U + 6.6)]

ABD = Catalyst Bulk Density (Lb/Ft3)
U = Bed Operating Superficial Velocity (Ft/S)
4.5 REGENERATOR DESIGN
Spent catalyst enters the regenerator laden with a covering of coke equivalent to about 1% of its
weight. Ideally we would like to burn off as much coke as possible to render the catalyst
regenerated. If the regenerator is well designed the carbon left on regenerated catalyst (CORC)
34
becomes a function of the burning kinetics. A well designed regenerator operating in complete
combustion (minimal CO in the flue gas) should achieve a CORC close to 0.05 Wt %.
A conventional regenerator (single stage) has a catalyst residence time between 5 and 10 minutes.
Bed superficial velocities are normally in the 2 to 3.5 Ft/S range; 2.5 to 3.0 Ft/S is typical. Dense
bed density can again be calculated by King's (1989) equation (Table 5). To keep regenerator
elevation down, LID's for the dense bed are about 0.3 to 0.7. Normally a freeboard height of 18 to
20 Ft exists between bed surface and cyclone inlets to minimize the catalyst loading in the flue
gas as it enters the cyclones. There is typically 0.5 Lb/Ft3 of catalyst at the cyclone inlets.
The key to good regenerator design is good air distribution and good distribution of spent
catalyst. Ross (1990) illustrates a number of spent catalyst distribution devices (Figure 16) for
FCC's like the one illustrated in Figure 6. Catalyst flows down the spent catalyst standpipe and is
distributed over a large area of the regenerator bed surface by troughs or slotted pipes. The slotted
pipes can also be submerged.
Spent Catalyst
.;
Figure 16. Spent Catalyst Distribution Designs for Various Regenerator Configurations
Ross (1990)
Good air distribution can be achieved by either a perforated plate grid or a pipe grid. Figure 17
illustrates a pipe grid; it can have branched header pipes (as shown) or have concentric ring headers.
Located on each header are a large number of nozzles from which air is introduced into the bed. A
cross-sectional view of the header pipe (Figure 18) illustrates that the nozzles can point up, down, or
at any angle. Typically there is at least one nozzle per square foot of regenerator bed cross-section.
Each nozzle in fact is a tube with a restriction orifice at the bottom. The nozzle pressure drop is taken
across the orifice but the nozzle tube is made long enough to contain the expanding gas jet. Since the
jet now sweeps the whole cross-section of the tube, it becomes difficult for the catalyst to backflow
into the header pipe where it would cause erosion problems. Air grid life is extended. Catalyst
attrition is also minimized because, when the gas first contacts the bed of catalyst it is moving much
slower than at the orifice (catalyst attrition varies with velocity cubed or worse).
To ensure that all nozzles are issuing air, grids are normally designed with a 1 to 2 psi pressure drop
(i.e., at least 30% of the bed pressure drop). A minimum operating pressure drop is normally 0.7 to
0.8 psi. If pressure drop gets too low, nozzles at the end of headers will pass little or no gas and
catalyst may backflow into the header. As the catalyst blows out through an operating nozzle, the pipe
grid will rapidly erode out. Eventually air distribution would become so bad that regeneration may
35
become unacceptable and/or circulation problems may result from e.g., underaerated catalyst flowing
into the regenerated catalyst standpipe (i.e., grid no longer supplying air in the vicinity of regenerated
catalyst draw off point).
Top View
Nozzle For I Header
Air Exit
i
A =Cross-Sectional Area
Figure 17. Example of a Regenerator Pipe Grid Air Distributor
Pipe Grid Header Details

I
Header Cross-Section
~~==::tt:::t- Restriction Orifice
Refractory
Header Pipe
Drain (Only at Specific Locations)
Figure 18. Example of a Regenerator Pipe Grid Air Distributor - Cross-Sectional View
Along Header Pipe
36
4.6 CYCLONES
A cyclone is a simple device that uses centrifugal force to separate solids from a gas stream. A brief
mention of cyclones is merited here because they are key to the successful operation of the
regenerator and the reactor. FCCs can be forced to shutdown because of a small hole in a regcnerator
cyclone results in unacceptable plume of catalyst leaving the regenerator stack.
Catalyst laden gas enters a cyclone tangential to the cyclone barrel (see Figure 19). The centrifugal
force flings the catalyst to the wall where it wends its way down as a rope (or spinning sheet) of
solids. The solids make their way to the bottom of the cyclone where they are collected and returned
to the bed via the dipleg. The gas separates from the solids and exits at the top of the cyclone.
Gas Outlet ---+E

Tube
Gas Inlet
Duct
Barrel
Cone--->-\liI
Dust Hopper
(Trap)
Dipleg - - -..I
Figure 19. The Basic Cyclone
API (1985) gives a method for calculating FCC entrainment rates (for conventional regenerators),
cyclone efficiency and pressure drop. A cyclone perfonnance curve is shown in Figure 20. As inlet
gas rate increases (at constant solids concentration), cyclone collection efficiency and cyclone
pressure drop both increase. Eventually efficiency declines at very high gas rates because the exiting
gas velocity is high enough to re-entrain previously "collected" solids.
As catalyst loading to a cyclone increases so does cyclone efficiency as illustrated in Figure 21 by

King (1992). Eo is the cyclone efficiency when it is lowly loaded (Eo is detennined by the cyclone
mechanical design and FCC particle properties in the API (1985) method). As solids concentration is
increased (at constant gas rate) collection efficiency climbs rapidly from say 85% at 1 grain/Ft3 to
99.985% at 1000 grain/Ft3. There are 7000 grains in 1 Lb. If Figure 21 is used in conjunction with
the API (1985) method, representative predictions for modem FCC cyclones will result (the API
(1985) method's own cyclone efficiency curves do not go to high enough loadings to be practical -
extrapolating those curves would result in FCC catalyst loss predictions orders of magnitude higher
than we observe commercially).
37
• Effect of Gas Inlet Velocity on Collection Efficiency and Cyclone Pressure Drop
100
____ - - - Theoretical Curve
---'---
i <f!-
,;;
-- --:..- :8
Practical Curve
"
I:
C!)
'(3
, - - - - - - - - - - - - - - - - - 1.0
'iii
ffi Q.
ti
.2
I:
c
e
U
~ 0.4 l!!
is J
u 1/1
1/1
l!!
~
0 ~~--------------------------------~o
0 100
Gas Inlet Velocity, FtiSec. - - . .
Figure 20. Example of Performance Curves for a Cyclone
99.999
~ 99.999 9 9.997
:g ........--: 99.994
99.99
! :::.- 99.985
.3
99.9 ~~ 99.965
99.955
99.935
99.B Eo:::99<)/o ~
99
Eo=910/~ ~' i -l-
98
95
Eo = 94% Eo=~ ,!..// /
90
f---- r-
~/
Eo $(Y
~o_= ,
80
I- '/ .-
60 I- Eo;::?l:JrJ/ c L
40
20
o
1 10 100 1,000 10,000
Loading of Solids in Inlet Gas, Grains of Solids/Cu Ft of Gas
Note: EO is the Smgle Particle Collection Efficiency (Cyclone at "Zero" Loading)
Figure 21. Effect of Inlet Loading on FCC Cyclone Collection Efficiency - King (1992)
In regenerators, sets of cyclones are operated as pairs in series to give a combined collection
efficiency of about 99.998% at an overall pressure drop of about 1 psi. In modem reactors with riser
separators, one stage cyclones are used with about a 99.995% collection efficiency and about 0.5 to
0.7 psi pressure drop. The modified API (1985) method can also be used for rough cut cyclones, i.e.,
cyclones attached to the end of feed risers as riser separators.
38
s. Reformulated Gasoline
In the U.S. the 1991 Clean Air Act Amendment will require the reformulation of gasoline in CO and
ozone non-attainment areas. A number of areas that are currently not non-attainment will also have
the right to opt for reformulated gasoline. Estimates of the volume of gasoline affected vary, but a
likely scenario is that about half of the gasoline sold in the U.S. could be reformulated in the 1990's.
The drive for reformulated gasoline is to reduce CO, NO" and hydrocarbon emissions.
The general direction that U.S. ga~oline is headed is given in Table 6.

A joint Auto/Oil Air Quality Improvement Research Program (1990 to 1991) has reported the effects
of changes in Aromatics, Oxygen content (added in the form of Methyl Tertiary Butyl Ether -
MTBE), Olefins and T90 (the 90% point on the gasoline boiling curve) on emissions from newer and
older cars.
Table 6. Directions in Motor Gasoline Composition in the 1990's
• Lower RVP
• Reduced Distillation -T90
• Increased Oxygen Content
• Reduced Sulfur Content
• Reduced Aromatics
• Reduced Benzene
• Constant or Reduced Olefins
Reducing aromatics, olefins, T90 and increasing MTBE in gasoline generally lowers emissions. In
addition, lowering RVP is expected to reduce hydrocarbon emissions during refueling and reducing
sulfur in gasoline is anticipated to extend the life of catalytic converters. Reducing benzene is required
because it is a known carcinogen.
5.1 THE FCC AS A LIGHT OLEFINS GENERATOR
FCCs will be operated at higher severity to produce the light olefins required for increased MTBE and
alkylate production. Table 3 from D.A. Lomas et al. (1990) shows how FCC yields will change as the
FCC moves from maximum gasoline mode to maximum light olefins mode. Reactor temperature is
increased to the 1000 to 1040°F range and cat/oil raised to a high value (e.g., 8 to 9). At this high
severity, conversion is not only increased but gasoline is overcracked to C3 and C4 olefins. Depending
on the catalyst, a third or more (45% is thermodynamic equilibrium) of the C4 = may be iso-butylene.
Iso-butylene is combined with methanol to produce MTBE (1 Bbl of IC4= plus 0.47 Bbl of methanol
yields 1.27 Bbl of MTBE). In CO non-attainment areas up to 15 Vol % of the gasoline will be MTBE
(2.7 Wt % oxygen in gasoline) during the winter months. Ozone non-attainment areas will need 11
Vol % MTBE in gasoline year round. For thc light olefins case given in Table 3, the IC4= produced
would make enough MTBE to give 3 to 4 Vol % MTBE in the refinery gasoline pool. A significant
contribution, especially since no other major source of IC 4= is readily available in the refinery.
The additional C] and normal C4 olefins (and even some C s olefins) can be made into alkylate.
Additional alkylate is welcome in the reformulated gasoline pool because of its low aromatics
content.
39
When operating at high reactor temperatures, the challenge for the FCC is to selectively produce
C 1 and C 4 's without producing excessive amounts of C2 and lighter gas. C,- production is
minimized if thermal cracking after the riser outlet is kept to a minimum. The standard riser
turndown is no longer sufficient because it still allows over 20 seconds for thermal cracking post-
riser outlet. One approach to reducing thermal cracking is to spray in quench at the end of the
riscr to rcducc the tempcraturc in the dilute phase. This can be effective, but it places increased
load on the FCC main fractionator.
One solution is to place the reactor cyclones very close to the riser outlet. This is the vented riser
design offered by UOP - Figure 22. Catalyst from the end of the riser impacts the head of the
reactor which now acts as a ballistic separator. The reaction mix turns 180 degrees as it leaves the
riser to exit quickly through the cyclone inlets positioned right next to thc riser.
Vented Riser Direct-Connected Cyclones

Rx Vapors ~--_
Direct-
Connected --~n
Cyclones
Prest ripping
Steam Plug-Flow
Riser
Figure 22. Advanced Riser Separators
To reduce riser-outlet-to-cyclone-inlet times to a minimum, the reactor cyclones can be directly

connected to the riser outlet as shown in Figure 22. Both Mobil (through Kellogg) and UOP offer
this type of technology. These are more sophisticated devices than simple rough cut riser
cyclones (vapor from rough cuts passes into the reactor dilute phase much like the vapor from a
40
simple turndown). Avidan et al. (1990) report that commercial experience with close-coupled
cyclones resulted in a 40% reduction in C2- gas make.
In addition to increased severity, catalyst additives such as ZSM-5 can be used to increase FCC
olefin yields. Hsieh et al. (in print) report on the use of additives in FCC including the family of
ZSM-5 type materials. Young et al. (1991) give examples from the pilot plant of olefin yield
increases (and gasoline yield losses) when employing 4% of a ZSM-5 type material.
5.2 CHANGING THE COMPOSITION OF FCC GASOLINE.
FCC gasoline is a major contributor of aromatics, olefins and sulfur to the refinery gasoline pool
(Table 7 bascd on NPRA survey results). As FCC severity increases to generate more light
olefins, aromatics will become even more concentrated in the gasoline.
Table 7. Refinery Gasoline Blendstock Properties
Aromatics, Olefins, RVP, Sulfur,

Vol % Vol % psi ppm RONC MONC
FCC Naphtha 29 30 7.0 626 92.2 80.0
Reforrnate 66 I 4.6 43 98.5 88.4
Alkylate 0 0 7.9 26 93.2 91.1
Cs + Isomerate 1 0 15.7 2 85.4 82.8
LSR Naphtha 3 I 13.3 155 74.1 72.1
n-Butane 0 3 58.5 14 94.2 89.6
Toluene/Xylene 95 0 1.2 7 110.3 100.9
MTBE 0 0 9.2 0 113.9 98.9
A new generation of catalyst being developed by Davison (RFG-I) has the potential to help solve some of
the reformulated gasoline issues. Early micro-activity testing ofRFG-1 is shown in Table 8 reported by
Young et al. (1991). Compared to a USY type catalyst and a USY with 10% ZSM-5 (additive OHS), RFG-
1 makes more light olefms (including isoamylene which can be used to make TAME - tertiary amyl methyl
ether - another potential oxygenate for gasoline blending). In particular, isobutylene is about 40% of C4=,
very close to thermodynamic equilibrium. Gasoline olefins are up, but aromatics arc down.
41
Table 8. RFG-1 Selectivity Comparison with USY and USY/ZSM-5

Young et al. (1991)
MAT 980°F, 30 Sec. Contact Time
90% USY
Catalyst LD. USY 10% OHS RPG-l
Cat./Oil 3.90 3.90 3.70

Conversion, Wt % 60.0 60.0 60.0
Yields, Wt %
H2 0.090 0.082 0.053
Total C 1 + C2 1.75 1.90 1.76
C= 4.3 8.2 6.1

J
Total C1's 5.0 9.1 7.0
I-Butene 1.2 1.6 1.6

Isobutylene 1.6 2.6 3.6
trans-2-Butene 1.7 2.4 2.4
csi-2-Butene 1.1 1.5 1.5
Total C4= 5.7 8.1 9.1
i-C 4 2.4 3.1 2.5
n-C 4 0.5 0.6 0.6
Total C4 's 8.6 11.8 12.2
Isoamylene 2.5 3.1 4.0

Total C3 ' C4 ' CS' Olefins 12.5 19.4 19.2
C s+ Gasoline 42.4 34.9 37.1

RONC 91.2 93.4 93.6
MONC 80.2 81.5 80.2
LCO 23.8 23.3 18.5

640 o P+ HCO 16.2 16.7 21.5
Coke, Wt % Peed 2.20 2.20 1.91
Gasoline Composition
Paraffins 35.1 31.4 26.4
Olefins 25.7 29.1 42.6
Naphthenes 9.3 8.4 7.3
Aromatics 29.9 31.1 23.7
42
Apart from FCC reactor and catalyst upgrades, distillation changes will be required to enable FCC
gasoline to be compatible with reformulation. Akbar et al. (1986) report that for a full range gasoline,
the aromatics are concentrated in the higher boiling material. The sulfur is also concentrated there. A
lot of the olefms are in the front end of the gasoline. Under reformulated gasoline scenarios it is likely
that FCC "gasoline" boiling above say 390°F may be distilled out of the gasoline pool and processed
elsewhere (e.g., in a hydrocraker). The front of the FCC gasoline may also be distilled out,
particularly the normal Cs olefins (which may be sent for alkylation) and reactive isoamylenes (which
may be used in TAME production). Removing the Cs=also reduces the RVP of FCC gasoline.
6. Resid FCC
In the Pacific Rim (and in other areas) as the increasing demand for transportation fuels outpaces the
growth in demand for fuel oil, simple topping refineries (Figure 1) are being upgraded with resid
FCCs to alter the refmery yield slate to meet the changing product demand. Figure 23 shows how the
refinery flow scheme may be modified to incorporate a resid FCC. The VGO from the vacuum
column is blended with some of the vacuum resid and the mix is sent to the resid FCC. The mix (or
the vacuum resid only) may be hydroprocessed ahead of the resid FCC to improve the feedstocks
crackability (and reduce resid FCC SO, and NO, emissions). In some cases, no vacuum column may
be necessary as all of the atmospheric tower bottoms may be fed directly to a resid FCC. The addition
of a resid FCC can reduce fuel oil to below 10% of refmery products (Figure 3).
~B:..:u=ta:..:ne:..:s=a::.:nd:..:L:::,i9",ht::cer,---_ _ _ _ _ _ _ _ _ _ _ _-+:~~c~~~ Gas
Naphtha
Processing 1 - - - - - - - - - + Gasoline
CS-20S"C
and
Crude Atm. Gas Oil Treating 1 - - - - - - - - - + Gas Oil
Oil Dis!. 205-370°C
Oletins
Gasoline
Resid to FCC
L--'-''l'''ac'''u''''um''-'-'-'Re''''s''''id''''uu''''m''--_ _ _ _----'_ _ _.... Fuel Oil

BP >S40"C
Figure 23. Resid Cracking Refinery
Khouw et al. (1990) in Figure 24 illustrate the range offeed CCR (conradson carbon) and metals
(nickel and vanadium) compatible with today's resid FCC technology. CCR in the feed makes coke
and too much coke will result in excessive regenerator temperatures (i.e., above 1350°F) that will kill
catalyst activity. Nickel in the feed deposits on the catalyst and acts to produce hydrogen and more
coke. Increases in hydrogen production quickly take up existing wet gas compressor capacity.
Vanadium in the feed deposits on the catalyst and kills the catalyst activity by destroying the
zeolite structure. A state-of-art resid FCC may process feed of about 6 to 9 conradson carbon with
43
metals on equilibrium catalyst (nickel plus vanadium) up to 7000 ppm. In resid FCC, catalyst is
actively withdrawn from the unit and replaced by metals free equilibrium catalyst to keep nickel and
vanadium levels on catalyst in a reasonable range .
• '00
,oo~------------------~---+-----------------,
t t
IranHvy ArabHvy
IranLt
80
Kuwa it
~________~~R~~N~~~'O~____~~______~~
45 Sassen FCC- Future ~OITOI81
Front_eriS Wor1d Crude
40 Slttlea Reserves
Shengli
35 ArabLt
30r---~--..~
......- .-.~.----~Q~"-"~M~~
2S
20 Ekoflsk
"FIOl1a
~60
~~
......8
"O$..
Oman
••••
Esslder
10
Wt % Conradson Carbon in Feed
Figure 24. Resid (370°C+) Properties in Relation to FCC Processability

Khouw et al. (1990)
Humbach et al. (1990) have reported resid FCC yields for Arabian Light atmospheric tower bottoms
with the FCC in maximum gasoline mode (Figure 25). These yields should be contrasted with those
for the VGO of a similar crude in maximum gasoline mode as given in Table 3. With the resid,
conversion and gasoline yield is lower, but coke and C 2- gas make is higher. Typically the resid FCC
will operate at about 980°F reactor temperature and 7 cat/oil.
C3 Liquid 104.8 LV %
Properties of light Arabian

Atmospheric Crude:
API 18.3
Sulfur. WI % 2.94
Conradson CarbonI Wt % 7.2
Mela's. WI ppm
Nicke' 6.8
Vanadium 22.5
Figure 25. Typical Resid FCC Yields - Humbach et al.

(1990)
44
A full resid FCC design offered by Stone and Webster (and also Total) is illustrated in Figure 26. To
date, over ten units of this design are in operation. The reactor design resembles good VGO reactors
(atomizing feed nozzles, efficient riser disengager, etc.) but there are two regenerators. Spent catalyst
from the reactor stripper flows to the first (lower) regenerator which is operated in incomplete CO
combustion (i.e., low heat release per pound of carbon). Ross (1990) reports that 40% to 70% of the
coke is burned in the first regenerator (all of the hydrogen on coke is burned off in the first
regenerator). Partially regenerated catalyst is lifted up to the second (upper) regenerator where
additional air is supplied to complete the coke combustion. The second regenerator operates in
complete CO combustion (i.e., high heat release per pound of carbon) giving low CORC values.
There are separate flue gas lines from each regenerator. Regenerated catalyst flows from the second
regenerator to the feed riser.
Proprietary Riser
Termination
Regenerator Reactor
2
Regenerator
1 Feed Riser
Air
/' t
Air
to Air·Lift Feed
Figure 26. Stone and Webster Full Resid FCC
As the operator adjusts air rate to the first regenerator he is determining how much coke will be
burned to CO there and how much will be burned to CO 2 in regenerator two. He is in effect
controlling the temperature of the upper regenerator. The aim is to keep regenerator two
temperatures from exceeding 1350°F to prevent catalyst deactivation.
Lowering regenerator temperature by only allowing part of the coke to burn to CO2 has been
practiced for many years in conventional one stage regenerators. The two regenerator system
45
offers the increased flexibility to move overall CO/C0 2 ratios over a wide range [Ross (1990)
reports 0.3 to over I] and still achieve low CORC's typical of complete CO combustion
conditions.
UOP offers a resid FCC (RCC) with two regenerators (developed in conjunction with Ashland) as
shown in Figure 27 from Hemler (1989). The reactor design is again comparable to the best
available VGO designs. Spent catalyst from the reactor stripper flows to the first (upper)
regenerator where the hydrogen in coke and some of the carbon in coke is burned off. The
partially regenerated catalyst flows to the second (lower) regenerator to complete the
regeneration. Flue gas from the lower regenerator is passed through the upper regenerator to use
up any excess oxygen. By doing this only one flue gas line is required.
r-"------"~ Reactor
Product
Vented Riser
TWO-Stage
Regenerator
Primary ~
Ai r '-rr,----'
Feed
Catalyst +
Cooler Diluents
Lift Gas
Figure 27. UOP Resid FCC (RCC) Process - Hemler (1989)
In addition to the regenerator temperature control achieved by adjusting the burn between the two
regenerators, UOP offers increased control by including catalyst coolers that can cool the catalyst
as it flows from upper to lower regenerators. The UOP/Ashland design was the first modern
catalyst cooler design to be offered commercially. Now Kellogg and Stone and Webster offcr
catalyst cooler designs.
Shell and Kellogg have designed full resid FCCs with one stage regeneration and large catalyst
coolers. Shell's designs have been reported by Khouw et al. (1990). The Kellogg design
46
(modified Orthoflow F) is reported by Whittington and Niccum (in print). It has close-coupled
cyclones and a two stage stripper (steam distributors at two elevations in the stripper) that is
claimed to reduce the hydrogen content in coke.
The addition of a catalyst cooler to a VGO FCC can also give that unit resid cracking capabilities.
If a full resid FCC can handle feeds up to 6 to 9 conradson carbon, a modified VGO unit with a
catalyst cooler should be able to handle 2 to 4 conradson carbon feed (assuming the unit has a big
enough air blower, wet gas compressor and product recovery equipment). The catalyst cooler
scheme offered by Kellogg, Stone and Webster, and UOP is shown in Figure 28.
Flue Gas
Lift Air
Figure 28. Flow Through Catalyst Cooler
Catalyst coolers are really shell and tube heat exchangers with vertical U-tubes. Catalyst flows
downwards out of the regenerator through the cooler on the shell side and is air-lifted back into the
regenerator. Small amounts of aeration are supplied at the base of the cooler to keep the catalyst
fluidized. By adjusting cooler aeration and lift air rate, cooler duties can be adjusted from zero up to
about 150,000 KBtu/Hr in a standard design. Ross (1990) reports that overall heat transfer coefficients
for coolers are 75 to 125 Btu/Hr Ft2 F. In the case of the UOP high efficiency VGO FCC design
(Figure 8), a catalyst cooler can be incorporated in a standpipe flowing catalyst from the upper to
lower regenerators (the lower regenerator in this case provides the air lift).
In addition to "flow through" catalyst coolers, UOP also offers a backmixed design as reported by
Cabrera et al. (1987). This design does not have an air lift, but relies on aeration at the base of the
cooler itself to control the flow of regenerated catalyst in and out of the cooler by convection. This
design is simpler to install in a revamp and gives similar performance to flow through designs.
47
7. The Future
Advances in catalysis and advances in hardware have gone hand-in-hand over the 50 year evolution
of FCC. That will not change.
Predicting catalyst dcvelopmcnts is outside the scope of this paper, but expect many of those
improvements to be related to environmental issues. Commercialization of catalysts like Davison's
RFG-I will be required to meet the challenges of the probable worldwide reformulation of gasoline.
SO, reducing additives are already available, but there is as yet no commercially available FCC
additive to reduce NO, emissions. Because of greenhouse effect concerns, there may even be the need
for a catalyst to achieve high FCC conversions at ultra-low coke makes.
Increasingly the FCC will be required to minimize production of undesirable products such as fuel
oil and aromatic transportation fuels such as heavy gasoline and LCO (for diesel blending). Instead
the FCC will be required to more controllably and selectively crack feedstocks to "more acceptable"
light gasoline and olefins (that can be recombined in downstream alkylation and ether plants to
make the acceptable fuels of the future). The FCC will become increasingly selective in the products
it makes.
Quick contact has the potential to be one way of achieving more control over the cracking process.
Gulf (now part of Chevron) and Stone and Webster developed a short residence time vapor-solids
contactor for ethylene cracking. Figure 29 from Ross (1990) shows how that device might be used in
FCC. Catalyst and oil/steam are introduced at the top of the downer (a downward flowing riser!). A
downer is preferred to a riser because it is closer to plug flow. After a contact time of 500
milliseconds or less the spent catalyst and reaction mix is quickly separated and the vapor quenched.
The exact contact time will depend on the catalyst used. If a very active and selective catalyst were
available, controlled contact times of 100 milliseconds are not inconceivable.
Catalyst
Product Vapor
Oil/Stm. ~rt-h
• Short Residence Time 250-500 ms

• Plug Flow-No Backmixing
• Rapid Primary Separation to Quench-l00 ms
• Exploit Selective Catalytic Cracking
• Control Thermal Degradation
Figure 29. QC - Quick Contact Reaction System for FCC - Ross (1990)
48
Bartholic et al. (1991) have already reported on a commercial trial with a short contact FCC device
(called MSCC - millisecond catalytic cracking). The relative change in yields they observed
compared to conventional FCC is reported in Table 9. Those yields are encouraging, but represent
only the first step as the hardware and the catalyst are far from optimized.
Table 9. "Conventional FCC" Yields Versus MSCC Yields

Bartholic et al. (1991)
MSCC Compared to FCC

(L V % Percentage Change)
Ethane and Lighter, Wt % -45

Propane -18
Propylene -16
lsobutane +12
n-Butane -9
Butylenes +4
C s-430°F +13
430-680°F -5
680°F+ -1
Coke, Wt % -5
Absolute LV % Change
C,+ Yield +4.6
Conversion +1.1
Gasoline Efficiency +7.3
Raw Oil Charge MSCC FCC
°API 23.4 22.9

Sulfur, Wt % 0.90 1.15
Con Carbon, Wt % 1.2 1.2
Aknowledgement
The author gratefully acknowledges the assistance of Karl Bussey (Kellogg), Chuck Hemler
(UOP) and Jay Ross (Stone and Webster) during the preparation this article.
49
Notation
Included are U.S. oil industry standard abbreviations that may be unfamiliar to some readers.
ABO FCC Apparent Catalyst Bulk Density (Lb/Ft3, kg/m3)

Bbl/D Barrels per Day. One Barrel is 42 U.S. gallons
BP Boiling Point
CFR Combined Feed rate Ratio, (fresh feed + recycle)/fresh feed
COB CO Boiler
CORC Carbon On Regenerated Catalyst
CSDY Chemically Stabilized and Dealuminated Y Zeolite
C 2- Ethane, ethylene, methane and hydrogen.
o 'P Diameter of standpipe (Ft, m)
Eo Cyclone single particle ("zero" loading) collection efficiency
FF Fresh Feed basis
GRU Gas Recovery Unit
H Standpipe vertical height (Ft, m)
HCO Heavy Cycle Oil (also called Bottoms, Decant Oil, Clarified Oil)
HOT Hydrotreated
LCO Light Cycle Oil
LPG Liquefied Petroleum Gas
LVO/O Liquid Volume Percent
MON Motor Octane Number ("C" or "clear" indicates lead free)
RCSV Regenerated Catalyst Slide Valve
ReY Rare Earth Y zeolite
RON Research Octane Number ("C" or "clear" indicates lead frec)
RVP Reid Vapor Pressure (psi)
SCF Standard Cubic Feet (Ft3 at 60°F and 14.7 psia)
U Superficial gas velocity (Ft/S, m/s)
USY UltraS table Y zeolite
VGO Vacuum Gas Oil
W Catalyst flux down standpipe (Lb/S Ft2 , kg/s m 2 )
Standpipe catalyst density (Lb/Ft" kg/m')
References
Akbar, M., B. Claverin, M. Borleg, and H. Otto, "Some Experiences with FCC Octane Enhance-
ment," Ketjen Catalysts Symposium, Scheveningen, The Netherlands, May 25-28 (1986).
API Manual on Disposal of Refinery Wastes. Volume on Atmospheric Emissions, Chapter 11 -
Cyclone Separators. API publication 931, May (1985).
Auto/Oil Air Quality Improvement Research Program. Technical Bulletins No.1 to No.5 prepared
by/for Marathon, Mobil, Chevron, Ford, Conoco, GM, Amoco, Unio, Chrysler, Shell, BP,
Phillips, Arco, Exxon, Ashland, Texaco and Sunoco. December (1990) to June (1991).
Avidan, A.A., M. Edwards and H. Owen, "Fluid Catalytic Cracking - Past And Future
Challenges," 6th. International Confercncc on Fluidization, Banff, Alberta, May 7 -12 (1989).
Avidan, A.A., F. J. Krambeck, H. Owen and P. H. Schipper, "FCC Closed Cyclone System Elimi-
nates Post-Riser Cracking," NPRA Annual Meeting, San Antonio, Texas, March 25-27 (1990).
50
Bartholic, D.E., M. R. Keirn and M.Soudek, "The Simplified Approach to Residual Oil
Upgrading," NPRA Annual Meeting, San Antonio, Texas,March 17-19 (1991).
Cabrera, C.A., L. A. Lacijan and M. O. Lunda, "Mechanical Considerations in FCC Design,"
Ketjen Catalysts Symposium, Amsterdam, The Netherlands, May 27-30 (1984).
Cabrera, C.A., C. L. Hemler and S. P. Davis, "Improve Refinery Economics via Enhanced FCC
Operations," 8th. Katalistiks FCC Symposium, Budapest, Hungary, June 1-4 (1987).
Dean, R.R., J-L Mauleon and R. W. Pfeiffer, U.S. Patent 4,331,533(1982).
Denny, R.F., N. L. Gilsdorf, F. M. Hibbs, E. J. Houde, M. E. Reno and R. P. Silverman, Quoting
BP Energy Data as part of "The Refining Challenge for the 1990's," UOP 1990 Technology
Conference.
Hemler, C. L., "Fluid Catalytic Cracking. Reflections and Expectations," AIChE Summer
National Meeting, Philadelphia, Pennsylvania, August 22 (1989).
Hsieh, C. R., A. S. Krishna, A. R. English, T. A. Pecoraro and C. W. Kuehler,"Development and
Application of Catalytic Additives in FCC Units," to be published in the proceedings of
Interpec 1991.
Humbach, M. J., D. M. Cepla, B. W. Hedrick, C. L. Hemler and H. J. Niclaes," Residue
Conversion," UOP 1990 Technology Conference.
Jazayeri, B., "Optimize FCC Riser Design," Hydrocarbon Processing, May (1991).
Khouw, F.H.H., M. J. P. C. Nieskens, M. J. H. Borley and K. H. W. Roebschlaeger," The Shell
Residue Fluid Catalytic Cracking Process Commercial Experience and Future
Developments," NPRA Annual Meeting, San Antonio, Texas, March 25-27 (1990).
King, D.F.,"Estimation of Dense Bed Voidage in Fast and Slow Beds of FCC Catalyst,"
Fluidization VI edited by J. R. Grace, L. W. Shemilt and M. A. Bergougnou. Engineering
Foundation, New York (1989).
King, D.F., "Fluidized Catalytic Crackers: An Engineering Review," Fluidization VII edited by
O. E. Potter and D. J. Nicklin. Engineering Foundation, New York (1992).
King, D.F., R. M. Forde, P. W. Leaney, E. M. Makar and F. A. Zenz,"FCC Cold Modelling Helps
Solve FCC Standpipe Flow Problems," Fluidization VI edited by J. R. Grace, L. W. Shemilt
and M. A. Bergougnou. Engineering Foundation, New York (1989).
Lomas, D. A., C. A. Cabrera, D. M. Cepla, C. L. Hemler and L. L. Upson, "Controlled Catalytic
Cracking," UOP 1990 Technology Conference.
Murphy, J.R., and Y. L. Cheng,"The Interaction of Heat Balance and Operating Variables in Zeolitic
Catalyst Operations," 5th. Katalistiks FCC Symposium, Vienna, Austria, May 23-24 (1984).
NPRA survey as interpreted by G. W. Young. Private Communication.
Raterman, M.F., Oil & Gas Journal, January 7 (1985).
Ross, J.L.," Stone and Webster Technology Update for the 1990's," Stone and Webster RFCC
Symposium, Tokyo, Japan, October 17 (1990).
Whittington, E.L. and P. K. Niccum," Kellogg's Fluid Catalytic Cracking Process," to be
published by Japan Petroleum Institute's PETROTECH.
Young, G.W., T. G. Roberie, W. Suarez, W-C Cheng and E. T. Habib, Jr.," Reformulated
Gasoline: The Role of Current and Future FCC Catalysts," NPRA Annual Meeting, San
Antonio, Texas, March 17-19 (1991).
SCIENTIFIC ASPECTS OF NOVEL CATALYSTS FOR FCC
ALAN W. PETERS, W-C CHENG, and T.G. ROBERIE

w. R. Grace Co. - Conn.
Washington Research Center
7379 Route 32
Columbia MD 21044
ABSTRACT. This contribution reviews the most recent progress on the development of novel FCC
catalyst. The following subjects are considered: catalyst preparation and structure (matrix, binder, zeolite
component), catalytic selectivity (stability, mesoporosity, nonframework alumina, hydrogen transfer),
isobutene production for reformulated gasolines and FCC additives (CO promoters, SOx transfer catalysts,
and octane additives).
1. Preparation and Structure of FCC Catalyst
An FCCU (Fluid Catalytic Cracking Unit) utilizes a catalyst in the form of a coarse powder with
an average particle size of about seventy microns. The catalyst is fluidized by the oil vapor in
the reactor and by air and steam in the regenerator as it alternately passes between the reactor
and regenerator (1). At the bottom of the riser hot catalyst mixes with and heats the relatively
cooler oil to about 500-550°C. The oil expands as it heats up and, in the presence of the
catalyst, converts to lighter products. The expansion of the oil plus products blows the catalyst
and the oil up the riser into the reactor. A series of cyclones serves to separate the catalyst from
the reaction products including gasoline, light gases, and heavy oil. The catalyst passes through
a stripping section where steam helps remove entrained hydrocarbon from the catalyst. From the
stripper the coked catalyst discharges into a regeneration vessel. Air is injected into the
regenerator and the coke is burned to CO, C02, water, and trace amounts of sulfur and nitrogen
oxides. The heat of this reaction is enough to increase the temperature of the catalyst in the
regenerator to - 750°C. The hot catalyst travels down a standpipe to the reactor where the hot
catalyst again mixes with the oil, and the cycle repeats.
The typical FCC catalyst consists of active zeolite, an inert, a matrix, and a silica/alumina
binder (2, 3). The zeolite may comprise from 10% to 50% of the catalyst, the binder 5% to
20%, with the rest consisting of an inert such as clay or a matrix component composed of silica
alumina or alumina. The components are slurried in water and spray dried to give desirable
physical properties such as attrition and density. If the zeolite is faujasite it will be exchanged
with enough ammonium ion and rare earth to give the desired chemical composition.
Faujasite is normally prepared at a silica to alumina ratio of about 5: 1 and contains about 13%
soda (Na20) as synthesized. The sodium may be removed by exchange with ammonium or rare
earth ions either before or after the preparation of the catalyst. Modern FCC catalysts are often
prepared using USY or DEALY, a form of faujasite prepared by partially removing sodium to
51
H.I. de Lasa et al. (eds.), Chemical Reactor Technologyfor Environmentally Safe Reactors and Products, 51-69.
© 1993 KILMer Academic Publishers.
52
a level of 3% to 5% and subsequently removing aluminum from the framework. After

dealumination the sodium level is further reduced to 1 % or less (zeolite basis) on the final catalyst
(3).
1.1. THE MATRIX AND BINDER
The average size of a typical FCC catalyst particle is about 65 /L with a small amount of fines in
the 0 /L to 40 /L range. The density of the catalyst defined as the Average Bulk Density (ABD)
is typically 0.65 to 0.85 g/cc. The physical properties of the catalyst, controlled by the preparation
process and can have a significant impact on catalyst performance. Fluidization and flow
properties in the standpipe depend in part on the properties of the catalyst. The particle density
as well as the particle size distribution and to an extent the shape of the catalyst particle are all
important (4). Fluidization properties can be adjusted by adjusting the amount of fines or the
ABD in the manufacture. The retention of the catalyst in the cyclones during the separation of
the catalyst from product on the reactor side or from the flue gas on the regenerator side depend
strongly on the attrition resistance and particle integrity of the catalyst as well as on the particle
size, shape and density (5).
Catalytic performance also depends on the formulation and preparation. The selectivity and
bottoms cracking of the catalyst depends strongly on the type and the amount of the matrix
component. Matrix activity can be provided by silica alumina formulations similar to the older
pre - zeolite catalysts. Bulk alumina has been identified as a component in a commercial catalyst
(6). Silica alumina matrices have also been evaluated for use in FCC catalysts (7). Thermally
and chemically treated clays have been used (8). Clays treated by newly developed procedures
(9) have been suggested as matrix components with improved selectivity. The relative stability
of the matrix and zeolite components can also be important. If the matrix is more stable than the
zeolite, during use the catalyst will acquire the selectivity characteristics of the matrix and the
improved gasoline selectivity characteristic of the zeolite will be lost. On the other hand, a
catalyst with a less stable matrix will have poorer selectivity for bottoms cracking. The binding
technology can also playa major role in catalyst activity and selectivity. Superior binding
technology can result in catalysts containing more of the active components, zeolite plus matrix.
1.2. THE ACTIVE ZEOLITIC COMPONENT
The zeolite has the largest effect on the activity and selectivity of the catalyst. The zeolite most
used in current cracking catalyst formulations is a dealuminated and stabilized form of faujasite.
As it occurs in an operating FCCU catalyst, faujasite is not a simple structure. As a result of the
high temperatures and the presence of steam the faujasite dealuminates in the regenerator during
operation. Several types of nonframework alumina are formed which mayor may not have
catalytic activity. As the framework dealuminates large holes in the lattice develop forming a
system of catalytically active mesopores. The mesopore system can have a major effect on
bottoms cracking activity. As the framework dealuminates it becomes more stable. The
aluminum sites remaining in the framework become more isolated and consequently both the
activity and the selectivity for coke, light gases, and octane can change dramatically. Besides
modified forms of faujasite, there are other useful and potentially useful zeolites. Currently
additives containing ZSM-5 are available. These additives have been useful in providing a higher
octane gasoline along with more light olefins used to produce alkylate. Catalytic compositions
have also been described that are useful in producing increased amounts of isobutene, a feedstock
component for MTBE (Methyl Tertiary Butyl Ether) production. MTBE is currently an octane
53
additive of choice for the production of reformulated gasoline, an environmentally motivated

higher octane gasoline formulation. In the following we will discuss all of these issues.
1.2.1. Faujasite. Faujasite has the framework shown in Figure 1. It consists of tetrahedral
silicon and aluminum atoms connected by oxygen bridges as shown. In the as-synthesized form
about 25% to 50% of the tetrahedra are aluminum and the rest are silicon. Since the unit cell
contains 192 tetrahedra, 50 to 96 of the tetrahedra will be aluminum and the rest will be silicon.
The aluminum atoms have a formal negative charge that is neutralized by a positive sodium ion.
The sodium in the faujasite can be exchanged with ammonium ions in a water solution to give
an ammonium sodium form containing 1 % to about 5% sodium. Calcination decomposes the
ammonium zeolite salt releasing ammonia and leaving behind the protonated acidic form of the
zeolite.
°
Figure 1. Structure of Faujasite, showing a portion of the unit cell and possible arrangements of
silicon, aluminum and oxygen atoms. Protons are located on 01 and 3 , M Czjzek, H. Jobic,
A.N. Fitch, and T. Vogt, J.Phys.Chem., 96, 1535 (1992).
1.2.2. Dealuminated Faujasite (USY. DEALY). The presence of large amounts of aluminum
destabilizes the framework. The effect is probably a result of either the acidity or the ionic
character associated with the aluminum. It is known that aluminum oxygen aluminum bonds are
sufficiently unstable in zeolites that structures involving neighboring aluminums do not occur, and
structures having high amounts of aluminum in second nearest neighbor structures are relatively
unstable, especially in hydrothermal environments. It has been found that dealuminated faujasite
has greatly improved stability in the FCCU regenerator.
S4
There are two procedures used to prepare dealuminated zeolites. One procedure involves a
rapid hydrothermal dealumination at a relatively high temperature of ~ 500°C (10,11). The
resulting material contains a network of larger zeolitic mesopores within the crystal and
connecting directly to the zeolitic pore system. Another procedure uses silicon hexafluoride at
a relatively low temperature, :s;; lOOoe (12). The result is a slow dealumination with the
formation of much less mesopore structure. The two procedures result in zeolites that differ in
the distribution of active framework aluminum sites as well as in the presence or absence of
mesoporosity. The liquid phase dealumination results in a zeolite with the active aluminum sites
preferentially removed from the outside of the zeolite particle or crystal. Further, during the
dealumination process, additional silicon is deposited on the zeolite surface (13). The exact
opposite happens during hydrothermal dealumination. While the framework is more or less
uniformly dealuminated, the aluminum atoms removed from the framework do not remain within
the pore system, but are observed to migrate to the outside of the zeolite particle (14).
Consequently, unless the alumina is removed, the outside of the zeolite particle is alumina rich.
In both cases post dealumination chemical treatments are necessary. In the case of the use of
silicon hexafluoride dealumination, it is necessary to remove every trace of fluoride in order to
preserve stability (15). In the case of hydrothermal dealumination, additional sodium is removed,
and nonframework alumina mayor may not be removed as desired.
1.2.3. The Zeolite in the Operating FCCU. The dealumination procedure used to prepare
ultrastable Y zeolite only removes about 30% of the original framework alumina. The
framework undergoes additional and profound structural changes in the hydrothermal environment
(-740 e, -0.4 atm. steam) of the FeeU. Typically between 50% and 80% of the remaining
0
alumina is finally removed from the framework and is deposited in or near the zeolite particle
as nonframework alumina. The degree of dealumination in the regenerator can be controlled by
the degree of rare earth exchange (16). Nonframework alumina has been observed to form three
chemically distinct structures, one or more of which may be catalytically active. The formation
of additional mesoporosity is another consequence of further dealumination with the catalytic
consequence of improved bottoms conversion and coke selectivity. Further, as the framework
dealuminates, the remaining aluminum sites become more isolated and the catalytic activity and
selectivity of the framework change dramatically. Increased site isolation is associated with
decreases in hydrogen transfer activity and improved coke selectivity.
2. Catalytic Selectivity of FCC Catalysts Containing Dealuminated Faujasite
In the following sections the catalytic effects of the three major structural changes in the operating
dealuminated zeolite will be discussed. These structural changes include the formation of
nonframework alumina, the formation of mesoporosity, and a reduction in the number of
aluminum acid sites in the framework.
2.1. THE STABILITY OF FAUJASITE IN THE FCC CATALYST
Faujasite stability is frequently interpreted as the retention of zeolite surface area after steaming
where the surface area is estimated using the t-plot method (17, 18). However, the zeolite
framework will initially contain 15% to 18% alumina. During deactivation and dealumination
in the regenerator most of this alumina will be removed from the framework. Microprobe studies
have shown that the alumina migrates to the outside surface of the zeolite particle during the
55
dealumination process, probably through the mesopore system. Since this alumina is lost from
the zeolite structure there is a real loss of surface area of about 10% to 15%. A similar loss will
also be observed using XRD measurements.
There will be a further apparent loss in zeolite surface area resulting from the formation of
mesoporosity. In the analysis of FCC catalysts, surface area in the small pore range is assumed
to be zeolite, and surface area in the mesopore range is assumed to be non zeolitic. For a
perfectly stable zeolite one might expect about an 85% retention of surface area in the zeolite
range, or 100% if a correction is made for the loss of i11umina from the framework. However,
a zeolite with 800 m2 /g may develop as much as 100 m2 /g of meso porosity during dealumination
with an apparent loss of as much as 200 m2 /g of apparent zeolite surface area associated with the
development of the 100 m2/g mesoporosity. Even if the alumina loss is corrected for and the
framework remains intact so that none of the silicon in the framework is lost, one expects an
apparent loss of 20% of the surface area depending on the amount of mesoporosity formed.
Since the apparent loss will not affect XRD (X-Ray Diffraction) intensities as strongly, in zeolite
systems containing mesopores there may be a significant discrepancy in the stability measured
by t-plot and XRD methods.
2.2. MESOPOROSITY
Mesoporosity is a characteristic of hydrothermally dealuminated zeolites identified in the early

1980's. Since then a considerable amount of TEM (19, 20) and adsorption (21) evidence has
accumulated concerning the size and surface area of the mesopores as well as the potential
activity and selectivity benefits associated with mesoporosity. It appears that mesoporosity is
formed during the initial period of rapid dealumination. Although the use of slow, low
temperature dealumination procedures do produce some mesoporosity, the amount is much less
than is produced by high temperature rapid hydrothermal dealumination techniques. This is
illustrated in Figure 2 where the mesoporosity development of two sieves, one hydrothermally
dealuminated to 2.454 nm unit cell is compared to the same zeolite dealuminated using silicon
hexafluoride to 2.452 nm. Both USY faujasites were subsequently treated hydrothermally to
further reduce the unit cell size. There is a significant difference in the amount of mesoporosity
developed after both the initial and subsequent hydrothermal treatments.
It has been shown that gas oil and certainly resid cracking is a diffusion controlled process.
Size effects on both activity and selectivity have been shown (22). The mesoporosity has the
same effect as reducing the zeolite particle size, but without compromising the stability of the
zeolite. Results from a previous study showed that the effect of mesoporosity is similar to the
effect of smaller sieve crystallite size on bottoms cracking (23). While there are no studies
comparing the selectivities of an alumina matrix with mesopores for bottoms cracking, one would
expect differences in coke yields as well as selectivities in the presence of metals. The actual
surface area generated by mesopores in a high sieve catalyst can be similar to the surface area
generated by a high matrix catalyst. In practice, both mesoporosity and an active matrix
component are often present.
2.3. CATALYTIC EFFECTS OF NONFRAMEWORK ALUMINA
As the zeolite lattice dealuminates, the aluminum can form three chemically distinct non
framework aluminum species identifi.able by 27 AI MASNMR. Octahedral and tetrahedral species
commonly occur in alumina and in silica alumina materials including zeolites and are identifiable
by a chemical shift of about 0 (octahedral) (24) and 52 ppm to 62 ppm (tetrahedral) (25). It is
56
the tetrahedral coordination which produces the acidic character associated with aluminum sites
in zeolites and in amorphous silica aluminas. The chemical shift for the tetrahedral peak in
faujasite is about 59 to 61 ppm, while for the amorphous materials the peak is slightly broader
and the shift is 54 ppm to 56 ppm. These differences probably reflect differences in charge
distribution or in bond angle distributions around the aluminum. Other zeolites such as HZSM-5
also have a shift in the 54 ppm to 57 ppm range. After a severe hydrothermal dealumination new
peaks appear at about 0 ppm, an octahedral species, and at about 30 ppm, a peak identified as
a pentacoordinate species (26). The tetrahedral peaks broaden but do not shift. These results are
illustrated in Figure 3 showing the spectra of clay, a silica alumina cogel, and faujasite after
hydrothermal dealumination. In all cases all three peaks are present. The pentacoordinate peak
is characteristic of hydrothermally treated silica alumina materials. It is found in nature in
andalusite, an aluminum silicate mineral. It has also been suggested that the 30 ppm peak could
be due to an aluminum in a distorted tetrahedral environment. However the relatively low shift
in frequency with field strength suggests a smaller degree of asymmetry than would be required
for assignment as a distorted tetrahedral environment. In dealuminated faujasite a nonframework
tetrahedral peak has been identified by 2 dimensional 27 Al MASNMR as well as in conventional
spectra. It occurs as a shoulder at about a 55 ppm and is just barely resolved from the peak at
60 ppm due to the tetrahedral framework alumina (27), Figure 4.
100
80
111
Q)
<'i:
(])
0
60
111
"t
::J
(/)
(])
15
a.
40
0
(/)
Q)
~
20
0
5 16.25 27.5 38.75 50
# AI Removed/Unit Cell
Figure 2. Mesoporosity of Zeolites determined by the t-plot method. The sample of USY
prepared by low temperature dealumination (0) involving the removal of about 28 aluminum
atoms per unit cell produces significantly less mesoporosity after subsequent hydrothermal
dealumination than a sample of USY prepared initially by hydrothermal dealumination (x).
The catalytic activity of these materials has been the subject of considerable discussion. A
prominent role has been proposed for nonframework alumina in generating strong acidity
57
responsible for the activity and selectivity of dealuminated zeolites generally and particularly
faujasite catalysts (28, 29). It is proposed that some of the nonframework coordinates with
isolated sites in the framework to generate strong acidity. These strong sites then are responsible
for some of the unique activity and selectivity of USY based FCC catalysts. The involvement
of octahedral aluminum in the formation of these super acid sites is viewed as unlikely, as is the
involvement of the pentacoordinated species based upon experimental work. Samples of zeolite
containing varying amounts of nonframework alumina have been prepared, Table 1. Catalytic
cracking results using catalysts containing these zeolites have not shown significant variations in
either activity or selectivity, Table 2.
27.7! f: 2.0
55.6(\\
a
1_.
/ . 32.0 f)
4 .1
~ 56.6~V
I
32.4 b
~2.7
\
400 300 200 100 o ·100 -200 ·300 ppm
Figure 3. 27Al MASNMR 104.3 MHz spectra of hydrothermally treated a) clay, b) an amorphous
silica alumina, and c) faujasite, A.W. Peters, G.C. Edwards, M.P. Shatiock, T.G. Roberie,
K. Rajagopalan, and E.T. Habib, Actas del XI Simposio Iberoamericano de Catalisis,
Guanajuato, Mexico (1988) Vo.III, 1417.
A nonframework tetrahedral alumina (NFT A) species is a more promising candidate since

tetrahedral aluminum oxides are acidic in other systems. The NFTA has been associated with
58
infra-red bands in the 3610 cm·! region typically associated with strong acidity (30) and also with
poor selectivity (31,32). In our laboratory we have been able to prepare a zeolite containing the
55 ppm peak: after a high severity steam calcination. In this case the zeolite has a high degree
of % crystallinity retention but relatively poor selectivity, Table 3 (33). The poor selectivity is
only circumstantially associated with the existence of the NFTA peak:. The occurrence of the
NFTA species is not associated with any particular dealumination procedure. Zeolites after both
silicon hexafluoride dealumination and after hydrothermal dealumination show the NFTA peak:
(34).
60,7
54.3
55
a b
120 tlO 40 o -40 120 40 o -40

PPM PPM
Figure 4. 27AI MASNMR spectra of faujasite dealuminated to a) 2.422 nm uc and b) 2.420 nm

uc showing a doublet in the tetrahedral region at 60.7 ppm and at 54.3 ppm for sample a). From
A.Corma, V.Fornes, A.Martinez, and J.Sanz, Fluid Catalytic Cracking, M.Occelli, ed., ACS
Sym. Ser.375, 1988, p.22.
In summary, the role of nonframework alumina is not clear. There are claims for a positive
role and claims of a more negative impact on selectivity. If there is an effect, it is probably
associated with the tetrahedral species.
2.4. THE REDUCTION OF SITE DENSITY IN THE ZEOLITE FRAMEWORK
One might think that the aluminum occurs at random throughout the lattice. This is not true.
Since the aluminum is a charge center, there is a degree of avoidance of closely neighboring
aluminum atoms due to charge repulsion. One result of the repulsion is that aluminum tetrahedra
are not directly linked in the zeolite lattice, a general rule known as Lowenstein's Rule (35). A
consequence of this rule is that the lattice will have a minimum Sil Al ratio of 1, and generally
Si/AI > 1. Another consequence is the hydrothermal instability of zeolites containing high
amounts of aluminum and with a low Si/AI ratio. The Si-O-AI bonds are easily hydrolyzed in
the presence of the acid associated with the lattice. The hydrolysis is self catalyzed, and the
59
the presence of the acid associated with the lattice. The hydrolysis is self catalyzed, and the
highly polar lattice rapidly dealuminates. Consequently the FCC catalyst industry has gone to
USY based catalysts with a fresh SilAl ratio of about 4. In the operating catalyst the ratio is in
the range of about 20 or 40 to one. Compared to the older, higher unit cell catalysts these
catalysts are more hydrothermally stable, a little less active, and contain more zeolite. They give
a more olefinic and higher octane gasoline and are much more coke selective.
Table 1. Preparation of Chemically and Hydrothermally

Dealuminated Y Sieves
DEAL Method Hydrothermal SiF6=
As Prenared
% Alumina 23.5 17.5 11.3 12.0
% N~O 0.80 0.12 0.29 0.22
# FAl!uc 52 38 25 27
Unit Cell, nm 2.462 2.450 2.443 2.447
After Deactivation 1500°F, 100% Steam, 4 Hrs.

Unit cell, nm 2.423 2.422 2.427 2.425
# NFAl!uc 47 34 17 20
It is currently not possible to quantify the degree of site isolation in these catalysts at a given
unit cell. At a unit cell size of 24.47 there will be about 32 aluminum atoms per unit cell, and
it is theoretically possible to achieve complete site isolation provided there is a strong enough
tendency for aluminum atoms to be as far apart as possible. On the other hand without a strong
tendency towards separation one expects a distribution such that there will always be some second
nearest neighbor sites. Current results show that there is some continuing tendency towards site
separation at low unit cell sizes, but it is not complete. Specific building blocks with a specific
aluminum siting within the blocks have been suggested (36), but there is no evidence for these
structures beyond simple compatibility with the MASNMR spectra. Rather, the spectra are
compatible with a number of specific structures consistent with a tendency towards second nearest
neighbor aluminum - aluminum avoidance (37).
2.5. SELECTIVITY CONTROL BY HYDROGEN TRANSFER
Activity is more or less linear with the amount of framework alumina for ZSM-5 and high silica
alumina faujasite provided no non-framework alumina is present (38, 39). Selectivity is a
somewhat more complicated issue. Both an octane increase (40) and a coke decrease (17) have
been associated with site isolation. A very sharp increase in the olefin content of the gasoline
as well as an increase in the light gas is observed as the unit cell drops below 2.430 nm. The
increase in light olefin content from 10% to as much as 25 % of the gasoline is responsible for
most of the octane increase. Coke varies in a different way. It decreases more slowly as the unit
cell decreases, and levels out for unit cell sizes below 2.430 nm. These results imply that the
hydrogen transfer activity involved in coke formation is different from the activity responsible
60
for high olefin yields. The unit cell is only a measure of the average aluminum content of the
framework. The selectivity results imply that a more detailed knowledge of the distributions of
sites and the degree of site isolation is desirable.
Table 2. Selectivities of SiF= and Hydrothermally Dealuminated Y Catalysts
DEAL Method Hydrothermal Chemical Octacat
# NFAI/uc 47 34 17 20
Deactivation 1500°F, 100% Steam, 4 Hrs.
% Xtal. Loss 30 25 10 10
CIO 4.0 3.8 3.9 4.0 4.0
Wt. %
Conv 62.0 62.8 62.3 57.4 61.5
H2 .07 .09 .10 0.09 .09

Cl + C2 1.76 1.84 1.81 1.96 1.76
C3 5.2 5.6 5.2 5.3 5.2
C4 3.4 13.5 13.3 8.6 8.9
C5+ Gaso. 43.5 43.0 43.9 39.1 43.6

Sel. 0.702 0.685 0.705 0.681 0.712
RON (GC) 91.1 91.4 91.5 91.8 91.2

MON 80.2 80.8 80.3 80.3 80.3
LCO/HCO 1.53 1.63 1.69 1.32 1.57
Coke 2.2 2.5 2.1 2.1 2.0
o Pentacoordinate and octahedral nonframework aluminas have no significant

effect on activity or selectivity.
o Removal does increase apparent crystallinity by XRD (a test artifact).
One possibility is that site density in the sense of the number of sites per unit cell plays a role.
If hydrogen transfer is a bimolecular reaction, then it is reasonable to suppose that as the zeolite
dealuminates and the site density decreases the occurrence of hydrogen transfer also decreases.
This result has been found by A. Corma (41). He measured the adsorption isotherms for heptene
over a series of zeolites dealuminated to different extents. He found a significant decrease in
adsorption for the more dealuminated samples. A similar approach is to suggest that there are
two kinds of sites, isolated and paired. Isolated sites result in cracking, but not in hydrogen
transfer (36). Paired sites represent the ability of the zeolite to adsorb two molecules in close
proximity resulting in both cracking with a high degree of hydrogen transfer. The total olefin
content would be roughly proportional to the ratio of isolated to total sites. For moderate
61
conversions the olefin content of the gasoline should be independent of catalyst to oil ratio as well
as conversion.
Table 3. Selectivities of catalyst containing nonframework

alumina observed at 55 ppm by 27 Al MASNMR.
Sieve Preparation SID SID 55 ppm NFA

steam/acid 3x
%Na20 0.037
%AI203 2.86
%Xtal 86
UC 24.26
Catalyst Properties (35% sieve)
%Xtal 25
UC 24.25 24.25 24.25
Catalytic Selectivities, wt. %.
Conv. 69.3 45.6 45.0
H2 0.07 0.03 0.101
C1 0.68 0.34 0.60
C1+C2 2.09 1.13 1.79
C3= 4.9 3.0 3.2
C3 1.1 0.5 0.7
IC4 4.1 1.9 1.4
NC4 0.8 0.4 0.4
C4= 5.2 3.7 4.1
Gasoline 47.7 33.7 30.8
Gasoline Sel. 0.69 0.74 0.68
Coke 3.2 1.4 2.4
It has also been proposed that hydrogen transfer rates are proportional to the time the reacting
species stay on the active site, and so may be inversely related to acid strength (42). An
increase in acid strength results in higher turnover numbers, less time on the site and therefore
less hydrogen transfer. It is likely that both site densities and the time on site affect hydrogen
transfer rates.
Whatever the explanation, there is no doubt that different zeolites even at the same relative
aluminum and silicon contents have dramatically different relative rates of isomerization and
hydrogen transfer (43). Using the reaction of cycIohexene to form either cycIohexane,
cyclopropane, or cycIopropene the relative rates of isomerization for three different zeolite
structures were measured for samples prepared at the same Si/AI ratio - 12. The results showed
significant differences of nearly an order of magnitude in the relative rates of isomerization to
hydrogen transfer. The structural details that provide these differences remain elusive.
2.6. ISOBUTENE PRODUCTION IN THE FCC FOR REFORMULATED GASOLINE
Gasoline reformulation in the USA is motivated by environmental concerns. There is a desire

to reduce the aromatic content of gasoline, to reduce the vapor pressure, and to add oxygenates
62
for a cleaner burning fuel (44). Recent results show that the addition of oxygen in the form of
ethers such as MTBE (Methyl Tertiary Butyl Ether) or TAME (Tertiary Amylene Methyl Ether)
produces less carbon monoxide (45, 46). Reducing the vapor pressure has an obvious effect on
fugitive hydrocarbons. The beneficial effects of reducing aromatics on tailpipe aromatics has also
been demonstrated (47 - 49). The ethers are prepared by the acid catalyzed relatively low
temperature reaction of methanol or ethanol with isobutene or with isoamylene. The proposed
composition of 2 % to 2.7% oxygen implies that about 15% of the reformulated gasoline will be
an ether. This in turn requires a significant increase in the production of C4 and C5 isoolefins.
It is known that faujasite based catalysts do not produce equilibrium concentrations of isobutene,
and recent studies in a riser suggest that less than equilibrium concentrations of isoamylene are
produced. Consequently there is a need for a catalyst that produces at least equilibrium amounts
of isoamylene and isobutylene. Although there was initial concern with high olefin concentrations
in the FCC gasoline, some of that concern has abated with the recent conclusion from the
Auto/Oil Air Quality Research Program that olefins in gasoline, along with end point reduction,
can significantly reduce hydrocarbon tailpipe emissions (50).
As a consequence of these results, the production of olefins and especially isoolefins in the
FCCU becomes an important priority. Examples of gasoline compositions obtained from the use
of various faujasite based catalysts are shown in Table 4. Although there is some improvement
in isoolefin production with decreases in the unit cell of the faujasite USY based catalyst, the
amount of isobutene produced is far short of the amount thermodynamically available. In the
case of C5 olefins the difference is much smaller, depending on what thermodynamic compilation
is used, Table 5. Besides differences in olefin branching, another significant difference between
catalytic composition and the thermodynamically predicted composition is in the amount of the
trans isomer. In the case of the C5 olefins, all the current estimates (51-53) show that the cis and
trans isomers should occur at about the same concentration. This result is not found catalytically.
The observed abundance of the trans isomer is about twice the abundance of the cis isomer. The
originally published thermodynamic results (54) are in agreement with this result, in contrast to
current results. In this case of considerable practical importance there is some question
concerning the accuracy of the thermodynamics.
Table 4. Distribution of C4 and C5 olefins as a result of gas cracking over faujasite at

different unit cells.
Unit Cell Sizelnm Equilibrium (33) 2.426 2,429 2,431 2,439
C40lefins
1-C4= .1401 .216 .228 .228 ,256
c2C4= .1660 ,173 .186 ,195 ,205
t2C4= .2452 .295 ,320 .317 .368
iso C4= .4486 .317 ,266 ,260 ,171
C50lefins
1-CS= ,0485 .081 ,089 .084 .093
c2Cs= .1162 ,124 ,132 .139 .142
t2Cs= .1199 .223 .237 .249 ,255
2mlC4= ,2365 ,183 ,177 ,164 .164
2m2C4= .4271 ,367 ,346 .350 .329
3mlC4= ,0519 .021 ,019 .015 ,020
The ability of new catalyst formulations to enhance the production of C4 olefins, to achieve
thermodynamic yields of isobutene with a minimum gasoline loss has been discussed (55). The
effect of the addition of ZSM-5 in the form of a commercially available additive is shown in
63
Table 6. The amounts of isobutene increase, but at the expense of gasoline. The effect of an
experimental catalyst, RFG-l, is also shown in Table 6. Approximate thermodynamic ratios of
both C5 and C4 olefins are achieved.
Table 5. Thermodynamic and catalytic distributions of C5 olefins as a result of gas oil cracking
over faujasite.
Equilibrium
Alberty (33) Rossini (31) Kilpatrik (34)
Slull(J2) ~ ~
Unit Cell Size/nm ~ 2MQ
l·pentane .05 .04 .06 .08 .10

trans-2-pentene .12 .10 .14 .23 .26
cis-2-pentene .12 .11 .10 .13 .16
2-methyl-l-butene .24 .32 .28 .18 .16
2-methyl-2-butene .43 .39 .37 .36 .30
3-methyl-l-butene .05 .05 .04 .02 .02
These results show a significant variation in branching with catalytic composltlOn. One
proposed explanation for this result is a variation in hydrogen transfer rates (56). It has been
proposed that the isoolefins undergo hydrogen transfer more readily than the straight chain
olefins. This leads to an overabundance of monomethyl branched paraffins relative to normal
paraffins, and to the disappearance of isoolefins. Thus there is present in the cracking product
higher than expected amounts of 2-methyl and 3-methyl pentane as well as isobutane and
isopentane.
3. Specialized Catalytic Functions - FCCU Additives
In order to enhance unit flexibility and efficiency, both solid and liquid additives have found
application in catalytic cracking. The key advantage of an FCCU additive is the ability to quickly
alter FCCU performance. Unlike FCC catalyst which requires significant unit turnover before
the full effects are seen, an additive can be injected to obtain an almost instantaneous response.
The refiner has control over the size of the effect and is in a better position to optimize the
refinery operation and, since additives tend to be expensive, to minimize the cost.
Examples of liquid additives currently in use include bismuth and antimony based additives for
passivation of nickel contaminants. A number of solid catalytic additives have been developed
that are specific for certain functions. Approximately two-thirds of North American units utilize
a noble metal promoter to reduce emissions of CO as well as provide beneficial yield effects.
During the early to mid-1980's, SOX removal additives came into use due to tighter
environmental restrictions. A ZSM-5 based additive for octane enhancement and light olefin
production was developed during the mid-1980's and is used commercially. Additives have also
been proposed as metal traps especially for vanadium passivation. These solid FCC additives
have become an increasingly important tool by which refiners meet yield and environmental
requirements .
Recent interest in reformulated gasoline has created the potential for another special function
catalyst, one with greatly reduced hydrogen transfer characteristics for the production of
64
isobutene and isoamylene in the FCC unit. The selectivities and properties of this catalyst were
discussed above.
Table 6. Yield structures of catalysts modified to obtain

maximum isoolefin production.
Catalyst LD. 90%OCTACAT OCTACAT RFG-l

10% ADD O-HS
C/O 3.90 3.90 3.90

Conversion, wt.% 60.0 60.0 60.0
YIELDS, WT.%
H2 0.082 0.090 0.053
Total C1+C2 1.90 1. 75 1. 76
C3= 8.2 4.3 6.1

Total C3's 9.1 5.0 7.0
I-Butene 1.6 1.2 1.6

Isobutylene 2.6 1.6 3.6
trans-2-Butene 2.4 1.7 2.4
cis-2-Butene 1.5 1.1 1.5
Total C4= 8.1 5.7 9.1
i-C4 3.1 2.4 2.5
n-C4 0.6 0.5 0.6
Total C4's 11.8 8.6 12.2
Isoamylene 3.1 2.5 4.0
Total C3+C4 Olefins 16.3 10.0 15.2
C5+Gasoline 34.9 42.4 37.1
WRC PONA RON 93.4 91.2 93.6
WRC PONA MON 81.55 80.2 80.2
Gaso. Sel. 0.58 0.71 0.62
LCO 23.3 23.8 18.5
640+HCO 16.7 16.2 21.5
Coke, wt.% Feed 2.20 2.20 1.91
1-Butene/C4= 0.20 0.21 0.18
Isobutylene/C4= 0.32 0.28 0.40
trans-2-Butene/C4= 0.30 0.30 0.26
cis-2-Butene/C4= 0.19 0.19 0.16
3.1. CO COMBUSTION PROMOTERS
One of the first additives to become commercial is the CO oxidation promoter consisting of a
noble metal, usually platinum, either on the catalytic particle at low concentrations, 1-2 ppm, or
on an alumina based support at higher concentrations, 300 to 1000 ppm (57-60). A CO promoter
is used in the FCCD to promote the CO to C02 reaction in the regenerator. Without promoter
the gas phase oxidation of CO to C02 is relatively slow. The C02/CO ratio is about 1 with
about 20% of the total gases exiting the regenerator being CO + C02. A CO combustion
promoter catalyzes the reaction of CO to C02 and reduces the CO concentration by several
65
orders of magnitude to the few hundred ppm range. The additional heat provided by the
complete combustion of CO can increase the FCCU regenerator temperature by as much as 50°C.
The operating advantages of CO promotion are summarized below.
o Reduced carbon on regenerated catalyst, increased catalyst activity and selectivity.

o Reduced coke yield and increased liquid recovery.
o Reduced afierburning and unwanted temperature excursions.
o Reductions in CO emissions.
o Maintenance of unit heat balance, especially with the use of low coke catalysts.
FCCU combustion promoters are a small portion of the total catalyst addition rate, falling in the
range of 2-25 Kg. per day compared to catalyst addition rates of 500 to 25000 Kg per day.
3.2. SOx TRANSFER CATALYSTS
Descriptions of the chemistry of SOx reduction are available in the literature (61-63). The SOx
comes originally from the 0.3% to about 3% sulfur in the feedstock. During the cracking
reaction in the FCCU reactor, much of the feedstock sulfur ends up in the coke. During the coke
burning step in the FCCU regenerator, the sulfur in the coke is converted to S02 (>90%) and
S03 ( < 10%), i.e., SOx. The SOx produced in the regenerator becomes part of the flue gas and
is discharged to the atmosphere. It is this discharge of SOx to the atmosphere which can be
controlled by the use of catalysts. These catalysts are called SOx transfer catalysts, or more
simply, SOx catalysts. They capture SOx in the FCCU regenerator then release it, as H2S, in
the FCCU reactor and steam stripper. The H2S leaves the FCCU with the reaction products.
The H2S is subsequently removed in downstream treating units.
For a typical FCCU not utilizing an SOx catalyst,SOx emissions are in the range of 500 to
2000 ppm. With the use of an SOx additive, SOx emissions can be reduced by up to 80 %. The
SOx additive usage rates vary from 1% to 10% of the fresh catalyst addition rate, depending on
the degree of the SOx reduction required.
Because of greater restrictions on refinery SOx emissions, sulfur reduction additives have found
numerous applications including:
o Reducing SOx emissions to meet environmental restrictions.
o Limiting SOx increase despite use of higher sulfur feeds.
o "Slug" additions to maintain FCCU SOx compliance during hydrotreater turnarounds.
3.3. OCTANE ADDITIVES
The addition of a separate octane additive catalyst to the FCCU is effective in upgrading gasoline
octane when used in conjunction with a conventional cracking catalyst. The active component
in this additive catalyst is ZSM-5, a shape selective zeolite developed by Mobil. Commercial
experience has shown that the addition of from 1 to 5 wt% of this additive to the FCCU under
conventional cracking operations can increase the octane by about 1 to 3 RON. This increase
occurs because the ZSM-5 preferentially cracks straight chain, low octane paraffins and olefins
in the gasoline boiling range to C3 and C4 olefins and, secondly, has been shown to isomerize
low octane linear oletins to more highly branched and higher octane oletins (64,65).
Unfortunately, this octane enhancement occurs at the expense of gasoline yield. However, if the
additional propylene and butene are alkylated, the alkylate yield increase greatly outweighs the
gasoline decrease, resulting in an increase in total gasoline plus alkylate yield. Commercial
66
applications of ZSM-5 based octane additives include the following:

o Increasing gasoline pool octane and reducing sensitivity.
o Maintaining FCC gasoline octane while in an LCO maximization mode.
o Maintaining pool octane with decreased reformer severity.
o Increasing isobutene yield for MTBE feed.
o Increasing light olefin yield for petrochemical applications.
Because such a small quantity of catalyst is required as compared to the total inventory of
catalyst, the refiner is afforded greater flexibility in commercial cracking operation, since the
additive can be quickly and easily introduced. The refiner can efficiently control the magnitude
of the octane increase by controlling the addition rate of the additive. This flexibility can be
useful in situations where the feed composition changes, where the demand for high octane
gasoline fluctuates, or where capacity for alkylation varies because of mechanical problems or
overall changes in refinery operations.
3.4. EFFECT OF ATTRITION RESISTANCE ON ADDITIVE PERFORMANCE
An FCCU consists of two fluidized beds, one on the reactor side and one on the regenerator side.
The catalyst abrades and/or fractures under these conditions and forms finer sized particles that
are then lost from the cyclones on either the reactor or regenerator side.
Each unit is unique in terms of its ability to retain catalyst due to its mechanical design and the
operating conditions employed; however, a general rule is that the additive should exhibit similar
physical properties to the cracking catalyst. This philosophy is particularly true with CO
promoters which are added at much less than 1% of the cracking catalyst addition rate. From
an economic standpoint, FCC additives are all significantly more expensive than FCC catalyst.
CO oxidation promoters are twenty to fifty times more expensive while ZSM-5 based octane
additives or SOx removal additives are about five to ten times more expensive than cracking
catalyst. As a result, it is critical that the maximum amount of additive be retained in inventory
for its useful (active) life.
4. References
P. B. Venuto and E. T. Habib, Fluid Catalytic Cracking with Zeolite Catalysts, Marcel
Dekker, New York, 1979.
2 J. M. Maselli and A. W. Peters, in Catalysis and Surface Science, Marcel Dekker, Inc.,
1985, H. Heineman and G. A. Somorjai, eds., p 223.
3 J. Scherzer, Octane Enhancing Zeolitic FCC Catalysts, Marcel Dekker, Inc., 1990,
p.70.
4 D. Geldart, Characterization of Fluidized Powders, in Gas Fluidization Technology, John
Wiley & Sons, 1986, D. Geldart, ed., p 33.
5 D. Geldart, Particle Entrainment and Carryover, in Gas Fluidization Technology, John
Wiley & Sons, 1986, D. Geldart, ed., p 123.
6 D. P. Leta, W. A. Lambetti, M. M. Disko, E. L. Kugler, and W. A. Varady, Fluid
Catalytic Cracking II, ACS Symposium Series 452, 1991, M. L. Occelli, ed., p
279; also reference 2, p. 53.
7 W-C. Cheng and K. Rajagopalan, Fluid Catalytic Cracking II, ACS Symposium Series
452, 1991, M. L. Occelli, ed., p 198.
67
8 P. F. Schubert and C. A. Altomare, Fluid Catalytic Cracking, ACS Symposium Series

375, p. 182, M. Occelli Ed., Amer. Chern. Soc. (1988).
9 R. J. Lussier, J. Catal. 129,225-237 (1991).
10 J. W. Ward, J. Catal., 1li, 348 (1970)
11 C. V. McDaniel and P. K. Maher, U. S. Patent Nos. 3.292,192 (1966); 3,449,070
(1969).
12 D. W. Breck, H. Blass, and G. W. Skeels, U. S. Patent No. 4,503,023.
13 Q. L. Wang, M. Torrealba, G. Giannetto, M. Guisnet, G. Perot, M. Cahoreau and J.
Caisso, Zeolites, 10, 703 (1990).
14 M. B. Ward and J. B. Lunsford, J. Catal., 87,524 (1984).
15 Q. L. Wang, G. Giannetto, and M. Guisnet, Zeolites, 10, 301 (1990).
16 K. Rajagopalan and A. W. Peters, J. Catal., 106, 410-416 (1987).
17 Marvin F. L., Johnson, J. Catal., 1978,52,425.
18 ASTM Standards on Catalysts, Third Edition, ASTM, 1916 Race Street, Philadelphia,
PA 19103, USA,1988.
19 J. Lynch, F. Raatz, and P. Dufresene, Zeolites, 7, 333 (1987).
20 F. Mauge, A. Auroux, J. C. Courcelle, Ph. Engelhard, P. Gallezot, J. Grosmangin,
Studies in Surface Science and Catalysis, Vol. 20, Catalysis by Acids and
Bases,Elsevier, New York, 1985, p. 91.
21 H. Stach, U. Lohse, H. Thamm, and W. Schirmer, Zeolites, Q, 74 (1986).
22 K. Rajagopalan and A. W. Peters, Applied Catalysis, 23, 69 (1986).
23 A. W. Peters, K. Rajagopalan, and E. T. Habib, Jr., 12 Simposio Ibero - Americano
0
de Catalise, Rio de Janeiro, 1990, IBP/CAT, P 421.

24 C. A. Fyfe, G. C. Gobbi,1. S. Hartman, J. Klinowski, and J. M. Thomas, 1. Phys.
Chern., 86, 1247 (1982).
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NOVEL TECHNIQUES FOR FCC CATALYST SELECTION AND
KINETIC MODELLING
H. DE LASA D. KRAEMER
Chemical Reactor Engineering Centre Esso Petroleum Canada
University of Western Ontario Research Department
London, Onto N6A 5B9 Sarnia, Onto
Canada Canada
ABSTRACT. The present contribution reviews the state-of-the-art on various aspects of catalytic cracking
chemistry, catalyst formulation, catalyst preparation and FCC reactor engineering. Special consideration
is given to the matters that relates to kinetic modelling. A detailed discussion is also presented on the
characteristics and performance of a novel unit named Riser Simulator of particular value for FCC catalyst
testing and kinetic modelling.
1. Catalytic Cracking Overview
1.1. DEVELOPMENT OF CATALYTIC CRACKING
Catalytic cracking of gas oil is considered one of the most important and most profitable unit
operations of the petroleum-refining industry. The basic operation involves the breakdown of
large hydrocarbon molecules found in the heavier oil streams from crude distillation into smaller
ones by means of contacting the oil for a short time with hot catalyst. It serves as a major
refinery tool to produce high quality motor fuel, heating fuel and raw petrochemical feedstocks.
According to Occelli (1988), in the United States approximately one-third of all processed crude
oil is converted by fluid catalytic cracking (FCC) requiring the use of over 500 tons of catalyst
daily. This process is the work horse of the modern refinery for gasoline production and
research and development efforts over the last 50 years have been very profitable (Venuto and
Habib, 1978).
Several reviews on the historical development of catalytic cracking and the technological
changes were published in the literature (Avidan et al., 1990a; Jahnig et al., 1980, 1984;
McKetta, 1981; Squires, 1986; Reichele, 1988; Wrench et al, 1986; Nieskens et al, 1990; de
Lasa, 1982). Avidan et al. (1990a) lists important dates of the many innovative developments in
the cracking process. Only the major issues that specifically refer to the interrelated matters of
engineering and kinetic modelling of catalytic cracking will be reviewed in this contribution.
The introduction of high activity zeolite catalysts in the 1960s resulted in a revolution in FCC
designs (de Lasa, 1982). The work by Plank et al. (1964) showed that by incorporating zeolite
into a silica-alumina matrix, 100-1000 times improved activity could be achieved as compared
to the amorphous silica-alumina and improved hydrogen transfer capability was also possible
which would increase gasoline yields significantly. Plank (1984) reviews the invention of zeolite
71
H.I. de Lasa et af. (eds.). Chemical Reactor Technology for Environmentally Safe Reactors and Products, 71-131.
72
cracking catalysts and the developments that took place at Mobil.

The advent of these new zeolite catalysts into the market (Gussov et aI., 1972; Montgomery,
1972) resulted in a shift to shorter contact time cracking. The requirement for long residence
times in dense fluidized beds was no longer valid since the high activity catalysts became
excessively coked and overcracking resulted in large amounts of light gases. Efforts were made
to modify existing units to take advantage of the activity and selectivity of the new catalysts
generating a new FCC concept. In fact, reaction began in the transport line conveying the
catalyst to the reactor hence these lines were lengthened to provide a 3-4 seconds reaction time
followed by a shallow dense bed in the reactor (Blazek, 1973; Strother et aI., 1972; Whittington
et al., 1972; Bunn et aI., 1969).
New FCC designs were then patented in the late 1960's and early 1970's based on all 'riser'
cracking where reaction occurred only in the transfer line such as Exxon's F1exicracker, the
Texaco FCC process, the UOP straight riser, Gulf's riser unit and the Orthoflow F unit from
M.W. Kellogg (Murcia et al., 1979; Murphy and Soudek, 1977; Finnerman et al., 1974; Pierce
et al., 1972; Bryson and Huling, 1972). Shell had invented a short-residence time FCC riser
reactor almost a decade before the use of zeolite cracking catalysts (Avidan et aI., 1990a). The
up-flow reactor with short contact times, high temperature and other concepts was ahead of its
time.
Since the switch to riser cracking other improvements and advances in FCC technology
emerged due in part to catalyst development, advances in metallurgy, need to process heavier
feeds and environmental concerns. The legislated reduction of CO emissions led to the use of
combustion promoters such as platinum deposited in small concentrations on the cracking catalyst
to ensure complete combustion of CO to CO2 within the regenerator (Hartzell and Chester, 1979;
Chester et aI., 1979). With increased oil prices and a new demand pattern for oil products (high
octane gasoline without lead additives) it was necessary to crack heavier crudes which contained
high levels of nickel and vanadium metals leading to excess coke and light gases as well as
catalyst deactivation (vanadium degrades zeolite structure) (Hemler et al., 1985; Elvin, 1983;
Otterstadt et al., 1986). The use of metal passivators such as antimony (patented by Phillips
Petroleum to reduce nickel dehydrogenation by 50%), and bismuth have been used as well as
vanadium traps and new families of zeolitic catalysts (Redsicat, GRZ) to overcome these
problems (Davies, 1977; Dale and McKay, 1977; Magee et aI., 1979; Edelman et al., 1979).
Furthermore, FCC units were modified to process heavy oil and Heavy Oil Cracking process
(HOC) was developed by M.W. Kellogg and Phillips Petroleum. Later in the mid 1970's
Ashland Oil and UOP Inc. patented the RCC process (resid catalytic cracking) and Total
Petroleum developed the R2R process which used two regenerator stages (Johnson et aI., 1985;
Hemler et aI., 1984; Mauleon and Sigaud, 1987). Also, Shell has developed resid FCC
technology as reviewed by Nieskens et al.(1990) which includes a more compact reactor with a
few seconds residence time, a high-efficiency riser-end-separator, an integral swirl-tube separator
inside the regenerator vessel, single stage regenerator cyclones, complete or partial CO
combustion, larger capacity catalyst coolers, and reduced unit catalyst inventory.
Features of these designs include better mix temperature control in the riser through advanced
multiple nozzle feed injection systems (Murphy, 1984; Galtier and Pontier, 1989), catalyst coolers
in the regenerator to handle larger energy inventory as a result of higher coke make from the
heavier feeds (Mauleon and Courcelle, 1985) and dual stage regeneration as in the R2R process.
The first stage regenerator operates at approximately 700°C with insufficient oxygen to burn most
of the hydrogen present in the coke. In the second stage high temperature combustion (900°C)
takes place in the absence of water vapour obtaining near to complete combustion and minimizing
deactivation of the zeolite.
73
Figure 1 shows a typical catalyst density profile as a function of riser height. With the initial
solidsloil contact, pneumatic transport occurs and the rapid molar expansion of cracking causes
a sharp increase in vapour velocity. The catalyst accelerates over a few seconds from a low
initial velocity to one close to the vapour velocity (Hemler et a!., 1985). The difference in
catalyst-vapour velocity is the slip velocity and is normally assessed using the ratio of catalyst
residence time to vapour residence time (Pohlenz, 1963). This ratio can be as high as 1.5 over
the entire reactor length. However, high exit gas velocities of above 25 mls can significantly
reduce this ratio close to unity which is desirable to avoid backmixing and hence overcracking
(Venuto and Habib, 1978).
1 REACTION ZONE
(MINIMUM SLIP/PLUG FLOW)
SPEr.T CATALYST INITIAL CONTACTING ZONE

ACCELERATION
REGENERATED CATALYST (HIGH SLIP/BACK MIXING)
DILUENT
RISER DENSITY --+
Figure 1: Density Profile along the height of a riser Reactor (Helmer et a!., 1985).
l.2. CATALYTIC CRACKING CHEMISTRY
The reactions taking place during the cracking of hydrocarbons over acidic catalysts have been
studied extensively by several researchers (Greensfelder and Voge, 1945a; 1945b; 1945c;
Greensfelder et al., 1945; Plank et ai, 1964; John and Wojciechowski, 1975a; 1975b; Thomas
and Barmby, 1968; Nace, 1969a; 1969b; Moscou and Mone, 1973; Jacob et al., 1976; Corma
et al., 1986; Abbot and Wojciechowski, 1985a). Several reviews concerning the reactions and
chemistry of catalytic cracking are available in the literature (Gates et al., 1979; Venuto and
Habib, 1978; McKetta, 1981; Decroocq, 1984; Scherzer, 1989; Magee and Blazek, 1976;
Wojciechowski and Corma, 1986).
The transformations that occur when gas oil is catalytically cracked are complex with many of
the primary products undergoing secondary reactions. Cracking reactions involve the rupture of
carbon-carbon bonds and are thermodynamically favoured by high temperatures due to the
endothermic nature of the reaction. A summary of the main reactions according to Gates et a!.
(1979) is given below showing how cracking can occur:
1. Paraffins are cracked to give olefins and smaller paraffins;

ego C 16H34 ---> C9H 18 + C7H 16
74
2. Dlefins are cracked to give smaller olefins;

ego C 1zH24 ---> C7H I4 + CsHIO
3. Alkyl aromatics undergo de-alkylation;

ego CJIrCnH"'+1 ---> CJI6 + CnHz.
4. Aromatics also undergo side-chain scission;

ego CJIs-C1zHzs ---> CJIs-CsHls + C4H lO
5. Naphthenes are cracked to give olefins;

ego C~40 --- > C1zH24 + CSHI6
Secondary reactions occurring after the initial cracking steps include hydrogen transfer (eg.
naphthene + olefin ---> aromatic + paraffin), isomerization, alkyl-group transfer, condensation
reactions and disproportionation of low molecular weight olefins (Gates et al., 1979). These
reactions are important in determining the final product compositions. Side reactions such as
isomerization, alkyl-group rearrangement and dealkylation of aromatics occur only to a moderate
extent at equilibrium under cracking conditions. Reactions such as paraffin-olefin alkylation,
aromatic hydrogenation and olefin polymerization (except for ethylene polymerization) cannot
proceed to any appreciable extent.
The endothermic reactions always predominate in cracking processes with the heat effect
depending on the feedstock, catalyst and reaction conditions. Hydrogen transfer reactions are
exothermic such as the case of cyclohexane combining with c-2-butene to yield benzene and n-
butane with a heat of reaction equal to -259 BTU lIb whereas the cracking of n-decane to yield
n-pentane and I-pentene has a heat of reaction equivalent to + 249 BTU lib (Leuenberger and
Wilbert, 1987). Thus, using a rare earth exchanged zeolite catalyst, which promotes hydrogen
transfer reactions, can raise the overall heat of cracking.
1.3. REACTION MECHANISM
The differences in product distributions between thermally cracked and catalytically cracked
hydrocarbons can be explained in terms of the reaction mechanism. Free radical mechanisms are
postulated for thermal cracking whereas the intermediate formation of positively charged organic
species, called carbocations is generally accepted for catalytic cracking (Decroocq, 1984; Gates
et al., 1979; Scherzer, 1989). Carbocations include both carbenium ions (the charge-carrying
carbon atom can be di- or tricoordinated) and carbonium ions (charge-carrying can be tetra- or
pentacoordinated). Carbocations are most stable in the tertiary form followed by secondary then
primary ones. Thus, primary carbocations tend to isomerize to the more stable tertiary and
secondary forms.
The mechanism was first proposed by Whitemore (1948) who suggested a carbonium ion as the
intermediate in the low-temperature acid-catalyzed reactions such as alkylation and
polymerization. The concept was applied to catalytic cracking and many previous experimental
observations could then be correlated, resulting in the general acceptance of the mechanism
(Davis and Hettinger, 1983). It has been postulated that the active sites on the surface of the
zeolite catalyst includes a combination of Lewis acid sites (AP+ ions with empty p orbital) and
Bronsted acid sites (proton-donating hydroxyl groups). Scherzer (1989) describes two proposed
mechanisms with the first involving the formation of carbenium ion intermediates and the other
assumes the formation of pentacoordinated carbonium ion intermediates.
75
The carbenium ions are initially formed from the supposed protonation of olefins, present as
impurities or from thermal cracking, at the Bronsted acid sites or by hydride abstraction from a
paraffin on a Lewis acid site. Once a carbenium ion is formed, cracking occurs by scission of
the carbon chain at a bond located '6' to the charged carbon atom to give an a-olefin and a
smaller primary carbenium ion:
R-CHl-CH 2"'-CH+-CH2-CH 3 ----> R-CH+ + CH 2=CH-CH 2-CH 3

(carbenium ion) (carbenium ion) (olefin)
Next a more stable secondary carbenium ion is formed which can undergo 6 scission to give
more a-olefins or further re-arrangement:
The carbenium ion can undergo chain transfer to form a paraffin thus preventing the cracking
from continuing to the smallest possible fragment. The chain reaction is also terminated when
the carbenium ion loses a proton to the catalyst and is converted to an olefin. The intermolecular
hydride transfer between the carbenium ion and a paraffin propagates the reaction and is the rate-
determining step of the cracking reaction (Scherzer, 1989). In competition with the scission
mechanism there are other steps such as the tendency of the carbenium ion to find a more stable
configuration and carbenium ion interaction with a double bond which provides a route for
cyclization.
It is speculated that the mechanism concerning pentacoordinated carbonium ion intermediates
(eg. RcCH3 +-CH 2-R 2, R 1-CH2+= CH-R2' CJI1 +) occurs at temperatures above 500°C with the
intermediates undergoing 6-scission to smaller paraffins and carbenium ions. As well, the
carbonium ions are converted to carbenium ions through the loss of hydrogen, present as
molecular hydrogen in the cracking products. This mechanism is also favoured by low
conversion, low hydrocarbon partial pressure and high constraint indexed zeolites (Scherzer,
1989).
1.4. CATALYTIC CRACKING OF GAS OIL
1.4.1. Primary Reactions. The primary products of catalytically cracked gas oils are gasoline
range (C s to C 12) paraffins and olefins, n-butane, butenes and propylene. The gasoline range
paraffins reach a maximum yield with conversion and then undergo further cracking usually
referred to as 'over-cracking'. The gasoline range olefins also reach a maximum yield but at a
lower conversion before they over-crack (John and Wojciechowski, 1975a). Butenes are
considered unstable primary products which undergo further secondary reactions. Propylene and
n-butane are stable primary products which are not significantly converted to other products after
their initial formation.
1.4.2. Hydrogen Transfer. Hydrogen transfer plays a key role in the gas oil cracking process
(de Jong, 1986). Many of the acid catalyzed secondary reactions involve intra- or intermolecular
hydrogen transfer and the final composition of the cracked products depends on the relative rates
of these reactions. Hydrogen transfer is important because it reduces the amount of olefins in
the product, influences product molecular weight distribution, increases gasoline selectivity,
influences gasoline quality and contributes to coke formation and hence catalyst deactivation
(Gates et al., 1979).
76
Hydrogen transfer occurs through the transfer of bimolecular hydrogen from a naphthene to
highly reactive olefins to form a stable paraffin and aromatic which are less prone to secondary
cracking:
3 CnH2n + CmH2m --- > 3 CnH2n + 2 + CmH2;"-6

Olefin Naphthene Paraffin Aromatic
In terms of gasoline quality, as determined by the octane number method, the formation of
aromatics is beneficial since they show the highest octane of the various hydrocarbon groups (next
are olefins and naphthenes with n-paraffins possessing low octane values). However, the loss of
olefins and naphthenes from the hydrogen transfer reaction results in a net loss of octane and
some of the aromatics formed end up in the light oil fraction and also contribute to coke
formation. The benefit of increased gasoline yields from hydrogen transfer reactions comes at
the cost of lowered gasoline octane.
Hydrogen transfer can also occur by olefins abstracting hydrogen from aromatics or other
hydrogen-deficient products to form more paraffins and coke (Scherzer, 1989). Zeolites such as
REY and REHY readily catalyze hydrogen transfer between olefins and naphthenes because of
the high density of acidic sites. In such catalysts the concentration of hydrocarbon reactants in
the pore structure is presumably high which also enhances bimolecular hydrogen transfer.
1.4.3. Coke Formation. Coke formation reactions are probably the least well understood of
those involved in catalytic cracking. Coke is formed in almost all catalytic hydrocarbon
conversion reactions and typically consists of hydrogen deficient mono-and polycyclic aromatic
rings connected by aliphatic and alicyclic fragments with characteristics similar to graphite. A
chemical and physical characterization of coke deposited on a catalyst indicates the presence of
carbon, hydrogen, sulphur and oxygen giving a molecular weight ranging from 940 to lOtO
(Wolf and Alfani, 1982; Fetting et al., 1984). Rapid decay in the activity of the catalyst occurs
when these highly unsaturated, high molecular weight compounds become adsorbed to the catalyst
surface. Catalyst activity is renewed by combustion of the coke deposits.
Some results suggest that the rate of coke formation may be related to olefin formation rates
and to an overall hydrogen balance (Nace, 1969). In general, the rate of coke formation
increases with increasing acid strength and acid-site density on the catalyst. Usually coke
formation requires a source of hydrogen (coke precursor) and a sink for hydrogen (olefin)
showing that hydrogen transfer plays an important role. Appleby et al. (1962) showed that in
catalytic cracking coke formation proceeds through intermediate aromatic structures of increasing
size and complexity. They also found that the coke forming tendency of many aromatics and
their alkyl derivatives correlates well with their basicity and the mechanism of coke formation
is that of intermediate carbenium ions. Overall, the mechanism of coke formation is complex
involving a multistep reaction sequence comprising: adsorption, dehydrogenation, condensation-
polymerization, and cyclization of hydrogen-deficient fragments to form polynuclear residues.
In the FCC process coke yields are classified into four categories:
1. Catalytic coke - from the acid catalyzed cracking reactions shown to be residence time
dependent
2. Contaminant coke - from the catalytic action of metal poisons such as nickel and vanadium
3. Conradson coke - hydrogen deficient, high coking tendency feed components which correlates
directly with the basic nitrogen and average molecular weight of the feedstock, as well as the
Conradson carbon analysis
4. Cat-to-oil coke - hydrocarbons which are not stripped by steam in the stripper and are left
77
adsorbed to the catalysts surface and thus burned in the regenerator.
1.5. EFFECTS OF SOME OPERATING VARIABLES
Several operating variables play an important role in determining overall conversions, selectivities
and product quality in the FCC process. Optimization of these variables is essential to obtain
good unit performance.
The effect of increasing reactor temperature at constant conversion is to decrease the Cs+
gasoline yield and coke yield while increasing dry gas and total butanes yields (McKetta, 1981).
In addition, olefin yields increase; C 1 and C2 yields increase; C3 and C4 paraffin yields change
only slightly; Cs+ paraffin yields decrease; and Motor and Research octane numbers of the
gasoline fraction increase. The increase in octane numbers with increasing temperature (RON
enhanced more than MON) can be explained by the lower hydrogen transfer rates occurring at
the higher temperature levels in comparison with cracking rates (Gates et al., 1979). This results
in more olefins and aromatics present as compared to paraffins especially in the heavy gasoline
fraction. The increased role of thermal cracking at higher temperatures does not favour the
formation of branched hydrocarbons but does favour olefin formation resulting in increased
gasoline sensitivity (Scherzer, 1989). The refiner must optimize the trade-off between lowered
gasoline yields (but increased conversion) and more attractive octane numbers at higher
temperatures .
The mass of catalyst fed to the reactor per unit mass of gas oil injected is normally referred to
as the catalyst to oil ratio (c/o). This variable can be increased, at constant space velocity and
temperature, to increase conversion (McKetta, 1981). As well, pilot plant and commercial unit
studies show that at constant conversion, reactor temperature and catalyst activity, an increase
in the c/o ratio gives increased coke yields, decreases hydrogen and C 1 to C4 yields and has little
effect of Cs+ gasoline yield or octane number (Moorman, 1954).
The residence time of the catalyst and oil mixture within the riser is one of the most important
parameters. With high activity catalysts the contact between oil and catalyst is kept at a few
seconds in order to minimize excess coke formation and secondary reactions.
The effect of operating pressure in the FCC process does not playa significant role since most
units operate close to atmospheric pressure (typically 1-3 atm) (pohlenz, 1963). Lowering the
partial pressure of the reacting gases with steam is used mainly to aid the feed injection system
in atomizing the feed to small droplets which vapourize quickly. Increasing the amount of inert
steam in the process lowers the partial pressure of hydrocarbons and thus lowers conversion.
Also, lower oil partial pressures result in increased gasoline RON due to an increase in gasoline
olefinicity (Scherzer, 1989). Working at higher pressures is not feasible because of the
condensation of unsaturated compounds to form coke, difficulty in feed vapourization and
increased polymerization reactions which leave a solid residue deposited on the catalyst
(Vermillion, 1974).
1.6. CRACKING CATALYSTS
The catalyst development at Mobil in the 1950s resulted in the introduction of zeolites as cracking
catalysts (plank, 1984). These molecular sieves whose active sites are located in controlled pores
gave more selective cracking and hence less coke formation (Davis and Hettinger, 1983).
Zeolites were found to be more active than amorphous silica-alumina due to greater concentration
of active sites and greater effective concentration of hydrocarbons in the vicinity of a site
resulting from the strong adsorption in the fine micropore structure. The zeolite material was
78
embedded in a silica-alumina matrix to form the cracking catalyst which revolutionized FCC
operation.
The fir:;t zeolite used in catalytic cracking was the rare earth exchanged form of X-type zeolite.
This was soon replaced by Y-type zeolite which had improved thermal and hydrothermal stability
because of a higher silica/alumina ratio. The basic Y zeolite structure has since been chemically
modified to produce HY (a hydrogen form of Y zeolite) and ultra-stable Y (USY) which is a
stabilized form of HY (Yanik et al., 1985).
With the switch from amorphous silica-alumina to zeolite catalysts a significant advantage in
addition to the higher activity was the better selectivity obtained. Yields of products increased
in the Cs to C IO range and decreased in the C3 to C4 range when using the zeolite catalyst. The
reason for this is attributed to the zeolites greater hydrogen-transfer activity as compared to chain-
scission reactions. Hydride-ion transfer to the carbenium ion and hydrogen transfer to olefins
stops the cracking of carbon chains in zeolites and gives products with higher molecular weights
(Gates et al., 1979).
The higher gasoline yields obtained with zeolite catalysts came at the expense of lowered
gasoline octane numbers (Desai and Haseltine, 1989). Subsequently, octanes were increased by
the use oflead additives in the 1970s to maintain these increased gasoline yields. Then, with the
legislated elimination of lead in gasoline (Weiszmann et aI., 1986; Pierce and Logwinuk, 1985;
Culberson et al., 1985) octane catalysts based on USY and modified USY type zeolites were
implemented to overcome the octane debit. The FCC catalyst based on USY was actually
introduced to the market in 1964 but refineries chose to use the rare earth ion-exchanged Y
zeolite catalyst (REY) because of its lower cost (Tsai et aI., 1989). The USY catalysts increase
octane by attaining lower silica/alumina ratios hence decreasing acid site density. This effectively
reduces hydrogen transfer reactions giving a more olefinic gasoline.
Another change which stimulated FCC catalyst development was the shift in feedstock from
conventional gas oils to heavier feedstocks (bottom of the barrel). Residual feeds contain high
levels of vanadium and nickel which result in higher coke and dry gas yields and faster
deactivation of the catalyst. Also, the presence of increased basic nitrogen containing molecules
in resid feed can result in loss of catalyst activity from poisoning of the acid sites by the basic
compounds (Corma et aI., 1987; Fu and Schaffer, 1985). The larger molecules present in heavy
feedstocks exhibit diffusional problems in the zeolite pores (Rajagopalan et al., 1986; Tauster et
al., 1987; Maselli and Peters, 1984) and thus new catalysts were explored and developed to
include active matrices which could crack the heavier oil compounds (Sterte and Otterstedt, 1988,
Tsai et al., 1989; Ritter et aI., 1981; Upson et aI., 1990). Including an active amorphous
component as the matrix is beneficial for bottoms conversion where heavier compounds are
cracked on the matrix and then the lighter compounds diffuse through the matrix to the active
zeolite sites. However, too much matrix activity may be an unfavourable option because it
results in a degradation of product selectivity (Young and Rajagopalan, 1985).
To handle the increased metal levels found in residual oils, elements such as boron, bismuth,
tin and antimony can be impregnated on the metal contaminated catalyst through injection of an
organic complex with the cat-cracker feedstock (Ritter et ai, 1981; Heite et aI., 1990) or could
be introduced in the catalyst as part of its formulation (Farag et al,1991). These elements react
with the nickel to form an inert residue on the catalyst surface which is less effective for
dehydrogenation reactions.
The diffusion of molecules in zeolites is unique due to the very small size of the channels and
is also not well understood (palekar and Rajadhyaksha, 1986). Numerous investigations have
been made on the subject including attempts to extend the theory of diffusion of reactions in other
porous catalysts to zeolites (Gelbin and Fiedler, 1980; Hsu and Haynes, 1981; McLaughlin and
79
Anthony, 1985; Ruthven, 1983; Pachovsky and Wojciechowski, 1973; Best et al., 1971).
Palekar and Rajadhyaksha (1986) state that it is difficult to visualize the existence of a free gas
phase in intracrystalline cavities. The diffusion regime in zeolites is different from the Knudsen
diffusion observed in other porous catalysts and is referred to as 'configurational diffusion'.
Diffusivities for this regime are lower by a few orders of magnitude than Knudsen diffusivities.
Methods of evaluating intraparticle diffusional inhibition usually involve testing different
particle sizes of the catalyst. However, with FCC catalysts a change in particle size does not
change the size of the zeolite crystal which is embedded into the matrix and represents in fact the
controlling step for diffusion. This presents a challenge to determine diffusional limitations since
one would have to obtain at least two catalysts with different zeolite sizes dispersed throughout
the matrix.
Coke formation can cause diffusional limitations as well, indicated by a decrease in activation
energy and a decrease in product selectivity (Gates et al., 1979). Pore-mouth plugging of the
zeolite crystallite by coke prevents hydrocarbon molecules from entering the fine channels.
The octane rating of FCC gasoline is affected by feedstock type, operating conditions of the
unit and type of catalyst used to process the oil. Catalysts can be specially manufactured to
enhance the octane rating of the gasoline by approximately 3 RON and 1-I.S MON (Magee et
al., 1985). Octane catalysts in general consist of a zeolite component, which has the most
significant effect and a matrix component. Additives included as part of the catalyst matrix or
as separate particles are also used to boost octane. Octane FCC catalysts can consist of an
octane-boosting Y zeolite in an inert matrix or in an active matrix or can contain REY and an
additive such as ZSM-S (Scherzer, 1989; Ritter et al., 1986). An octane-boosting Y zeolite is the
ultra-stable Y form and is synthesized by careful thermal and hydrothermal treatment of
ammonium Y zeolite. Ultra-stabilization results from the removal of aluminum ions from the
zeolite framework and decomposition of the ammonia ions thus giving a highly siliceous hydrogen
form of faujasite.
Gasoline octanes have also been shown to increase by using ZSM-S additive to the USY catalyst
(Magee et al., 1985; Biswas and Maxwell, 1990; Anderson and Dwyer, 1984; Santilli, 1990;
Donnely, 1990). Other zeolites such as the erionite-type and silicon-enriched ZSM 20 have also
been used (Marcilly et al., 1989; Huss and Schwartz, 1990). The smaller pore size of ZSM-S
restricts the access of branched and cyclic hydrocarbons but allows straight chains to enter.
These straight chain molecules, which have lower octane, are then cracked to form lighter
compounds. Typically linear C7 to C 13 molecules in the heavier end of the gasoline are cracked
forming C3 to Cs compounds. The result is a net loss in gasoline yield since light gases were
formed, but an increase in octane since the linear paraffins have been converted.
It has been postulated that the ZSM-S provides some isomerization activity resulting in the
conversion of n-paraffins to branched paraffins which would increase the octane number (Magee
et al., 1985; Anderson and Dwyer, 1984; Abbot and Wojciechowski, 1985b, 1985c). However,
Biswas and Maxwell (1990) obtained results indicating no increase in gasoline component
branching with the use of ZSM-S. They found significant losses in gasoline yield and suggest
that the higher octane is due to a concentration effect. They argue that cracking of linear
compounds (especially the paraffins) leaves a greater concentration of aromatics and naphthenes
which gives the higher octane number.
1.7. CATALYST STEAMING
Catalytic cracking catalysts can deactivate by the extended exposure to water vapour at very high
temperatures. In a commercial cracking unit such conditions can occur in the regenerator vessel
80
where the burning of coke produces water vapour and heat. After burning of CO in the dilute
phase and cyclone regions can cause high enough temperatures for irreversibly deactivating the
catalyst. This hydrothermal deactivation involves the loss of active sites in the zeolite through
crystal destruction as well as changes in the surface area and pore size distribution in the matrix
(Chen et al., 1977a; 1977b).
As mentioned in the previous section, the zeolite undergoes dealumination where high
temperature hydrolysis of the silica-oxygen-alumina bonds causes the expulsion of aluminum ions
into nonframework positions. Subsequently, the gaps in the framework structure are filled by
silica resulting in a higher silica/alumina zeolite and thus a lowered unit cell size. This
deactivation process in combination with other causes of activity loss (metals loading, attrition),
amounts to a zeolite catalyst life in a commercial unit between 20 and 100 days (Chen et al.,
1977a). The unit is maintained at a constant catalyst activity by continuous addition of fresh
catalyst and withdrawal of spent catalyst from the regenerator.
The dealuminated state of the catalyst represents the so-called 'equilibrium' condition of the
catalyst which is achieved after several cycles of reaction and regeneration. For studies done on
a laboratory scale this type of equilibrated condition must be closely simulated in order to obtain
meaningful results. Using fresh catalyst would certainly give different results in terms of
conversion and selectivity than an aged catalyst because of the differences in unit cell size,
surface area and porosity. It has been suggested that the only way to obtain an aged catalyst
is to run a laboratory unit under commercial operating conditions (Letzsch et al., 1976) but this
is practically impossible because of the cost and time involved for such a procedure. Thus, the
generally accepted method involves a severe steaming treatment of the fresh catalyst (Chen et al.,
1977a; 1977b; Chester and Stover, 1977; Larocca, 1988; Berak and Manik, 1982; Mauge and
Courcelle, 1986; Hettinger et al., 1983; Campagna et al., 1986). Chen et al. (1977) point out
that such a method likely does not duplicate the true composition of a catalyst aged by
commercial operation and may not be representative of the heterogeneous inventory in the unit.
Steaming of fresh catalyst samples for laboratory performance studies has been done in fixed
or fluidized bed units. Several factors such as temperature, steam partial pressure and total time
of the treatment can influence the final results. The catalyst can be steamed in the presence of
100% steam or as low as 10%. Temperature can vary from 500°C to 850°C, pressures from
1 to 3 atm and steaming times from 2 to 36 hours. There seems to be no consistent agreement
on the optimum conditions to be used with most researchers finding appropriate conditions based
on equipment available and the catalyst used.
Chen et al. (1977) found that accelerated deactivation occurred with temperatures above the
normally accepted maximum dense bed regenerator temperatures of 700°C. Their results showed
no significant catalyst deactivation under normal regenerator conditions (7OO°C and 190 mmHg
water partial pressure). At temperatures of 760°C, which can be obtained in the dilute phase
regenerator or during upsets, the catalyst was deactivated (as determined by X-ray analysis). In
general, steaming at 1 atm with 100% steam for 4 hours at temperatures 50 to 80°C higher than
regenerator bed temperatures is considered adequate to simulate an aged condition similar to a
commercial equilibrated catalyst (Speronello and Reagan, 1984).
Steam treatment severity has been varied to match commercial equilibrium catalyst activities
and other properties. One measure of a suitably steam-aged catalyst is the surface area which
should be in the range of 51 to 200 m2/g (Ritter, 1985). Perhaps a more meaningful measure is
to use a bulk property of the zeolite, the unit cell size, which is measured by X-ray diffraction.
Typically, the unit cell size of USY zeolites are reduced to below 24.26 A whereas RE-USY
zeolites equilibrate to 24.26-24.32 A and REY zeolites to 24.5 A in the FCC unit (Scherzer,
81
1989). These shrinkages are dependent upon initial unit cell size, type of cations present and on
steaming severity.
2. Kinetic Modeling of Catalytic Cracking
In developing a kinetic model for the catalytic cracking of petroleum oils the usual approach has
been to use lumping techniques (Wei and Kuo, 1969; Kuo and Wei, 1969; Weekman, 1979).
This is because of the large number of individual species present in gas oil feedstocks. Normally
FCC feeds have boiling points ranging from about 220°C to higher than 530°C in which tens of
thousands of individual molecular species may be present (Sachanen, 1945). Such a diversity of
molecules makes it necessary to group or lump species together into a smaller number of
pseudospecies to obtain a feasible and manageable system of kinetic equations.
The basic theory in lumping strategy is that species should be lumped together only if the
dynamic behaviour of the resulting pseudo species is independent of the composition of species
(Coxson and Bischoff, 1987). The first proposed and most widely used reaction scheme for
catalytic cracking was the three lump model based on the feedstock, gasoline and light gases plus
coke (Weekman and Nace, 1970). Later, with the development of lumping theory higher
lumping models were used where the feedstock was further lumped to account for molecular type
(Jacob et a1., 1976). A discussion of the various models will be given below.
A further complication in modelling catalytic cracking is due to coking reactions which cause
the catalyst to quickly lose activity with time as well as to change its selectivity (yates, 1983).
Despite these complications kinetic models have been developed and incorporated into reactor-
regenerator models used to predict the performance of commercial units.
2.1. THE THREE LUMP MODEL
The early work of Blanding (1953), Andrews (1959) and Weekman (1968) describe the kinetic
behaviour of catalytic cracking in terms of conversion behaviour only. Weekman (1969) and
Weekman and Nace (1970) then developed a model which also accounted for the product
selectivity resulting in a triangular reaction scheme. This three lump model consists of a
feedstock lump, a gasoline lump (boiling fraction of Cs to 220°C) and a dry gas lump (C4 and
less plus coke). The gasoline fraction is the most profitable component of the cracked products
and thus this scheme allowed for an understanding of the interaction between process variables
and the kinetic parameters. The three lump model is shown below where A represents the gas
oil, B the gasoline, and C the light gases and coke:
In this triangular scheme, the gas oil can crack either to form gasoline as given by the rate
constant kl or to form C-Iump components as given by rate constant kJ • The overall gas oil
cracking rate is described by ~ which is the summation of kl and kJ . The gasoline formed may
also undergo further cracking to C-Iump as described by rate constant k2 •
82
The reaction kinetics for the cracking of the gas oil lump has been found experimentally to
follow a reaction order close to two (Weekman, 1968; Pachovsky and Wojciechowski, 1971;
Blanding, 1953; Kraemer, 1987). Pure hydrocarbons are known to crack according to a first
order rate law (Nace, 1969a). Since gasoline is a mixture of hydrocarbons having a limited range
of boiling points then it is assumed to behave as a pseudo-pure component exhibiting a cracking
order of one (Weekman and Nace, 1970). On the other hand, gas oil has a broad boiling range
of compounds with a large number of first order reactions (from individual species) acting in
parallel. The first gas oil molecules to crack show a much higher reaction velocity than
subsequent molecules which are more refractory. This depth of cracking effect due to the
distribution in crackability of components within the feed results in a decrease in gas oil reactivity
as the conversion increases.
Pryor and Young (1984) showed that a large variation in cracking rate exists from the low
boiling end to the high boiling end of a gas oil. It is well accepted that the feedstock crackability
seems to correlate well with boiling point where within many hydrocarbon classes crackability
increases with molecular weight and the relative concentration of the more crackable groups is
greater in the high boiling fraction.
Furthermore, during the cracking process there is an increase in the number of moles of
products being formed from the gas oil. In a riser, which is normally modeled as a plug flow
reactor, this results in a decrease in the massic vapour density. If the concentration of the
reactants is defined at a constant volumetric flow, the apparent order also increases because the
actual concentration decreases much faster than expected as the conversion increases. A pseudo-
second-order reaction has been normally used to account for these non-linear effects (Weekman,
1968). However, the reaction order should be independent of the reaction system used and an
additional term to account for the increased vapour velocity in a flow unit should be used to
define the formal kinetics (Shaikh and Carberry, 1984).
According to the three lump model, the rates of gas oil cracking and gasoline cracking may be
written as:
(1.1)
(1.2)
Pachovsky et al. (1973) used a more fundamental approach by assuming a gas oil reaction order
of (1 + W) where W represents the oil refractoriness accounting for feedstock crackability and
catalyst characteristics. Essentially, W is left as an extra parameter to be solved for which is
feedstock dependent.
The deposition of coke on the catalyst results in rapid activity decay and hence a catalyst decay
function is multiplied by the intrinsic rate to give the actual rate. It is normally assumed that the
same active sites will crack both gas oil and gasoline molecules, therefore the activity decay
functions 4>, and 4>z are assumed equal (Weekman, 1968). In general, the catalyst activity is
dependent on the carbon laid down and is thus related to the time the catalyst is exposed to
hydrocarbons. Then, to completely describe the kinetics of cracking according to the three lump
model involves the determination of the parameters ~, kb kz and the deactivation function 4>.
The three lump model has been successful in adequately describing gasoline selectivity
behaviour from laboratory experimental data from studies done for one specific feedstock with
one particular catalyst (pachovsky and Wojciechowski, 1971, 1975a, 1975b 1975c; John and
Wojciechowski, 1975; Campbell and Wojciechowski, 1969, 1971; Gross et al., 1974; Corella
et al., 1985). As well, the model as been used in commercial and pilot transfer line units with
reasonable success (Shah et al., 1977; Paraskos et al., 1976; Corella et al., 1986).
83
The work of Nace (1970, Nace et al. (1971) and Voltz et al. (1971) showed that the rate
constants of this model changed with gas oil composition and that they could be correlated to the
paraffinic, naphthenic and aromatic compositions of the feed. Gross et al. (1974) verified that
feedstocks with the highest content of paraffins and/or naphthenes showed the highest rate
constants for cracking and gasoline formation and the lowest rate of catalyst deactivation.
Therefore, rate constants obtained using the three lump model are adequate for the range of
feedstocks used and extrapolation to unknown feedstocks can be done with little confidence. It
became evident that the chemistry of the feedstock would have to be accounted for by the use of
higher lumping models to be able to obtain rate constants independent of feedstock composition.
2.2. THE TEN-LUMP MODEL
A ten-lump model developed by Mobil researchers (Jacob et al., 1976) identifies lumps whose
rate constants are independent of initial gas oil composition. The reaction scheme they
developed, as shown in Figure 2, is an extension of their earlier 3-lump model (Weekman and
Nace, 1970). The ten lumps are based on groups of paraffins, naphthenes, aromatic rings, and
aromatic substituent groups in light (220°C to 345°C) and heavy oil (345°C+) fractions. The
gasoline (G) and light gases plus coke (C) lumps remain the same as in the 3-lump model. The
kinetic scheme shows that a heavy paraffinic molecule (P.,) can crack to form a light oil paraffinic
molecule (PJ and molecules in G lump and C lump. PI molecules can crack to form G and C
lump components. The same network is given for the naphthenic compounds. No interaction
terms are included between the paraffinic, naphthenic and aromatic groups. It was determined
that such interaction terms did not significantly improve the model (Jacob et al., 1976).
I. ilQl'loo! f>'acl>C<" \220 I.e JoII~ C\
~.~OIi".tClIOO':l<ISC.)
Figure 2: Kinetic Scheme for the 10-lump model (Jacob et al., 1976)
The aromatic hydrocarbons are further subdivided into two categories one representing
substituent groups attached to the rings in both heavy and light oil fractions (Sb and SJ and the
other representing aromatic rings in heavy and light oil fractions (Ab and AJ as determined by
the n-d-M method. The aromatic rings are shown to form coke species and not gasoline due to
their refractoriness and coke precursor characteristics. The fact that aromatic rings with side
chains can form gasoline when a side chain is cleaved and the ring drops into the gasoline
fraction is accounted for in the rate constant for the substituent group. As well, an interaction
term is used to include the reaction where Sb molecules crack to form Al molecules (such as a
three-ringed aromatic with a side-chain cracking to form a bare three-ringed molecule in the light
oil fraction).
The gasoline fraction is maintained as a single lump to avoid further complexity involved with
such a model that would distinguish between P, N and A molecules in this group. Such a scheme
84
would however allow the prediction of gasoline composition and quality (Jacob et a1., 1976).
The overall reaction network results in ten-simultaneous equations which can be solved in a
step-wise fashion due to the irreversible reactions. The matrix of rate constants is lower
triangular involving 20 kinetic constants (plus deactivation function parameters).
The ten-lump model has shown success in adequately describing selectivity and conversion
behaviour in pilot plant and commercial risers for a wide variety of feeds without modification
of the rate constants. However, the simplicity of kinetic representations such as the ones for the
three-lump modeJ are partially lost. In using higher lumping models where the number of
parameters is significantly increased means that greater amounts of experimental data are also
required.
Coxson and Bischoff (1987) have shown that the ten lump model can be represented by a six
lump model based on statistical methods. They used cluster analysis which determines the error
(additional sum of squares error) associated with using successively smaller numbers of lumps.
Starting with the 8 oil lumps the number of lumps were reduced by fusing lumps together that
statistically fell into similarity classes. In reducing the number of oil lumps to 4 it was found that
the error increase went form 0.019 to 0.537 whereas a further reduction to 3 clusters gave an
error of 1.44. Thus it was concluded that without a significant increase in error, the 4 clusters
could be adequate. The resulting lumps consisted of Ph, Nb and NI as one lump; Sb' SI and PI as
a second lump with the Al and Ab lumps remaining the same. The reaction paths included the
first lump forming compounds in the second lump which may be questionable since it does not
make sense chemically that light naphthene molecules would form heavy aromatic substituent
groups during cracking.
Cox son and Bischoff (1987) also comment on the inherent tradeoff in lumping systems which
are not exactly lumpable. Using higher lumps will lead to successive model improvement but
at the expense of the advantage of having a small number of lumps. They suggest a criterion for
choice of the number of lumps based on comparing the clustering error with the actual
experimental errors. The use of more lumps involves an increased number of experiments which
leads to increased experimental error. However, with the improvement of analytical techniques
and rapid advances in computing technology and capacity, higher lumped models will be
favoured. One must also weigh the benefits of the additional information obtained from the more
complex model against the additional time and cost involved in obtaining the extra experimental
data.
2.3. OTHER MODELS
Some other models have been used in evaluating the kinetics of catalytic cracking. Yen et al.
(1988) expanded the three lump model into a four-lump model by separating the coke and the C4
and lighter gases in the original C-Iump. The kinetic model considers instead of three kinetic
constants, six since both the gas oil and gasoline can crack to form coke as well as light gases.
This model is more of a process model and provides information on coke yield and selectivity.
The amount of coke formed is important for the heat balance in the FCC process as well as in
determining the extent of reaction and primary product yield. Although the model is claimed to
predict better coke yields it suffers the same weakness as the three-lump model in that the
chemistry of the feed is not accounted for.
Another approach has been to subdivide the oil from the four-lump model into boiling fractions.
Takatsuka et al. (1987) presented a six-lump model for residual oil cracking where the oil lump
was divided into a residual oil fraction, a vacuum gas oil/heavy cycle oil fraction and a light oil
fraction. The cracking of the resid fraction and the VGO fraction was taken as second order and
85
the light oil was assumed to crack with first order kinetics. Each of the oil lumps can crack into
the subsequent lighter fractions as well as to gasoline, gas and coke.
2.4. CATALYST ACTIVITY DECAY FUNCTIONS
One of the earliest and most important studies on the kinetics of coking was published by
Voorhies (1945). The simple rate law developed from his work has played a vital role in the
design of most commercial FCC units. The amount of coke deposited on both natural and
synthetic clay catalysts at various temperatures and with a wide variety of charge stocks was
studied by Voorhies. He showed that coke formation was primarily a function of catalyst to oil
contact time or catalyst time-on-stream, t:
(1.3)
where Ce is the mass fraction of coke on the catalyst and f and m are constants (m being about
0.5). Later, studies by Rudershausen and Watson (1954) on cyclohexane cracking and by Prater
and Lago (1956) on cumene cracking verified Voorhies formulation. A difficulty with the
Voorhies equation, as pointed out by Yates (1983), is its implication that the coking rate is
independent of reactant composition, extent of conversion and space velocity. Further work done
by Voltz et al. (1971) showed that, for a wide variety of charge stocks with a zeolite catalyst,
Voorhies law was quite adequate. However, Ozawa and Bischoff (1968) reported higher initial
coking rates than the Voorhies rate law would predict.
Froment and Bischoff (1961, 1962) examined the effect of catalyst decay and reactor
performance when coke is produced from both products and reactants. They showed a Voorhies
type law holds over certain operating ranges and defined a deactivation function as the fraction
of active sites remaining active on the catalyst. They related this function, ~, to the coke
content, C" by the following two empirical relationships which are equivalent at low coke
concentrations:
~ = exp(-aC e) and ~ = 11(1 + aCe) (1.4)
where ais a constant.

Levenspiel (1972) and Wojciechowski (1968) developed similar expressions but based on the
catalyst time-on-stream as the main variable. This approach also used by Gustafson (1972) and
Weekman (1969) includes a decreasing exponential decay function. This so-called exponential
law is a particular case of a more general power law function which has been used in various
forms by various researchers to fit their particular experimental data (Wojciechowski, 1974;
Pachovsky et al., 1973; Newson, 1975; Mann et al., 1986; Mann and Thomson, 1987; Tan and
Fuller, 1970; Forzatti et al., 1984; Fuentes, 1985; EI-Kady and Mann, 1982a, 1982b).
It is evident that there are two general approaches used in modelling catalyst activity decay due
to coking. One relates activity to the time-on-stream (Wojciechowski, 1974) and the other relates
activity to the amount of coke deposited on the catalyst (Froment and Bischoff, 1979; Hatcher,
1985; Nam arid Kittrell, 1984). From a mechanistic point of view the catalytic activity should
be related to coke concentration on the catalyst. However, the time-on-stream theory which
ignores the relation of hydrocarbon concentration with the fraction of active catalyst sites, has
been used for plant simulation (paraskos et al., 1976; Shah et al., 1977; Jacob et al., 1976)
86
because of simplicity and the fact that the residence time of the catalyst in a riser is an important
parameter.
Szepe and Levenspiel (1971) showed that many of the rate laws proposed can be readily derived
by assuming that the rate of decay is a function of the number of active sites. The general
equation for aging by coke deposition on a catalyst of homogeneous surface can be written as a
function of the fraction of active sites or as a combined function of the fraction of active sites and
the concentration of gas oil to the power two:
- d~/dt = k.i ~ (1.5a)

- d~/dt = k.i' C/ ~ (1.5b)
where ~ is the fraction of active sites remaining, t is the catalyst time on stream, kd and k.i' are
deactivation kinetic constants, n is the order of decay and CA is the gas oil concentration.
Equation (1.5b) assumes that the relationship between the fraction of active sites, ~, and the
fraction of active sites covered by coke, ~c, is ~ = (1-~c).
The two popular forms of Equation (l.5a) used to describe decaying catalysts during catalytic
cracking are the exponential law and the power law given by the following equations:
Exponential : ~ = exp(-kd t) (1.6)

Power Law: ~ = DrN (1.7)
where D = [(n-I)kJ-N and N = lI(n-I).
The exponential decay form is derived from assuming first order decay (ie. n= 1) and
integrating equation (1.5a) with ~= 1 at t=O. The power law given by equation (1.7) is the
integrated form of equation (1.5a) with the unrealistic limits of ~ equal to infinity at zero contact
time. A more adequate form of the general power law is given by Wojciechowski (1974) which
is the integrated expression of equation (1.5a) with ~= 1 at t=O:
~ = [1 + k.it(n-l) )"N (1.8)
From equation (1.8) it is apparent that two parameters, kd and n, are required to describe the
decay kinetics. Thus, authors such as Nace et al.(1971) and Corella et al.(1985) who used the
decay function of the form ~ = DrN did not evaluate kd but instead included it in their overall
kinetic constant, a combined cracking and decay constant. This is certainly sufficient from an
empirical stand point but to adequately describe the deactivation kinetics the value of k.i must be
assessed. As well, the activation energy from these studies represents the combination of the
energy of activation of gas oil cracking and the activation energy for the loss of active sites.
Another approach taken in describing the kinetics of catalyst deactivation in the FCC process
has been to consider the catalyst as having a non-homogeneous surface that is, with active sites
of different strength or acidity (Corella et al. 1985; Corella and Menendez, 1986). At least three
types of acid sites are considered being strong, medium and weak in acid strength. Corella et
al. (1985) showed, that with first order kinetics the decay function results in a summation of at
least three different exponential decay functions. The relative contribution of each exponential
function varies with time-on-stream similar to the decreasing order of deactivation with increasing
time-on-stream using the power law function.
The work done by Weekman (1968), Nace (1970), Nace et al. (1971), Gross et al. (1974),
Paraskos et al. (1976) and Shah et al. (1977) using the same decay function based on the time-on-
stream theory obtained different values for the deactivation parameters. Corella et al. (1985)
87
showed that the discrepancy in values obtained by Nace et al. (1971) and Weekman (1968), who
used relatively high contact times (from 1.2 to 40 min.), and the values reported by Paraskos et
aI. (1976) and Shah et aI. (1977), who used shorter contact times (from 0.1 to 10 s), was due
to the variation in mechanism and observable order of the catalyst decay with time. This type of
modelling, taking into account the distribution of acid strengths in the catalyst and using a
summation of exponential functions, describes the deactivation kinetics using a sound mechanistic
approach. This may become important for developing a way to predict the kinetic behaviour of
cracking from a change in catalyst properties. However, there is still uncertainty as to which
parameters in addition to reaction testing, should also be incorporated in the model. As well, it
suggests that in the first seconds of cracking, which are the most important ones in an industrial
riser, one could use a simple first order decay model to describe the catalyst deactivation
adequately. Of course, the value of ~ obtained would be valid only for the short contact time
periods covered and for the particular catalyst and gas oil used.
3. Reactors Used For FCC Studies
Many different types of laboratory catalytic reactors are available for assessing kinetic rate
parameters including fixed bed, fluidized bed, stirred batch, continuous stirred tank, re-circulating
transport, differential, recycle, straight-through transport and pulse reactors (Doraiswamy and
Tajbl, 1974; Weekman, 1974; Sunderland, 1976). In the case of studing catalytic cracking
reactions on a bench scale, fixed bed and fluidized bed reactors have been traditional choices
(Weekman, 1968; Gross et aI., 1974; Campbell and Wojciechowski, 1970; Weekman and Nace,
1970). However, most of the kinetic data from these studies were obtained using reaction times
greater than 2 minutes which are not representative of commercial riser contact times.
Tubular fixed bed reactors for studying FCC reactions are also somewhat limited by large
temperature gradients due to the highly endothermic nature of cracking and pressure drops across
extremely fine fluid catalyst beds. These deficiencies can be eased to some degree by using a
micro-reactor with catalyst dilution (Nace, 1969; Collyer, 1987; Larocca, 1988).
Fluidized bed reactors are quite suitable for handling fast, complex reactions with good
temperature and mixing control. These systems are also very appropriate for fast aging catalysts
because the possibility of removing them easily from the reactor as in the case of FCC units.
Some disadvantages are that residence time distribution of reactants in the reactor are uncertain
and attrition is a problem. As well, these reactors are very complex to model and operate.
However, differential aging within the catalyst bed is possible for integral gas phase reactant
conversions across the reactor giving a reaction rate directly.
For moving bed reactors, Sunderland (1976) suggests that the disadvantages (catalyst attrition,
separation of catalyst and reactants, high ratio of gas to catalyst volume) usually outweigh the
advantages.
In general, for obtaining reliable kinetic data that is representative of riser cracking, equipment
must be used that allows for short contact times and under conditions that closely simulate those
in a riser.
3.1. THE MICROACTIVITY TEST (MAT) REACTOR
A great need exists for reliable FCC performance tests which can be used for the evaluation of
feedstocks and catalysts (O'Connor and Hartkamp, 1988; Mitchell and Moore, 1988). With the
hundreds of catalyst variations available the choice of a suitable catalyst becomes complex and
88
the ability to predict unit performance rests on the evaluation test used. This catalyst choice is
crucial since small changes in yield structure will have a large impact on FCC economics. Most
laboratories have unique testing programs with wide differences in both catalyst steaming methods
and catalysts activity test procedures (Moorehead et aI., 1988).
The traditional Micro Activity Test (MAT) remains the main tool for basic FCC research and
catalyst and feedstock evaluation (O'Connor and Hartkamp, 1988; Campagna et al., 1986). This
test was developed because of its simplicity, reproducibility and quickness of evaluation in
comparison to pilot units. The MAT method is an ASTM procedure (ASTM D-3907-80) which
comprises a fixed bed of 4 grams of catalyst, operated with continuous oil vapour feed for 75
seconds at a temperature of 482°C under a cumulative catalyst to oil ratio of 3. This specific
form of the MAT procedure has not been successful in predicting commercial unit performance
and provides only very limited information on selectivity (Carter and McElhiney, 1989; Mauleon
and Courcelle, 1985; O'Connor and Hartkamp, 1988). In general, catalyst choice based solely
on MAT data is questionable and rarely done and it is not suited for simulating commercial
operation. Its main use is in the relative comparison of activity of FCC catalysts (Humphries and
Wilcox, 1990).
Mott (1987) outlines the shortcomings of the original MAT test which seriously question the
reliability of the results. He suggests that the MAT activity is commonly misinterpreted because
of the indirect interactions of the catalyst with the dynamics of the heat balance. In some cases
catalysts with very high MAT activity were observed to perform poorly in FCC units. For
example, an uItrastable zeolite catalyst with low coke selectivity introduced into a unit that had
been running on a rare earth zeolite catalyst with high coke selectivity, gave good performance
despite having a low MAT activity (Davison, 1984).
Recently, Sapre and Leib (1991) indicated that there exists, as described in Figure 3, systematic
differences between the conversion and catalyst activity and coke selectivity in catalysts tested in
MAT and fluidized beds(FFB). These differences also exist with the conversions observed in riser
units.
100 ~--------------------------------------~
75
FFB
Conv.,.lon, % 50
25
50 7S 100
MAT Conversion, %
Figure 3: Comparison of MAT and FFB conversions. Lines correspond to model predictions.
89
The basic problem lies in the fact that in the MAT unit the catalyst remains fixed while in a
FCC riser reactor the catalyst moves along with the hydrocarbon vapours. Mott (1987) describes
this in terms of the number of active sites. In the MAT unit the number of active sites is fixed
while in real operation the number of active sites delivered to the riser per unit of feed is dynamic
and will change according to the heat requirements and the combined coke-making tendencies of
the feed and catalyst. Thus, the most effective FCC catalyst should be determined by the number
of active sites it can bring to the reactor per mass of feed which may not necessarily be the
catalyst with the highest MAT activity (Mott, 1987).
In general, the MAT procedure has the following five drawbacks:
1. Long contact times (75 seconds) which are not representative of commercial units (less than
10 seconds),
2. The partial pressure of reactant hydrocarbons is much lower than in commercial units (0.05
atm instead of 1 atm),
3. Coke profiles exist in the 150 mm long catalyst bed, making coke a function of the axial
position inside the reactor and creating the possibility of channelling,
4. There is no standard test for the steam deactivation procedure thus making the observed
activity value a function of steaming conditions,
5. The method is unable to predict commercial performance because it reports an average specific
activity per mass of catalyst.
As a result of the above describe inadequacies of the MAT method, modifications have been
made to provide a more reliable method which has been called the 'micro-selectivity test' (Carter
and McElhiney, 1989) and the 'microscale simulation test' (O'Connor and Hartkamp, 1988).
These modified tests provide detailed yield structure information and an economical and quick
means of comparing catalysts which is very valuable to the refiner (McElhiney, 1988;
Montgomery and Letzsch, 1971; Mott, 1987; Yatsu and Keyworth, 1990; Mauleon and
Courcelle, 1985); Tsai et aI., 1989). The modifications include higher reactor temperatures,
shorter oil feed durations and better reactor design. A usual criterion is to use the catalyst mix
temperature as the operating temperature of the test which is 25 to 45°C higher than the riser
outlet temperature (Maul eon and Courcelle, 1985). Run times of 15 seconds with 2 to 4 seconds
of vapour contact time have been reported giving yield breakdowns and trends which correspond
very well with actual FCC data (O'Conner and Hartkamp, 1988). The modified MAT has also
been used in combination with improved gas chromatographic analysis of the product to give
gasoline properties (GC-RON, GC-MON, front end olefinicity, mid-cut branching, aromaticity
and GC-bromine number) that can predict quite well actual refinery results (yatsu and Keyworth,
1990).
Despite the improvements to the MAT test it still has the shortcomings of developing coke
profiles in the catalyst bed, due to the nature of the fixed bed operation and also in achieving
non-isothermal conditions. These two facts are very undesirable in terms of performing catalytic
studies to determine kinetic parameters for riser cracking (Larocca et aI.1989). Kinetic modelling
of catalytic cracking reactions using the MAT test then becomes difficult and certain
approximations are necessary (Forissier and Bernard, 1989). This can lead to inaccurate and
unreliable data to be used for modelling commercial units.
3.2. THE PULSE-MICROCATALYTIC REACTOR
A pulse reactor used for kinetic studies usually involves cumbersome mathematical equations due
to the unsteady state condition of the reacting system. However, the pulse technique has been
demonstrated to be successful (Bett and Hall, 1968; Matsen et aI., 1965; Desay and Anthony,
90
1987; Kalthod, 1985) and has been used for kinetic FCC studies (Nace, 1969a, 1969b; Collyer,
1987; Morely, 1987; Larocca, 1988,Larocca et aI, 1990).
The pulse-microcatalytic technique applied for catalytic cracking studies as proposed by Larocca
et al.(1989) involves as described in Figure 4 the passage of a small pulse of vapourized oil (in
the order of 0.5 mL) through a small bed of catalyst diluted with inert solids. The effluents from
the reactor can be sent directly to a gas chromatograph for on-line analysis. The system can be
kept under isothermal conditions because of the small amount of catalyst in a large heat sink.
Other advantages include simple design and construction with low cost. Also, the results from
each pulse injection give directly the instantaneous values for kinetic parameter evaluation.
o L
8
Figure 4. Schematic diagram of experimental apparatus: (A) filter, (B) flow control, (C) TCD
box, (D) six-port valve, (E) three-way valve, (G) syringe injector, (H) reactor, (J) high-
temperature valve, (1) gas chromatograph, (K) mass spectrometer, (L) vent valve, (M) gas loop
(Larocca et aI., 1990).
The technique is particularly suited for deactivation studies since the catalyst activity is assumed
constant during every single pulse (hence instantaneous rate measurements). In one particular
unit, the time-on-stream is defined on a cumulative basis over several injections of 5 J1.L of gas
oil and a reverse flow of gas between injections fluidizes the bed of solids (0.1 grams of catalyst
diluted with 2.3 grams of inerts) and therefore prevents the development of coke profiles because
of the uniform mixing of the particles (Larocca, 1988). In terms of simulating riser cracking,
this type of approach is somewhat equivalent to riser operation with multiple feed injection points
along its height, a possible most valuable alternative for riser cracking. This is a result of the
several pulse injections with fresh oil which are summed to give a cumulative catalyst to oil ratio
and coke make.
3.3. PILOT PLANTS UNITS
For the advancement in FCC technology it is necessary to have a successful scale-up procedure.
The ability to bridge lab-scale performance results to commercial units is crucial. Circulating
riser pilot units potentially provide the best small-scale simulation of commercial FCC yields
(Carter and McElhiney, 1989). Different types of pilot units have been used including once
through or 'sling-shot' reactor systems, fixed fluid bed, moving fluid bed and folded riser systems
(Young and Weatherbee, 1989; Leuenberger et aI., 1988; Humes, 1983; Corella et al., 1986).
The types of pilot plants most favoured are those which have riser reactors and include
91
continuous regeneration of the coked catalyst (young and Weatherbee, 1989).

The once through pilot unit offers simple design and operation but does not include continuous
regeneration. Large inventories of catalyst are required and thus these systems are limited to the
type of studies that can be done. Some of the large pilot plants process 1-5 barrels per day
requiring in the order of 40 feet height which is fairly capital intensive (Young and Weatherbee,
1989). ARCO licenses technology for their smaller circulating pilot plant with continuous
regeneration (LABFCC). Folded riser reactors were later employed along with pressurized
operation and computer control (Humes, 1983). Young and Weatherbee (1989) state the major
deficiencies of this design:
1. Limited ability to process heavier resid feeds

2. Inability to closely simulate commercial riser with high temperature regeneration
3. Folded riser design has operating uncertainties at commercial pressures
4. Inability to simulate the interrelation of process variables
5. Isothermal temperature instead of adiabatic as in the commercial process.
Technology offered by Davison in their Davison Circulating Riser (DCR) unit overcomes some
of these limitations. The DCR involves an adiabatic riser reactor where the reactor temperature
is maintained by controlling the circulation rate of hot catalyst from the regenerator to the
reactor, identical to commercial operation. In this way the temperature profile in the reactor is
determined automatically as the natural result of the unit operating conditions (reactor exit
temperature, catalyst temperature and feed preheat temperature). A schematic of the DCR unit
is shown in Figure 5 which is a small scale unit of approximately 12 feet in height where the
catalyst residence time in the riser is about 6 seconds and the vapour residence time is about 3
seconds (Young and Weatherbee, 1989). Davison claims that the DCR can effectively match
commercial yields and can be applied to resid processing and can be used for process or catalyst
studies. As well, the riser reactor can be operated in an isothermal mode to perform kinetic
studies.
CAS
ANALYSIS
OIL on. z
fUO filED :!
STORAGE SlORAGIE ::
o
'1 12 o
>-
...
II:
i5
...
o
II:
DEIONIZED H,O
Figure 5. Schematic diagram of the Davison Circulating Riser unit (young and Weatherbee,
1989).
Although pilot units can provide the best simulation of commercial yields, these units are
92
expensive to purchase and operate and are usually not suited for testing large numbers of
samples. Small continuous pilot plant units (2-3 m height; 1-2 cm diameter) could show other
limitations concerning the combinations of catalyst/oil ratios and residence times allowed to be
explored (Corella et a1., 1986). For example, the increase in space time in a tube reactor is
limited by the height of the tube, as determined by the choking velocity for the unit.
Furthermore, to perform kinetic studies, isothermal conditions are much preferred which may be
difficult to achieve in pilot units.
3.4. RECYCLE REACTORS
Internal recycle reactors have evolved into a useful device for catalyst testing and kinetic studies
since they can be run at very close to large-scale reactor operating conditions including mass
velocities. They are particularly suited for obtaining kinetic data on heterogeneous vapour-phase
fixed bed reactions where mass and heat transfer effects are minimal (Berty, 1974, 1979, 1984;
Mahoney, 1974; Kuchciniski and Squires, 1976; Caldwell, 1983; Carberry, 1969; Hannoun and
Regalbuto, 1988). Kinetic data from laboratory and pilot plant reactors can be obscured by these
physical processes occurring simultaneously with the catalytic reaction especially for gas-solid
systems.
The concept of internal recycle reactors as discussed by Berty (1974) is to sacrifice geometric
similarity completely in order to maintain similarity for the flow, thermal and kinetic regimes of
the catalyst pellet. It must be realized that in scale-up or scale-down, the catalyst pellet size
remains the same. The reactor itself, with appropriate design and high recycle ratio,
approximates the performance of a CSTR. Two designs are commonly employed: The spinning
basket type in which the catalyst moves through the reactants (Carberry, 1969); and the Berty
type in which the reactant mixture moves through a stationary catalyst bed (Berty, 1974). Both
are referred to as gradientless because they are designed to suppress all gas-phase internal
gradients. With regards to the spinning basket type, there is some doubt as to how fast the gas
actually moves past the catalyst particles and temperature measurement in the vicinity of the
catalyst is difficult due to the movement of the basket (Mahoney, 1974). The Berty type reactor
has been used for modelling fixed bed reactions by using a stationary bed of catalyst in a bench
scale internal recycle reactor under continuous flow conditions. For simulating catalytic cracking
reactions similar to those taking place in riser reactor, a fluidized bed of catalyst (to avoid coke
profiles and possible channelling of gas flow when using fine FCC particles in a fixed bed) and
a short reaction time batch type operation would be more appropriate. This was the design basis
for a novel unit developed at the University of Western Ontario, named Riser Simulator (de
Lasa, 1991; Kraemer, 1987). It was envisioned that the use of an internal recycle reactor with
an impeller located above the catalyst basket could provide a fluidized bed of solids as well as
appropriate recycle rates to provide an environment to simulate the reaction regime in a riser.
This system, which can be classified as an internal recycle fluidized batch reactor, is a novel
approach for studying catalytic cracking reactions on a bench-scale level that appropriately
simulate the reaction regime in a riser reactor.
4. Modelling the Reaction Regime in a Riser Simulator
As stated above for catalytic cracking simulation under the reaction conditions of FCCs a bench
scale internal recycle batch reactor was proposed by de Lasa (1991, 1992). It has to be pointed
out that this objective is not easy nor straight forward considering the complex fluid-dynamic
93
interactions that take place in riser reactors. These include phenomena such as solids 'raining'
down at the wall, slip velocities and differences in solids density from top to bottom. However,
if one considers an ideal riser (approached in a down flow riser) where a given mass of vapour
and a given mass of catalyst travel through the transport line in nearly plug flow, then the
simulation of the reaction regime becomes more manageable. Therefore, on a bench scale level
the approach taken was to simulate the case of an ideal riser with plug flow of both the gas and
solids.
The advantage of using an internal recycle reactor for this application is that gas phase mixing
can approach ideality thus minimizing concentration gradients. In general, recycle reactors on
a small scale approach conditions close to ideally stirred tank reactors (Berty, 1984). With a high
degree of volumetric re-circulation, this well mixed gas phase can continuously contact the
catalyst so that these particles see a changing hydrocarbon environment with time similar to solids
flowing in a riser. . , -_ _ _ _ _ SHAFT
SEAl
COJUNG
CD JACKET
NCONEl
BlOCK
CD IUPEllER
GASKET
INJ EATERS
POAT
CATAl YST
s.o.sKET
® GRiO
Figure 6. Schematic diagram of the Riser Simulator (Kraemer and de Lasa 1988a).
A schematic diagram of the Riser Simulator is shown in Figure 6 indicating the essential design
features. The unit differs from conventional Berty reactors (Berty, 1974, 1979) by the important
fact that the catalyst bed is fluidized. This condition is achieved by locating the impeller in the
upper region of the reactor, above the catalyst basket. Upon rotation of the shaft, gas is forced
outward from the center of the impeller towards the walls. This creates a lower pressure in the
center region of the impeller thus inducing flow of gas upwards through the catalyst chamber
from the bottom of the reactor annular region where the pressure is slightly higher. The small
clearance between the impeller and the top of the catalyst basket avoids gas from re-entering the
impeller region through this pathway. The overall direction of gas flow is indicated by the
arrows in Figure 6, where gas if forced to swirl downward in the annular region and then upward
through the catalyst bed generating a re-circulating pattern.
The incentive for this novel fluidized internal recycle design (de Lasa, 1991, 1992) was to
provide intense mixing of gas and solids, preventing the formation of coke profiles that could
develop during cracking and possible channelling of gas that could exist in a fixed bed of fine
solids such as FCC catalyst (60 I'm average particle size). The catalyst sample can then be
considered, at a specific contact time, homogeneous from the point of view of its activity. This
represents one important advantage over an MAT unit in which the first layer of catalyst particles
94
see the highest concentration of gas oil resulting in higher coke deposits in this layer. Subsequent
kinetic interpretation becomes difficult and not representative of riser cracking.
A further design aspect of the reactor that differentiated it from other internal recycle units was
the condition of batch operation. It is essential when trying to simulate riser-type cracking since
the catalyst moves along with the reaction vapours as it passes up the conduit. Therefore catalyst
particles undergo a batch cracking operation where they 'see' a changing hydrocarbon
concentration as they move up the riser with a declining activity due to coke formation.
It is therefore important to reproduce in the Riser Simulator unit the same loading of catalyst
(less than 0.08 &a/cm3........ volume) and achieve a high re-circulation rate of fluid. As weIl, using
similar oil partial pressures (0.8 to 2 atm), catalyst to oil ratios (3 to 10), temperatures (500 to
550°C) and reaction times (less than 10 seconds) as those used in commercial operation then a
similar reaction regime can be achieved. For a desired set of conditions the cracking reactions
are then carried out by having the reactor loaded with a defined mass of catalyst then injecting
a gas oil sample through the injection port where it vapourizes instantly and contacts the catalyst.
At the end of the desired reaction time a sample of the reaction vapours is quickly trapped and
subsequently analyzed to give the product distribution. Additional details about Riser Simulator
design are provided in Kraemer (1991).
ml~l I I
Figure 7. Flow diagram for the experimental set-up (Kraemer et al., 1988a)
The Riser Simulator interconnected with a number of valves, as described in Figure 7, allows
the reactor to be operated in a continuous or a discontinuous mode. Valve V3 is used to switch
flow from argon (used as an inert gas in the reactor) to air which is used for regeneration of the
catalyst between injections of oil. The steps involved for a cracking run can be divided into five
parts:
1. Initial purge
2. Setting of vacuum pressure
3. Reaction period
4. Purging and sampling
5. Regeneration
In step 1 argon flows via line 1 into the reactor (4PV in reactor open position) and out through
line 3 then through the sample loop (6PV in load position), line 6, the vacuum chamber and
finally to a vent. Valve VI is a metering valve and can be used to control the flow of argon.
The reactor is set to 1 atm argon by closing VI and allowing for pressure equilibration. This
leads to step 2 where the 4PV is switched to the reactor closed position and then V6 is switched
to vacuum for setting the vacuum pressure as previously mentioned.
Step 3 involves the injection of the gas oil sample which denotes time zero. At the end of the
95
desired reaction time the 4PV is turned to the reactor open position allowing the vacuum chamber
to be connected with the reactor for rapid equalization of pressure. In this step vapours under
pressure in the reactor quickly flow into lines 4, 5 and 6 as well as the vacuum chamber because
of the lower pressure. The final equilibrium pressure is reached rapidly (I second) and is
measured using the pressure gauge connected to the vacuum chamber.
Step 5 involves switching the 6PV to the sampling position which allows line 7 to flush vapours
from the sample loop to the GC facility via line 8. The entire system can then be purged by
opening valves VI and V2 with V6 switched to vent. This allows argon to flow through the
reactor and vacuum system flushing remaining hydrocarbon vapours. Step 5 is accomplished by
turning V3 to allow air to pass through the reactor which has been heated to the regeneration
temperature to burn off the coke. Step 1 is then repeated to complete the cycle.
The products of the Riser Simulator were directed to a Hewlett Packard 5890A gas
chromatograph which gave quantitative analysis of the reaction vapours. The capillary column
used for separation of the various components in the reaction mixture was an Hewlett Packard
HP-I column. The chromatograms generated for each injection were produced using an HP
3393A integrator. A mass selective detector was also used for identification of several compounds
present in the cracked products and initial gas oil. Mass balance on the Riser Simulator were
conducted at the end of the reaction time period assessing the mass of hydrocarbons purged from
the reactor and comparing it with the total amount of hydrocarbons injected (Kraemer,1991).
Furthermore a number of checks were developed in this unit to confirm proper performance:
- Gas mixing in the reactor was assessed using nitrogen tracer tests with the reactor operated as
a CSTR. The ideal reactor volume was calculated using this distribution and was very close to
the measured reactor volume (43.8 mL versus 45 mL). Moreover, volumetric re-circulation rate
within the reactor was assessed based on observed flow patterns in the bed and certain simplifying
assumptions. From this analysis, the volumetric flow of gas through the bed was calculated to
be approximately 48 mLis which indicates that in one second, approximately 5 lower region
reactor volumes pass through the catalyst bed. This secures good gas re-circulation and overall
mixing in the unit.
- Close to isothermicity during reaction was confirmed. In fact, maximum temperature drop
during reaction was observed to be 5°C with a typical temperature deviation for most runs at
2°C.
- Adequacy and reproducibility of the vacuum-purge sampling system was checked using a
calibration mixture of hexane, toluene and hexadecane.
- Effect of external mass transfer from the bulk phase to the surface of the catalyst particle for
kinetic modelling was also estimated to be negligible even for the limiting case of stagnant flow.
- Fluid-solid mixing characteristics were also confirmed using a fibre optic probe. Light signals
were reflected by the particles as the impeller speed was varied under differing conditions of
pressure and inert gases. This indicates that under reaction conditions the bed is in fact intensely
fluidized and the condition of over-revving does not occur. Furthermore the analysis with fibre
optics shows that under initial conditions before oil injection the bed is in a state of fluidization
somewhat above minimum fluidization. Upon injection the resulting gas pressure increase (or
gas density increase) causes an increase in the impeller pumping rate vaulting the bed into a state
of intense fluidization, with a smaller catalyst bed density (or increased solids hold-up). The
overall effect is a high degree of agitation.
4.1. MODELLING AND KINETIC EQUATIONS IN THE RISER SIMULATOR
The rate equations in the case of the Riser Simulator can be formulated on a weight basis, which
96
is equivalent to using the mechanistically more correct partial pressures because in this unit the
gas volume is constant. In contrast, rate equations based on weight fractions for a flow reactor
must be corrected for volume expansion due to the increase in the number of moles generated
during the cracking reactions. Usually the velocity term in the plug flow riser reactor model
must account for the change in fluid density along the height of the reactor thus an additional
equation is required. The fluid density may be written in terms of the molecular weights of the
lumped components which adds extra complexity.
Since the Riser Simulator operates as a batch reactor, then the change in the number of moles
of gas oil with time is equal to the cracking rate of the oil. This can be expressed in terms of
molar concentrations (or equivalently as partial pressures) as follows:
(3.1)
where rA is the rate of gas oil cracking expressed in moles of oil per gram of catalyst per second,
CA is the concentration of gas oil expressed in moles of oil per reactor gas volume, me is the
mass of catalyst and VT is the total reactor gas volume.
4.1.1. Equations For The Three Lump Model. The three lump model as described in Chapter 2
involves three simultaneous equations describing the cracking of the gas oil lump (A), the
gasoline lump (B) and the light gases plus coke lump (C). Considering first the gas oil lump then
the rate of cracking, rA> in equation (3.1) can be expressed as:
(3.2)
A deactivation function 4> is needed to account for the catalyst activity decay due to coke
deposition on the catalyst. The various forms of this function were discussed in Chapter 2 where
4> can be a function of catalyst time-on-stream or more appropriately as a function of coke content
on the catalyst. The kinetic constant, k." is the overall gas oil cracking rate constant which is the
sum of kl and k3 from the 3-lump scheme. Substituting this value for rA in equation (3.1) results
in:
(3.3)
From the ideal gas law the concentration of gas oil in the reactor can be represented as follows:
(3.4)
where YA is the weight fraction of gas oil in the reactor, W T is the total weight of vapours in the
reactor (inert gas plus hydrocarbons) and MA is the molecular weight of the gas oil. This value
of CA can be substituted into equation (3.3) to obtain the gas oil mass balance equation in terms
of weight fractions:
(3.5)
With an appropriate expression for 4>(t) this equation may be directly integrated since all other
parameters are constant with time. The initial gas oil weight fraction is defined from the known
mass of injected oil and the initial mass of inert gas present in the reactor.
97
The mass balance for the gasoline lump can be obtained in a similar fashion with the rate of
gasoline formation containing two terms, one for the formation from the gas oil cracking and the
other for the disappearance due to gasoline cracking. The change in gasoline concentration (Co)
can then be written as:
(3.6)
where VI is the stoichiometric coefficient for gasoline formation from gas oil usually estimated
as the ratio of molecular weights (MAlMo). By using the relationship to express concentrations
in terms of weight fractions, as given in equation (3.4), then the following equation results for
the gasoline mass balance equation:
(3.7)
It should be mentioned that the stoichiometric coefficient cancels out in this transformation to
weight fractions. This equation, with the appropriate decay function can be solved numerically
where the value of YA is obtained from equation (3.5). Similarly the mass balance equation for
the light gases plus coke lump can be written as:
(3.8)
In general the gas oil and gasoline mass balance equations (equations (3.5) and (3.7» can be
used to solve for the kinetic parameters k." kh and k2 where k3 is calculated by difference from
the known values of ko and k l . A Marquardt regression technique for parameter estimation
combined with a Runge-Kutta method for solution of the differential equations can be used.
The various deactivation functions described in section 2.4 can be substituted for <J! in equation
(3.5). These three decay functions were used in the present study to evaluate kinetic and decay
parameters and the validity of each model was assessed. Substituting for clJ, as given by the
exponential decay function of equation (1.6), into equation (3.5) and integrating gives the
following for gas oil weight fraction:
(3.9)
where YAo is the initial weight fraction of oil. It should be noted that in equation (3.9) the
parameter ex is used instead of kd because it is most commonly used throughout the literature
when describing the exponential decay function (Le. ex = kJ.
Similarly, substituting into equation (3.5) for clJ from the power law decay function as given
by equation (1. 7) and integrating gives the following for gas oil weight fraction:
(3.10)
where k; = Dk.,. It is now evident that the deactivation constant, kd' which is included in the
parameter D, becomes combined with the cracking kinetic constant, ko, when using the power-law
decay function. Thus, the unknown parameters in equation (3.10) are N, related to the
deactivation order, and k; which is a combined cracking and decay kinetic rate constant.
It can also be shown (Kraemer et aI., 1991) that the activity decay function described equation
1.5b, which relates the catalyst activity to the amount of coke on the catalyst, has the following
98
form:
(3.11)
where k/ is the deactivation rate constant.

Substitution of this expression for q. in equation (3.5) does not give an analytical solution and
thus the differential equation requires a numerical solution (Kraemer et al,1991).
4.1.2. Equations/or an Eight Lump Model. An 8-lump model (Kraemer and de Lasa, 1988b;
1989; 1990) can also be used to further breakdown the gas oil lump of the 3-lump model into six
groups to account for the chemistry of the feedstock. This model is similar to the 10-lump model
but does not distinguish between bare aromatic rings and aromatic rings with substituent groups.
This distinction is somewhat complex considering available analytical methods available
(Kraemer, 1991).
I _ light oil IractlOf'1 (220 10 345 C)

h • heavy 011 /ractlon (345 C .)
Figure 8. Kinetic scheme for the 8-lump model (Kraemer and de Lasa. 1988b).
The 8-lump kinetic scheme, as depicted in Figure 8, divides the oil into paraffins, naphthenes
and aromatics in both a light fuel oil (LFO) and a heavy fuel oil (HFO) fraction. The LFO is
defined by the boiling range of 220°C to 345°C and the HFO fraction refers to compounds
boiling above 345°C. The gasoline lump (C 12 to 220°C) and the C-lump (C4 and less plus coke)
from the triangular model remain the same. This model involves 16 kinetic constants where the
HFO lumps (Ph' Nh, AJ can crack to light oil fractions, to gasoline and to light gases plus coke
(C-Iump). The LFO lumps (PI> N1, and A0 crack to form gasoline and light gases plus coke.
The gasoline lump formed from the oil lumps can further crack to C-Iump.
The six oil lumps each represent a reasonably narrow boiling range of compounds and thus the
cracking order is assumed to be one (Jacob et al., 1976; Weekman, 1979). The equations for
the Riser Simulator model can then be expressed as follows for the weight fractions of the three
heavy oil lumps:
(3.12)
where i = P, N, or A.
In these three equations the kinetic constant km is the overall heavy lump cracking constant and
is the sum of kibil> kibG , and kibc • A simplifying assumption is that the cracking sites are the same
for each lump (Le. the same active sites will crack P, N or A molecules) and thus the
99
deactivation function, <P, is the same for each lump.

For the three light oil lumps, the change in the weight fraction of the light oil lump with
reaction time can be written as:
(3.13)
where kil = kilO + k;IC'

Furthermore, for the mass balance on the gasoline fraction, the change in weight fraction can
be expressed as:
(3.14)
A similar expression can be written for the C-Iump formation but is not need in solving for the
coke formation kinetic constants. These values of ki1c and kihc can be found by difference
knowing the values of km and kil obtained from equations (3.12) and (3.13). The matrix of rate
constants is lower triangular thus the three equations for the heavy lumps described in equation
(3.12) can be solved independently from each other as well as independently from the light oil
equations and the gasoline equation. Similarly, the three light oil equations can be solved, in
conjunction with the known values from the corresponding heavy oil equation~, independently
of the gasoline equation. This result is due to the irreversible nature of the cracking network
leading to a stepwise solution (Jacob et aI., 1976).
The solution of the gasoline equation requires the input from the six oil lump equations
resulting in seven simultaneous differential equations which can be solved using a Runge-Kutta
algorithm. The solution strategy for the eight lump model is presented by Kraemer (1991).
5. Riser Simulator for Catalyst Testing
5.1. CRACKING OF GAS OIL
This section reviews examples of results obtained from the catalytic cracking runs conducted
in the Riser Simulator. These runs show the ability of the Riser Simulator to assess catalyst
performance. First, the trends in conversion of gas oils, yields of products and gasoline research
octane numbers will be discussed for both the commercial feedstocks and for the pure light oil
mixtures used. Then the kinetic parameters obtained from the 3-lump model and an 8-lump
model using various decay functions are presented. Additional details about product distribution
are provided in Kraemer (1991).
The definition of the conversion of gas oil was chosen to be consistent with the kinetic models
used. On this basis the unconverted gas oil was taken as the fraction of products boiling above
220°C which in turn corresponds to compounds eluting from the chromatographic column after
n-C I2 • Then, the GC-conversion of gas oil was defined as one hundred minus the weight percent
of unconverted gas oil. This value was then corrected to account for the yield of coke to define
the overall conversion.
100
TABLE 1. Properties of the gas oil feedstocks
Feedstock
Property A B
Specific Gravity 0.9117 0.9389

Aniline Point (0C) 79.4 59
Sulfur, wt% 1.19 0.24
Nitrogen, wt% 0.0012 0.102
Volumetric Average
Boiling Point (0C) 377.2 393
Molecular weight 344.8 331
Composition
(220 to 345°C):
Light paraffins, wt% 17.35 3.27
Light naphthenes, wt% 6.40 12.43
Light aromatics, wt% 6.25 10.88
(345°C +)
Heavy paraffins, wt% 43.03 5.52
Heavy naphthenes, wt% 20.08 25.13
Heavy aromatics, wt% 6.89 42.77
TABLE 2. Catalyst properties
Octacat GX-30
AI 20 3 (wt%) 26 34
Na(wt%) 0.22 0.37
REO (wt%) >2 4.5
Unit cell size (A) 24.24 24.40
(steamed)
Surface area (m2/g) 145 126
(steamed)
Two commercial feedstocks A and B, whose characteristics are reported in Table 1, were
cracked with both Octacat and GX-30 catalysts for different reaction times (3, 5, 7 and 10
seconds) and temperatures (500, 525 and 550°C) are shown in Figures 9 to 12. In these figures
the symbols refer to experimental results while the lines show model predictions (using the three
lump model with exponential decay). The trends in experimental conversion show that with
increasing reaction time conversion increases which is an expected result due to the nature of the
101
catalytic cracking reaction. As well, conversion levels were seen to increase with increasing
temperature which agrees with the fact that at higher temperatures the kinetic rate constants are
higher which results in faster reaction rates. Furthermore the levelling off of conversion at the
higher reaction times, as evidenced in Figures 9 to 12, is indicative of the reaction conditions
where the partial pressure of oil decreases because of the transformation of oil into products.
This is also enhanced by the effect of declining catalyst activity with increasing reaction time due
to the deposition of coke on the catalyst.
Another clear trend can be observed by comparing the conversion levels for the same feedstock
using different catalysts. For example, comparing Figures 9 and 10 it can be seen that aX-3D
gives a higher conversion of feedstock A than that obtained using Octacat for all experimental
conditions studied. The same is true for feedstock B (Figures 10 and 11). This result may be
explained because of the basic differences between these two catalysts. While both catalysts are
designed for octane enhancing purposes, aX-3D has been shown to give increased bottoms
cracking (Montgomery, 1985). Moreover, aX-3D has a much larger unit cell size (24.4 A) as
compared to Octacat (24.24 A) thus one would expect greater cracking activity for aX-3D
because of the postulation that increased unit cell size is proportional to increased acid site
density (pine et al., 1984). Another comparison can be made between conversion levels for the
two different feedstocks cracked with the same catalyst. In both cases it was observed that a
higher conversion level was achieved with feedstock A than with feedstock B. This result is
attributed to the compositional differences between the two gas oils where feedstock B is highly
aromatic and thus more refractive to cracking.
100,.----,-,.--r---,--,----,
• 500·C • SOO·C
• 525·C • S2S·C
80 • SSO·C 80 • SSO·C
..
..
! 60
z
o
Vi
a:
101
~
o
v
20
3 5 7 9 11 13 3 5 7 9 11 13
REACTION T1Io1E (sl REACTION TIME (sl
Figure 9. Conversion of feedstock A on Figure 10. Conversion of feedstock A on aX-3D

Octacat catalyst as a function of catalyst as a function of reaction time and
reaction time and temperature temperature (Kraemer 1991).
(Kraemer 1991).
\02
100 100
• 500·C • S2S·C
SOO·C
• 52S"C •. S50·C
80 .. 5S0·C 80
;.: ;.:
! !
z z
0 0
iii iii
ex: ex:
UI UI
> >
z z
0
0
u u
3 S 7 9 11 13 35791113
REACTION TIME lsI REACTION TIME Is)
Figure 11. Conversion of feedstock B on Figure 12. Conversion of feedstock B on GX-30
Octacat catalyst as a function of reaction catalyst as a function of reaction time and
time and temperature (Kraemer 1991). temperature (Kraemer 1991).
SOr---~---r--'---r--'r--' sOr---_r--~-,--_r--~~
PREDICTE D PREDICTED
• SOO"C • SOO'C
• S2S"C • S2S'C
40 .. 5S0'C 40 .. SSO"C
;.:
! " .!
0
...J
o
...J
UI UI
>= ):
UI
Z
::;
0
III
«
<!I
°O~--~--~~---L--L-~
1 5 7 9 11 13 1 57 '111l
REACTION TIME lsI REACTION TIME Is)
Figure 13. Gasoline yields for the cracking Figure 14. Gasoline yields for the cracking
of feedstock A on Octacat as a function of of feedstock A on GX-30 as a function of
reaction time and temperature reaction time and temperature
(Kraemer 1991). (Kraemer 1991).
103
The gasoline fraction was defined as those compounds leaving the reactor with carbon numbers
ranging from Cs to C12 • This corresponds to a Cs+ to 220°C boiling range fraction normally used
to define gasoline according to the kinetic models used (Jacob et al., 1976). To illustrate the
effect of the operating variables on the gasoline yields for the two commercial feedstocks cracked
with both catalysts, plots of gasoline yield versus reaction time and temperature are presented in
Figures 13 and 14). In these figures, the lines correspond to model predictions (which will be
discussed later) and the points refer to experimental values. The following general trends can be
observed:
- gasoline yield increases initially with reaction time (or conversion) then starts to level off at the
longer reaction time (10 s)
- the slope of the gasoline versus time curve decreases at the higher temperature levels.
The first point confirms the fact that secondary reactions, namely gasoline cracking, become
significant after a certain conversion level The second point, describing the temperature effect on
gasoline yield is better revealed by considering the selectivity to gasoline.
It is also possible to observe the differences in gasoline yields for the same oil cracked on a
different catalysts. Considering Figures 13 and 14 for feedstock A cracked with Octacat and GX-
30 respectively, the gasoline yields were higher for GX-30 at the temperatures of 500 and 525°C.
However, at 550°C the gasoline yield with GX-30 catalyst was significantly reduced and fell
below the yields for Octacat at all three temperature levels for reaction times greater than 3
seconds. This indicates that under these conditions there is undesirable over-cracking of gasoline
combined with preferential transformation of gas oil to light gases. The comparison of gasoline
yields for feedstock B cracked with Octacat and GX-30 catalysts showed a higher gasoline yield
for GX-30 except at 500°C where the yields were quite similar. This suggests that a higher
boiling feed containing more bulky and refractive molecules will give better yields when cracked
at higher temperatures using a catalyst with a larger unit cell size.
One example of light gas yields which were considered to be the C4 and lighter fraction of the
products, is shown in Figure 15. In this figure lines were drawn to help illustrate experimental
trends and do not represent model predictions (Le. model predicts C-lump which combines light
gases and coke). Expected trends were obtained when observing the effect of the operating
variables on light gases yield. For the two feedstocks and two catalysts used (Kraemer,1991),
the light gases yield increased with both increasing reaction time and temperature. The slope of
the yield curve was somewhat larger for higher temperatures reflecting the increase in product
selectivity towards light gas formation. This is explained by increased gasoline cracking and
more beta-scission type cracking at higher temperatures, which both produce larger amounts of
lighter molecules. Comparing the effect of catalyst on gas yields it is seen that yields are higher
at the same reaction time and temperature for the GX-30 catalyst, consistent with the fact that
conversion is also greater. As well, gas yields are higher for feedstock A than for feedstock B
when compared for the same catalyst, temperature and reaction time. Again this result is not
surprising since the same is true for conversion.
Coke formation results are illustrated in Figure 16 where coke yield was plotted versus reaction
time for the three temperatures considered. Lines were drawn in these figures to aid in
visualizing the trends of coke yield with the operating variables. In general, coke formation
increased with increasing reaction time due to greater conversion of gas oil. The effect of
increasing temperature was not the same for each catalyst-feedstock combination. For example,
feedstock A and B cracked with Octacat showed lower coke make at 525°C compared to 500°C.
Feedstock A with GX-30 showed roughly equal amounts of coke yield at the reaction times
below 5 seconds for all three temperatures. For the longer reaction times, as temperature was
increased so did coke yield. On the other hand for feedstock B on GX-30 the coke yields
104
changed only slightly with temperature showing a decreasing yield at the higher temperatures.
This result agrees with the general statement that coke formation generally decreases with
increasing temperatures for a constant conversion (Chen and Luki, 1986; Scherzer,1989).
However, since in a batch mode of operation as in the case of the Riser Simulator conversion
cannot be a fixed parameter, but rather increases with time (which is the case for gas oil
cracking) then it is difficult to observe coke yields on a constant conversion basis. The higher
coke yields at 550°C are likely due to the increased conversion levels.
~ 10r----,--~---r--,_--~~
• 500·C • 500·C
• 525·C • S2S·C
;-: I,() • SSO°C 8 • SSO·C
! ;-:
VI
I.tJ .!
VI
..: 30 ./
...:r
<l> /,J
./ '" ...
0 6-
6 · A ",,;'"
I.tJ
/
<l> ,YO ",' ~
:::; ,~
......
p
I.tJ 6,//
!II:
"-
0 20 0 4 ./
u
0
..J
I.tJ -1-""'-'-
~
1O~ 2
°0 3 5 7 9 11 13 °0 5 7 , 11 13
REACTION TIME (s) REACTION TIME (s)
Figure 15. Yield of light gases for the Figure 16. Coke yields for the cracking of
cracking of feedstock A on Octacat catalyst feedstock A on GX-30 as a function of reaction
as a function of reaction time and temperature and temperature (Kraemer 1991).
Temperature (Kraemer 1991).
It is also interesting to see that Octacat catalyst yielded less coke than GX-30 which has a larger
unit cell size than Octacat. A lower unit cell size can be correlated to a lower concentration of
acid sites for dealluminated zeolites (pine et aI., 1984) which in turn means a reduction in the
ratio of the rate of hydrogen transfer to cracking rate. This results in a reduced rate of
conversion of aromatics into condensed polycycles yielding less coke (Scherzer, 1989).
The calculated GC-RON values for the gasoline fractions obtained from the cracking of
Feedstocks A and B with both Octacat and GX-30 catalysts are shown in Table 3. Some general
observations can be made with regards to the effect of operating conditions on octane number.
Increasing reaction time (increased conversion) resulted, on average, in an increase of GC-RON
at the higher conversions although this was not a significant effect. In some cases the GC-RON
decreased when reaction time was increased from 3 to 5 seconds but then subsequently increased
at higher reaction times. The effect of increased temperature resulted in increased GC-RON
values for all cases as expected. For example, feedstock A cracked with Octacat showed an
average GC-RON of 100.3 (average of the 4 reaction times used) at 500°C and 102.4 at 550°C
resulting in a 2.1 octane increase. The increased olefinicity of the gasoline as a result of more
105
thermal cracking at higher temperatures is a major contributor to higher octane values. This also
corresponds to lowered hydrogen transfer reactions at the higher temperatures which means less
conversion of olefins and naphthenes into paraffins.
TABLE 3. Calculated GC-RON values for Feedstocks A

and B cracked with Octacat and GX-30 catalyst.
Octacat GX-30
t(s) T(°C) Feed A Feed B Feed A Feed B
3 500 100.3 99.1 100.1 99.0

5 99.9 101.5 98.8 100.1
7 100.3 101.5 99.1 100.2
10 100.8 101.7 99.2 99.9
3 525 101.8 101.6 101.0 100.0

5 100.3 102.0 101.2 101.9
7 101.7 102.2 100.3 101.8
10 101.8 102.7 100.4 101.8
3 550 101.9 102.1 101.6 101.2

5 102.3 102.4 101.5 102.0
7 102.5 103.0 101.5 102.7
10 102.8 103.1 101.8 102.9
The effect of feedstock on the GC-RON indicated that the more aromatic gas oil gave a slightly
higher octane gasoline. This is seen by the fact that on average the GC-RON values for feedstock
which is highly aromatic B are higher than for feedstock A which is mostly paraffinic. The result
is not surprising since aromatics show the highest octane rating of the hydrocarbon groups
(Scherzer, 1989).
It is also interesting to see that average octane values for the gasolines obtained using Octacat
catalyst are slightly higher than those using GX-30. This can be explained in terms of unit cell
sizes for the two catalysts. In general, the decrease in unit cell size and corresponding increase
in framework silica/alumina ratio favour the formation of compounds with a high octane value
(Scherzer, 1989). This is to say that a lower unit cell size results in lower total acidity hence
decreasing hydrogen transfer activity and giving a higher olefinic product. Thus, Octacat which
has a smaller unit cell size than GX-30 produces a higher octane gasoline at the expense of lower
conversion and selectivity.
The three lump model groups the C12 + hydrocarbons into one oil lump which is defined as the
unconverted feed and constitutes a wide range of hydrocarbon types. To take a more closer
account of the chemistry of the feedstock the eight-lump model subdivides this oil lump into six
groups: light paraffins (PJ, light naphthenes (NJ, light aromatics (AJ, heavy paraffins (PJ, heavy
naphthenes (NJ and heavy aromatics (AJ. Abbreviated notation will be used throughout the text
for simplicity. The light lumps are defined by a boiling range of 220°C to 345°C representing
light cycle oil (LCO) and the heavy lumps contain molecules boiling above 345°C which
106
represents heavy cycle oil (HCO). The cut point between LCO and RCO on the chromatogram
reports was taken as the n-C20 peak:, with n-C20 included in the LCO fraction.
20
PIIEO/CIID
FEEDSTOCK
A 8
•
.·
• 500·C
! 16
------
-.-
a • 525·
550·C [
.. K,· • ...
~
.
.i "'. , ..........- ---;---.-
~
.
~ 12
%
. -
., ......... ......
o 0 .-._.-;
~
~~-.A":~-=:y
0
_____0
.--~
o0 ) 579111l
REACTION TINE (s)
Figure 17. Yield of PI for feedstocks A and Figure 18. Yield of NI for the feedstocks A and
B on Octacat as a function of reaction time B on Octacat as a function of reaction time and
and temperature (Kraemer 1991). temperature (Kraemer 1991).
0
[FEEDSTOCK
A B
•
•. ·
• 500'C [
! 16 •
• • a 525'C
550'C [ ! \6 o
A
-="i---==t
«
~
~
/~.::..
v
« 2 ~
~
..
1
..i
~ 12
% %
i 0
a c 0: a
~ 0
~~~~-_s _____ ~
-~--§- ooJ
4
15OO'C
PIIEO/CTEO • ,..""
1515'CI·-----
IS5O"t
o
o )579111] ) 579111l
RUCTION TINE (s) RUCTION TIME (s)
Figure 19. Yield of Al for feedstocks A and Figure 20. Yield of Nh for the feedstocks A and
B on Octacat as a function of reaction time B on Octacat as a function of reaction time and
107
:.: ;:
--.
20
_.-..
26 R
.! ! ------
• I. II
2' 52S·C
til SSO·C
22
...~'"
.\
\II ·1
'"
v
2 20
VI
Q
\1 Q
11.1
11.1
~
\\.\ 11.1
11.1
11
12
\\. \
~
Q
z Q
...•«
z
"..... _....... _----.

« 14
\'~ :(
u ~.', 12
~ I
, ~
'--
v v 10
0 ........... 0
;: ~ I
i
z
%
, i 6
.£
~
~
0 0
....
Q
11.1 0 ....
Q
0
;: 0 5 1 t 11 1) 11.1
;: 0 ) 5 1 t 11 1J
REACTION TIME (s)
REACTION TIME (s)
Figure 21. Yield of Nh for feedstocks A on Figure 22. Yield of Nh for the feedstock B on
Octacat as a function of reaction time Octacat as a function of reaction time and
From the GC-MS analysis of the cracked products the weight fractions of each lumped species
were determined. It should be mentioned that the use of the word "yield" for the gas oil lumps
refers to unconverted oil and even though some LCO is formed from the cracking of HCO, it is
not included in the calculation for overall conversion.
To trace the compositional changes of the unconverted gas oil fraction during cracking, plots
of oil lump yield versus reaction time for the three temperatures used were made. Typical
examples are reported in Figures 17 to 19. Curves represent model predictions as obtained using
the 8-lump model with exponential decay and the symbols indicate experimental values. The fit
of the model to the data will be discussed later when the kinetic results are presented. Figure 17
shows yields of the PI lump for both feedstocks on Octacat. It can be seen that the amount of the
light paraffins decreased with increasing time and temperature as the cracking reaction proceeded.
The drop is more pronounced for feedstock A which has a higher concentration of light paraffins
than feedstock B. It appears that with Octacat catalyst, for the reaction times considered, the net
difference between rates of formation and consumption of light paraffins is high enough so that
no significant initial increase of the PI lump is observed as the model suggests and as was found
elsewhere (Jacob et al., 1976). This increase in the light paraffins would presumably be observed
for reaction times smaller than three seconds.
The pattern for the NI lump yields, as illustrated in Figure 18, showed initial increases with
a short reaction time and then decreased as the reaction proceeded. This is due to a fraction of
the heavy naphthene group cracking to form compounds in the NI group which simultaneously
are being cracked to gasoline and C-lump. This is consistent with the 8-lump model which
accounts for the cracking of heavy lumps into light lumps. When temperature was raised, the
initial rise in NI concentration was not as large and the subsequent decrease with reaction time
was more rapid indicating greater reaction rates at the higher temperatures as expected.
108
The yields of the Al lump with Octacat catalyst are shown in Figure 19 and exhibit similar
trends with respect to the ones observed with the Nilumps. The large initial increase in Al yields
is likely due to the cracking of alkyl aromatics in the heavy aromatic lump to give a more
refractory Al compound. For example, an ~ compound consisting of a three ringed aromatic
with a side chain group could crack at the linkage of the side group to the ring, forming a
gasoline compound and a refractory Al compound (three rings). This refractory Al species would
then not crack as rapidly as other alkyl aromatic Al molecules resulting in a net reduction of the
cracking rate of the Al lump.
The yields of the heavy lump compounds are shown in Figures 20 to 22 for the cracking of
both feedstocks on Octacat. The continuous decreasing amounts of heavy oil lumps with
increasing time were expected since conversion also increases and then levels off as the catalyst
becomes coked. The effect of increasing temperature, as discussed before, results in a decrease
of the heavy lump yields (Le. increased conversion). It can also be seen from the yield versus
reaction time curves that the heavy lumps decreased more sharply than the light lumps indicating
higher overall cracking rates for longer chain molecules.
Similar compositional changes of the two feedstocks cracked on GX-30 are reported by
Kraemer (1991) plotting each oil lump versus reaction time for the three temperatures. The same
general trends for product yields with temperature and reaction time as discussed for Octacat
catalyst were also observed with GX-30.
5.2. CRACKING OF PURE COMPOUNDS
In addition to the two commercial feedstocks, mixtures of pure hydrocarbons were prepared to
simulate the three light oillumps:- PI(19.5% tridecane, 19.8% pentadecane, 19.9% haexadecane,
20.5 heptadecane,21 % octadecane),- NI (9.7% tricyclodecane, 38%.5 dicyclohexyl, 13.07%
cyclodecane, 38.7% cYclododecatriene),- Al (17.7% phenylhexane, 23.0% cyclohexylbenzene,
12.2% dimethyl naphth.,22.8% dodecylbenzene, 12.1% Fluorene, 12.1 phenantrene). These
mixtures were cracked in the Riser Simulator to reduce the number of data points necessary with
just two feedstocks to solve the equations for the 8-lump model. The conditions used were
reaction times of 3, 5, 7 and 10 seconds at temperatures of 500 and 550°C using both Octacat
and GX-30 catalysts ..
For all three pure mixtures the conversion was greater when cracked with GX-30 catalyst as
compared to Octacat at 500°C. At 550°C this was also true except for the light paraffins which
showed a higher conversion when cracked with Octacat than with GX-30. This suggests a higher
activation energy for the pure light paraffins when cracked with Octacat. The fact that
conversion in general, with the only exception of light paraffins at 550°C, is higher with GX-30
as compared to Octacat can be related to the unit cell size. As the unit cell size decreases (Si/Al
ratio increases) the catalytic conversion or catalyst activity decreases. Therefore, since GX-30
has a larger unit cell size than Octacat, one would expect higher conversions for GX-30.
Comparing the different 'crackabilities' of the three pure lumps with GX-30 it is evident that
the pure light naphthenes achieved higher conversions for both temperatures studied, with light
paraffins next then the light aromatics. It has been reported (Decroocq, 1984) that naphthenes
and alkyl aromatics crack more readily than paraffins although for paraffins and naphthenes of
the same carbon number the rates are similar (Greensfelder et al., 1949). In this study the
aromatic mixture contained a combination of aromatic compounds including alkyl aromatics and
bare ring aromatics. The bare rings are more difficult to crack thus the combined mixture of
bare rings and rings with substituent groups would have a lower cracking rate than what could
be expected with just pure alkyl aromatics (Greensfelder et al., 1945). This explains the result
109
that the paraffins showed a higher conversion than the aromatics with GX-30 catalyst.
For Octacat, the pure light paraffins showed higher conversions than the pure light naphthenes
or the aromatics with the aromatics being the least reactive. This observation may suggest that
diffusional controls become important with Octacat catalyst where more bulky molecules, such
as naphthenes and aromatics have difficulty in moving through the fine porous networks.
The product for the pure light paraffins shows that the gasoline yields decreased as the
temperature was increased from 500 to 550°C for both catalysts. As well, the slope of the
gasoline yield versus time curve became more flat at the higher temperature level indicating the
increased overcracking of gasoline and the shift in product selectivity. This drop in gasoline
selectivity with temperature is quite sharp and the selectivity drops by an average of
approximately 15% with Octacat catalyst and by 9% with GX-30.
The yields of gasoline for the light naphthenes on Octacat showed an increase when the
temperature was increased from 500°C to 550°C. As well, at the higher temperature, the
gasoline yields decreased more sharply with increasing reaction time than at the lower
temperature level. Similar trends were observed with the pure light aromatics cracked with
Octacat catalyst. However, for both the pure light naphthenes and aromatics cracked with GX-
30, the gasoline yields at 550°C were slightly higher at low reaction times but then dipped below
the yields obtained at 500°C for higher reaction times. This is a result of conversion being
higher for the GX-30 catalyst and shows that the extent of gasoline overcracking also depends
on the conversion. It is also interesting to observe the effect of catalyst on gasoline selectivity.
The selectivity was higher for GX-30 catalyst than Octacat for the pure naphthenes and aromatics.
The light paraffins showed slightly lower selectivity with GX-30 compared to Octacat at 500°C
at 550°C higher values were observed with GX-30. The fact that gasoline selectivity was poorer
with Octacat is consistent with the fact that lower unit cell size catalysts tend to promote free
radical cracking relative to hydrogen transfer reactions, hence producing more light gases
(Scherzer, 1989). In addition, the effect of temperature on selectivity was more pronounced with
the GX-30 catalyst than with the Octacat catalyst, which is to say that selectivity dropped with
an increase in temperature from 500°C to 550°C. Also, selectivity values were much higher for
the pure light naphthenes and aromatic mixtures than for the pure paraffins.
Another general observation can be made regarding the effect of catalyst on coke yields for the
pure light mixtures. The coke yields were lower for the Octacat catalyst. These results are in
line with those obtained with the commercial feedstocks and are attributed to the effect of unit
cell size as explained previously.
6. Kinetic Parameters in the Riser Simulator
6.1. KINETIC PARAMETERS FOR THE THREE LUMP MODEL
To describe the kinetics of catalytic cracking the three lump model was used in combination with
three different catalyst deactivation model. Overall gas oil cracking kinetic constants (~ or Ie.')
along with the decay parameters for the three decay models were determined for four feedstock-
catalyst combinations. An example of these evaluations is presented in Table 4.
These constants were obtained by solving the gas oil mass balance equation for the three lump
model (see equation 3.5). For the case where the power law decay equation was used, the
overall gas oil cracking constant was called~' since it has different units than Ie. (equation 3.10).
Examining the kinetic values it can be seen that the ko values are of a similar order of
magnitude for the three separate decay models used. The values of Ie. for the exponential decay
110
law case were consistently lower than those values of Ie., from the Froment-Bischoff (F-B) model.
However, the differences between these values are not significant, which can be concluded
through the 95 % confidence intervals for each Ie., value. For instance, with feedstock A and
Octacat catalyst (Table 4), at 500°C Ie., for the exponential decay case has a value ranging from
0.845 to 1.305 m6/(kgmo1 .kg"".s). For the F-B decay case Ie., has a confidence interval between
0.924 to 1.564. This overlap means that the two values are not significantly different from each
other. This trend is repeated with the three other catalyst-feedstock combinations for all three
temperature levels.
Table 4. Overall gas oil cracking kinetic constant for

the 3-lump model using 3 different decay functions
(feedstock A with Octacat catalyst)
Decay: e-at rN F-B
T(°C) Ie., ct Ie.,' N Ie., kd
500 1.08 0.12 0.89 0.32 1.24 2.81

±0.2 ±.08 ±.05 ±.14 ±.32 ±1.78
525 1.65 0.16 1.26 0.40 2.09 4.75
±0.2 ±.12 ±.08 ±.17 ±.4 ±3.14
550 2.26 0.19 1.60 0.42 3.02 6.65
±.29 ±.09 ±.08 ±.11 ±.41 ±2.80
EA : 18.84 14.81 22.45
units of Ie.,: (m6/kgmo!.kgcat .s

units of Ie.,': (m6/kgmol.k~t.sl.N)
units of ct: lis
units of~: m6/kgmoF.s
units of EA : kcal/gmol
± denotes the 95 % confidence interval
A further examination of the confidence intervals on the parameters shows that the F-B decay
model gave the largest intervals and the power law decay model the lowest with the exponential
law model having confidence intervals somewhere in between. In some cases the F-B model gave
overlaps of the ko values at one temperature level to that at a higher temperature level which
would mean these two values are not significantly different from each other. This was not found
with the other two models which may indicate a somewhat better confidence with the results of
this study in the power law or the exponential decay.
Concerning the decay parameters for each model, no clear trend was established between the
catalyst decay constant and temperature. The decay constant, ct, for the exponential decay model
for the most part increased with increasing temperature, except for the combination of feedstock
B with GX-30. Here, ct decreased from 0.034 lis at 500°C to 0.012 lis at 525°C then increased
to 0.017 lis at 550°C (Kraemer,1991). However, it can be seen from the confidence intervals
on this parameter that the values overlap each other from 500°C to 550°C meaning they are not
significantly different. This implies that the decay constant, ct, is a weak function of temperature
III
and could be considered as a constant value. The effect of temperature on a, which is defined
as a kinetic constant for catalyst decay is also unclear in the literature. For example, Weekman
and Nace (1970) report a values decreasing with increasing temperature levels (hence a negative
activation energy for decay) whereas Paraskos et al. (1976) report an a increasing with increasing
temperature (positive- activation energy). These differences are likely due to the types of
equipment used to obtain the data. Weekman and Nace (1970) used a fluidized dense bed reactor
with relatively long catalyst times on stream while Paraskos et al. (1976) used a pilot-scale riser
unit to obtain their data.
For the F-B model, the trends in the decay parameter, k.t, with temperature were similar to that
for a. The 95% confidence interval on k.t is as well quite wide which dictates the result that k.t
values are not significantly different at higher temperatures. The same can be said for the value
of N in the power law decay model. However, this result is more plausible since N is
proportional to the order of decay, n, where n = (1 + liN) and is not a function of temperature.
Thus, for example from Table 4 for feedstock A on Octacat, a value of N = 0.4 for all three
temperature levels gives an order of decay of 3.5 (i.e. 3.5 active sites lost per deactivation event)
and for feedstock A on GX-30, the order of decay is approximately 4.5.
Effects of type of feedstock and type of catalyst on the kinetic constants can be seen by
comparing activation energies which were calculated by regression on the Arrehnius equation for
the three temperatures studied. The values of the activation energy for feedstock A on GX-30
are lower than the ones for Octacat for all three models examined. The same is true for
feedstock Bon GX-30 except for the power law model where the EA values are almost identical
for the two catalysts. It has to be further mentioned that the activation energies found in are
ranging from 16.76 to 22.05 kcal/gmol using the exponential decay model are in agreement with
other values reported in the literature (Decrooq, 1984; Wollastow and Haflin, 1975; Weekman,
1979).
It is now possible to see from the data obtained in the Riser Simulator, the effectiveness of the
three decay models studied. The kinetic parameters obtained, case of the ones reported in 4 (for
the four catalyst-feedstock combinations), were used for the simulation. As well, It can be seen
that each decay model gave nearly the same fit to the data. This is further evidenced by the
standard deviation values where for Octacat catalyst and feedstock A for example at 500°C the
standard deviations for the exponential law, power law and F-B model are ± 1.94, ± 1.44 and
± 1.7 respectively. As well, the power law decay gave the lowest standard deviation values of
the three, however the differences are not large. Furthermore, it would not be correct to reject
the other two models just based on the standard deviation values. In this analysis the lack of fit
of the data to each model was checked by using a 95% confidence interval for the F-distribution.
None of the decay models contradict the data which is to say statistically that there is no reason
to assume any of these models is inadequate. This result of model adequacy was also obtained
for the other 3 catalyst-feedstock combinations. The conclusion drawn from these findings then,
is that all three decay functions used can equally represent the data for the conditions used in the
present work. Thus the choice of the model to use for the catalyst deactivation could be based
on other factors such as simplicity and significance (Kraemer et al., 1990b). The use of the F-B
model which is an approach more fundamentally sound in describing catalyst decay does not seem
justified due to its complexity and the power law function uses a combined cracking and decay
kinetic constant and assumes the unrealistic limits that the catalyst decay is infinite at zero time.
From this point of view it is concluded that the use of the simpler exponential decay function to
describe riser cracking under short contact times is an effective model and a preferred one over
the other two. However, it should be pointed out that the use of a more generalized model which
accounts for variation in mechanism and observable order of catalyst decay with time (Corella
112
et a1., 1985) may be necessary for contact times greater than say 20 seconds as in the case of
dense phase FCC operation.
To complete the analysis of the three lump model the kinetic constants kl and k2 were estimated
from the gasoline equation (equation 3.7) using Marquardt's non-linear regression technique on
and then k3 was found by difference. As a comparison, both the exponential decay function and
the power law function were used to represent the catalyst decay. In general it can be stated that
the kinetic constant for the cracking of gasoline, ~, is small showing that for short contact times
there is no significant over-cracking of gasoline. In all cases the value of k3 was smaller than kl
which shows that the reaction is more selective for production of gasoline than for light gases and
coke.
It is also interesting to compare the kinetic constants (kl and k3) for two different feedstocks
cracked with the same catalyst. For example feedstock A produced larger values of kl and k3 than
feedstock B. If the three lump model were to be applicable for any feedstock this would mean
that these rate constants should be similar. However, they are significantly different from each
other (k1 for feed A is approximately 40% higher than for feed B) and the reason is due to the
difference in chemical composition of each charge stock. This result which has been reported
elsewhere (Voltz et a1., 1971) and shows the need for the appiication of higher lumping models
which account for the varying cracking rates of different species found in gas oils. In summary,
the results obtained with the Riser Simulator for the three lump model with feedstocks of
differing amounts of paraffins, naphthenes and aromatics are in general agreement with findings
in the literature that a more sophisticated cracking scheme is required to obtain a kinetic model
that could incorporate the effect of composition, making it feedstock independent. With this
incentive then, an 8-lump model was used to describe the cracking reactions.
6.2. KINETIC PARAMETERS FOR PURE HYDROCARBONS
The overall cracking constants for the pure hydrocarbon groups (PI' N" and A;) are presented
in Table 5. Values obtained using both the exponential decay function and the power law
function are presented. These constants were obtained by solving the light lump equation
(equation 3.13) in the 8-lump model with Yih set to zero. This is equivalent to using the three
lump model for each separate light lump oil mixture with first order kinetics.
Referring to Table 5 it is interesting to note that the values for the decay constant, 01, follow
the decreasing order aromatics, naphthenics, paraffinics on both catalysts at both temperatures
which indicates the coking tendency for the different lumps. The same is true for the constant
N of the power law decay function. Also, decay parameters are consistently higher in value for
GX-30 catalyst than with Octacat catalyst. Further, comparing rate constants of the individual
light lumps (exponential decay case) at both temperatures, it is observed that the light naphthenic
compounds show the highest reactivity followed by the aromatics and then paraffins with the AI
and PI groups being nearly the same for GX-30 catalyst. For Octacat the constants are very
similar for all the lumps, with the only exception of the aromatic lump at 550°C. This
comparison refers to pure cracking potential with no coke on the catalyst. However, when
considering the observed rate of cracking (in combination with coking of the catalyst) in the range
of 3 to 10 seconds it is highest for the light paraffins, followed by the naphthenes than the
aromatics.
In comparing the overall cracking kinetic constants for the pure light compounds obtained from
both catalysts used, it is observed that the values are consistently larger for the GX-30 catalyst.
This suggests that GX-30 has a higher concentration of acid sites than Octacat, which is also
consistent with its larger unit cell size, providing a higher cracking potential. This trend is less
113
pronounced for the values resulting from the power law decay function where ~ values for GX-
30 are only slightly higher than those for Octacat.
TABLE 5. Overall cracking kinetic constants obtained from the cracking of pure light oil
mixtures
Using Exponential Decay:
Octacat GX-30
T(°C) a ~ EA a ~ EA
PI: 500 .09 11.9 ± 1.9 13.2 .23 19.0 ± 1.3 10.7
550 .10 20.1 ± 1.7 .37 28.9 ± 2.2
N I: 500 .11 11.2 ± 2.1 14.4 .33 23.9 ± 1.1 10.1
550 .22 19.9 ± 3.0 .40 35.7 ± 2.4
AI: 500 .28 11.6 ± .07 6.2 .37 21.3 ± 1.8 8.8
550 .34 14.8 ± 1.1 .47 30.2 ± 2.1
[ a in lIs, ~ in cm3/gcat .s, EA in kcallgmol ]
Using Power Law Decay:
Octacat GX-30
T(°C) N ~' EA N ~' EA
PI: 500 .24 10.5 ± 0.6 12.6 .50 12.2 ± 0.7 3.0
550 .25 17.3 ± 1.5 .68 13.7 ± 1.1
N I: 500 .34 9.7 ± 0.9 7.7 .61 11.8 ± 1.5 2.9
550 .51 13.2 ± 090 .71 13.2 ± 2.1
AI: 500 .59 6.3 ± 1.3 1.7 .69 8.8 ± 0.8 1.9
550 .69 6.8 ± 1.1 .74 9.5 ± 0.9
[ kil ' in cm3/gcat.sl-N ]
To complete the description of the kinetic scheme for the pure light groups the values of the
kinetic rate constants of pure lumps cracking to gasoline ~G)' pure lumps cracking to C-Iump
(~c) and gasoline cracking to C-Iump (koc) are shown in Table 6. The summation of ~G and
kilc is equal to ~ and indicates the approximate selectivity of each pure group. Referring to
Table 6, the pure light paraffins show the lowest selectivity to gasoline ~G/ku) which is also
portrayed by the magnitude of kplc which is largest for the light paraffins. The pure light
naphthenes and aromatics show approximately similar selectivities. This trend was also observed
by Jacob et.al. (1976) for light oil lumps in their lO-lump model. A possible explanation for this
is attributed to the structure of the individual hydrocarbon types. For example, comparing the
cracking of a molecule from the pure light paraffin mixture such as n-tridecane and a molecule
114
from the light aromatic group such as I-hexyl benzene it can be envisioned that the straight
paraffin molecule has a higher potential to crack to smaller fragments (less than 4 carbon atoms)
than does 1-hexyl benzene. The paraffin molecule will crack more readily at the third carbon-
carbon bond from either end of the chain as compared to the first or second C-C bond with a
tendency to crack off fragments with three or more carbon atoms (Greensfelder and Vogue,
1945). After these initial ruptures or simultaneously, additional cracking of the larger fragment
continues. Thus products consist largely of C3 to C6 molecules. On the other hand, the 1-hexyl
benzene will undergo scission mainly and most readily at the link bond between the ring and the
alkyl group leaving two gasoline range molecules. It is possible that small fragments may result
from cracking in the alkyl side group, but most of this will occur as secondary cracking of the
new hexene molecule formed from the initial rupture from the benzene ring. A similar cracking
behaviour occurs for light naphthenic compounds such as dicyclohexyl where the main reaction
is cracking of the joining carbon bond between the two cyclo C6 rings. In this way the kinetic
values indicate that light paraffins produce more C-Iump molecules than the other two light oil
groups.
TABLE 6. Summary of the individual kinetic constants

obtained for the pure light oil mixtures using exponential
decay
Octacat
PI: 500 6.35 ±0.7 5.6 ±0.6 1.4 ±1.8

550 8.13 ±0.4 11.9 ±0.3 3.2 ±1.0
NI: 500 7.10 ±3.0 4.2 ±1.9 1.6 ±4.0
550 12.1 ±1.4 5.6 ±l.l 1.8 ±3.0
AI: 500 8.1 ±2.0 3.5 ±0.8 1.4 ±8.0
550 10.5 ±2.8 4.3 ±1.5 4.2 ±10.0
GX-30
TCC) leuo leu
PI: 500 9.1 ±1.1 9.8 ±1.0 1.6 ±3.3

550 11.5 ±2.5 17.4 ±2.0 2.8 ±8.7
N J: 500 21.2 ±4.9 2.7 ±3.1 3.4 ±8.7
550 29.2 ±3.1 6.5 ±2.3 6.4 ±4.7
AJ: 500 18.4 ±0.8 2.9 ±0.9 4.0 ±1.8
550 25.4 ±3.3 4.8 ±1.1 7.4 ±6.7
Values in cm3/gcat.s
115
6.3. KINETIC PARAMETERS FOR THE 8-LUMP MODEL
An 8-lump model can also be evaluated based on the cracking data from the two different
feedstocks and pure mixtures used in this study. The model is an extension of the 3-lump model
where the feed is subdivided into six groups to help account for the chemical make-up of gas oil
making it possible to use the kinetic parameters obtained for other feedstocks. A detailed outline
for the determination of the kinetic rate constants associated with the 8-lump model can be found
in Kraemer (1991). In solving for the kinetic parameters both the exponential decay law and
power law decay functions were used and both sets of data are presented here.
The overall kinetic rate constants for the six oil lumps, as described in the kinetic scheme of
Figure 3,9, are tabulated in Table 7 for Octacat catalyst and exponential decay. Referring to
Table 6.25, it is observed that the paraffins in both light and heavy fractions show the highest
reactivity for all three temperature levels although the differences are not large. The heavy
naphthenes and heavy aromatics have very similar cracking rates. The heavy aromatic lump
shows a comparatively high reactivity since it is a combination of alkyl aromatics which exhibit
high crackability and polynuclear aromatics which tend to be more refractory and favour coke
formation. -Similar trends were also seen for GX-30 catalyst and an exponential decay. Again
the paraffins show higher cracking rates than the naphthenes or aromatics, with the heavy
naphthenes and aromatics showing nearly the same values. Apparently both the GX-30 and
Octacat, which are octane enhancing catalysts, tend to crack heavy paraffi~s more readily than
the heavy naphthenes or heavy aromatics. As well, GX-30 catalyst gives higher rate constants
for the six oil lumps than for Octacat which is expected since GX-30 achieved higher conversions
and has a higher unit cell size (hence higher activity) than Octacat. Also, the rate constants for
the cracking of the heavy oil lumps are greater than for the respective ones for the light oil
fractions consistent with the fact that cracking rate increases with an increase in molecular weight.
The kinetic values obtained using the power law decay function show similar trends as
discussed above concerning order of reactivity among the oil lumps and catalyst effects. It is
noted however that the three light oil lumps show approximately the same cracking rates.
Furthermore, the 95% confidenc~ intervals for the parameter estimates are of similar magnitude
showing that either decay model is appropriate for use in the model for the reaction conditions
used in this study.
It is interesting to compare the overall rate constants for the cracking of light oil compounds
(k;J obtained from pure hydrocarbon mixtures and those obtained from the 8-lump model. For
example, leu for the light paraffins from the pure mixture data (for Octacat at 500°C) is 11.9
cm3/gcat.s as compared to 9.5 cm3/gcat .s obtained from the 8-lump model. At 550°C the same
values are 20.1 and 13.64 respectively showing relatively similar results. However, for the light
naphthenes and light aromatics larger differences are observed, especially for GX-30 catalyst
where for example the value of kNl at 500°C for the pure mixture is 23.9 cm3/gcat.s and the
corresponding value from the 8-lump model is 6.89 cm3/g"'t.s. The fact that the values for the
light lumps obtained from pure mixture data are higher than for the values obtained from the 8-
lump model indicate that interaction effects may be important. The presence of other
hydrocarbon species competing for active sites could explain the differences observed as well as
the fact that the partial pressures of the pure light oil lump mixtures were higher than for the light
oil lumps in the commercial feedstocks. Also, in solving for ~ in the 8-lump model, an averaged
value for the deactivation parameter based on the three different chemical species was used. For
the pure mixtures it was possible to assign to each group different values for the deactivation
parameter. This may help explain differences in the values of leu obtained from the two methods.
116
Table 7. Overall cracking kinetic constants for heavy

and light oil lumps of the 8-lump model with Octacat
catalyst using exponential decay.
Heavy Lumps
n°C) Paraffins Naphthenes Aromatics
~ kNb kAh
500 18.56 ±2.13 15.21 ±1.6 14.24 ± 1.4

525 26.31 ± 1.63 20.35 ±1.7 19.90 ±l.1
550 31.88 ±2.4 24.63 ±3.7 25.80 ±0.9
Light Lumps
n°C) Paraffins Naphthenes Aromatics
kp1 kNI kAi
500 9.49 ±2.1 5.28 ± 1.9 1.28 ±0.5

525 12.43 ±0.9 11.27 ±2.1 4.88 ± 1.2
550 17.64±1.0 16.04 ±2.4 9.55 ±2.1
NOTE:
• units of Ie; are cm3 /gcat ·s
• ± values denote 95 % confidence intervals
·km=kuw+kmo+kmc
·~=~o+~c
The deactivation parameters for the 8-lump model for both the exponential decay function and
power law function were obtained by averaging the. values resulting from the regression analysis
of the heavy oil lump equations for the paraffin, naphthene and aromatic lumps. For the
exponential decay parameter, 01, the values obtained for Octacat (0.228 S·1 at 500°C) and GX-30
(0.274 S·1 at 500°C) were quite similar. As well, the effect of temperature on ex was not
significant, a result also found using the 3-lump model. It is also observed that ex values obtained
using the 8-lump model are 2 to 3 times higher than those obtained using the 3-lump model For
the power law decay function values for N of 0.566 for Octacat and 0.55 for GX-30 were
computed which correspond to a deactivation order of approximately 2.8. This value is in
reasonably good agreement but slightly lower than the order of decay found from the 3-lump
model where for example feedstock A on Octacat gave N = 0.4 which results in a deactivation
order of 3.5. The differences observed here for the deactivation parameters obtained using the
3-lump and 8-lump models are likely due to the models themselves where the 3-lump model
assumes second order cracking of gas oil and the 8-lump model assumes first order cracking and
should be valid for any feedstock.
A limited comparison of rate constants with values found in the literature can be made. Table 8
shows some kinetic parameters obtained from Mobil workers (Gross et al., 1976) and values
117
obtained in the Riser Simulator. Only the paraffinic and naphthenic groups are compared here
since the Mobil lO-lump model further subdivides their aromatic lump into aromatics with side
groups and bare aromatic rings. As well, comparing kinetic parameters from different works is
not straight forward because of the varying conditions used which include type of catalyst,
temperature and catalyst steaming conditions. Thus, in Table 8 it was only possible to compare
the results from this work for the P and N lumps for Octacat and GX-30 at 500°C with the P and
N lumps for a 10% REY zeolite at 482°C, the only conditions reported by Gross et a1. (1976).
As can be seen, the overall kinetic constant for the heavy paraffins, kPb , obtained in this work is
in the range of the value reported by Gross et a1. (1976). The main difference in the individual
contributions for this overall constant is that kPbPI is less than kPbc in the Riser Simulator whereas
kPbPI is greater than kPbc for the values obtained by Gross et a1. (1976). Good agreement is also
evident for the overall cracking of the light paraffins kpl. The data of Gross et a1. (1976)
however show a value of kplo/kplC higher than the one obtained in the Riser Simulator.
The agreement for the values of ~ and kNI from the two studies was not as good as for the
case of the paraffins. Reported values by Gross et a1. (1976) of the overall cracking constants
for the heavy and light naphthenic lumps were at least twice as large as the values found in the
Riser Simulator. Reasonable agreement can be seen for kNbNl> kNbc and kNlc for the two sets of
data. It is important to mention that the Mobil experiments were performed at catalyst residence
times between 1.25 and 5.0 minutes whereas residence times in this work were 10 seconds and
less which is more representative of advanced risers. This difference is a probable contributor
to the difference in kinetic values between the two studies.
Using the kinetic parameter estimates for the 8-lump model with exponential decay the
compositional changes in the given feedstock were simulated as the cracking reaction proceeded.
For example, the predicted yield of Ph (on Octacat) fits the experimental data reasonably well for
all three temperatures (average standard deviation = ± 1.05 wt%). The response shows a smooth
drop in heavy paraffins as reaction time increases, levelling off at the higher reaction time. Good
fit of the model to the data for the heavy naphthenes and aromatics was also obtained with
average errors of ± 1.07 and ±0.82 wt% respectively.
The predicted yields for the light lumps on Octacat catalyst show the data fits well for the light
paraffins although for Feedstock B the model gives an under prediction of light paraffins yields
(average error = ±0.78 wt%). Nj yields on Octacat were in good agreement to experimental
values (error = ±0.70). At 500°C for feedstock B for example the model accurately shows the
initial increase in NI yields with a subsequent decrease at higher reaction times. The model
predictions are not as good for the Aj yields (± 1.41 wt%). The large initial increase in light
aromatics is not achieved by the model, but shows a more conservative increase at short reaction
times and a more level profile at the higher reaction times.
Predicted responses for light lump yields with GX-30 catalyst show similar results as with
Octacat. The fit is less accurate for the Al yields, especially at 500°C where a relatively flat
profile is predicted for both feedstocks. Averaged standard deviations for the predicted responses
for all three temperatures for PI> NI and Al yields are respectively ±0.85, ±0.89 and ± 1.41
wt%. Furthermore, the model responses for the heavy lump yields on GX-30 also showed good
predictions with average standard errors for the Ph, Nb and Ah yields of ±0.50, ± 1.67 and
±0.77 respectively.
The 8-lump model also predicts gasoline and C-Iump yields with reasonable accuracy for the
two different feedstocks. Calculated gasoline yields for both feedstocks cracked on Octacat
(exponential decay law case) show average standard deviation of ±2.0 wt% and the calculated
C-lump yields for the two feeds cracked with Octacat standard errors of ±2.85 wt%. As well,
with GX-30 catalyst deviations are slightly higher with the error for gasoline yields being ±2.93
lIS
and for the C-Iump yields, ±3.9 wt%.

It is interesting to note that using the power law decay function, the standard errors on
predicted gasoline and C-Iump yields were higher being ±2.1 and ±3.0 wt% for gasoline and
C-Iump yields on Octacat respectively and ±5.1 and ±5.7 wt% for gasoline and C-Iump yields
on GX-30 respectively.
TABLE 8. A comparison of kinetic constants obtained in this

work using the 8-lump model with data reported for a 10-lump
model (Gross et al., 1976).
lO-lump 8-lump lO-lump 8-lump
* ** *** * ** ***
~I: 5.75 1.88 4.13 kNhN1 : 6.25 4.56 5.05

Ic..t,o: 15.28 9.35 13.03 kNho :23.53 6.66 8.10
Ic..t,c: 2.18 7.32 7.92 kNhc : 4.13 4.00 5.13
------ ----- ----- ------
kPb: 23.21 18.56 25.08 kNh : 33.91 15.2218.28

kp1o : 6.62 5.06 5.57 kNho : 18.37 3.20 6.38
kp,c : 2.63 4.43 6.03 kN1C : 2.27 2.08 0.51
krl: 9.25 9.49 11.60 kN1 : 20.64 5.28 6.89
[units of Ie; are cm3 /gcat.s]
* Values obtained at 482°C using 10% REY zeolite FCC catalyst

** Values using Octacat catalyst @ 500°C
*** Values using GX-30 catalyst @ 500°C
In general the 8-lump model obtained from the two different feedstocks, along with pure
mixture data and the range of experimental conditions used, gives in the Riser Simulator
reasonable predictions for oil compositional changes during cracking as well as for the gasoline
and C-Iump yields.
7. Conclusions
The main direction of research in the FCC process is in the catalyst development and
manufacturing area (Occelli, 1988; Desai, 1989). Environmental concerns are in the spot light
for the 1990s and depending on government legislations, the oil industry will be challenged to
meet stringent levels set for acceptable products and emissions. Public awareness of global
warming and the greenhouse effect has resulted in regulations on CO, CO2 , SO.. NO. and
hydrocarbon emissions. Governments are now proposing reformulated gasoline and diesel fuels
to improve air quality and reduce human exposure to critical hydrocarbons (Unzelman, 1990).
The reformulations include lower aromatics and olefins, lower sulphur, reduced vapour pressure
119
and lower poly-nuclear aromatics. Some of these have been legislated in critical areas in the
United States and Canada.
The reduction of aromatics (due to their carcinogenicity) and lowered olefins (due to their high
atmospheric reactivity) in gasoline is a formidable challenge for refiners since these classes of
hydrocarbons are a major contributor to gasoline octane (piel, 1989). Now that lead additives
have been completely eliminated from gasoline, alternate high octane components will be required
to replace aromatics and olefins. Refiners will be forced to increase alkylation and isomerization
facilities to produce more highly branched paraffins which have high octane and are acceptable
components.
The FCC process is a major source of light olefins for alkylate and ether production. Thus,
according to Stokes et aI. (1990), its future primary role may be as a light olefin generator.
Modification of process operation and development of new catalysts (such as ZSM-S addition)
will be required for this scenario.
On top of environmental concerns, the oil price structure will cause a shift towards processing
heavier and more contaminated oils in the FCC unit. The development of dual function cracking
catalysts containing scavenging agents to deal with high metal levels is expected to be at the
forefront of FCC catalyst research and development.
The results described in this review demonstrate the importance of novel tools for kinetic
modelling and catalyst development. In this context it is proposed to adopt the Riser Simulator
to effectively represent the catalytic cracking reactions which take place in a FCC riser reactor.
The technique allows for similar conditions to be used such as temperature, catalyst to oil ratio,
partial pressure of hydrocarbons, solids loading and reaction time as those used in commercial
units. Moreover, the contacting of the hydrocarbons with the catalyst is more representative of
riser cracking where the catalyst moves in time with the vapours, than that achieved in the MAT
test.
Catalytic cracking of the two commercial feedstocks over the two commercial catalysts in the
Riser Simulator showed trends, in terms of conversions, product yields and gasoline research
octane numbers as those found in commercial FCC processes. The correlations between catalyst
characteristics and product yields showed that a larger unit cell size catalyst provides a higher
cracking potential due to the higher concentration of acid sites. As well, a lower unit cell size
correlated well with reduced coke make and higher octane numbers for the gasoline product,
though its yield was lower. These observations are in line with existing explanations of catalytic
cracking chemistry on octane catalysts.
Kinetic modelling in the Riser Simulator deals with batch kinetics resulting in relatively simple
equations as compared to other reaction systems. Also, there is no approximation necessary to
account for volume expansion during cracking, which occurs in a flow vessel due to the increased
number of moles being generated, since the reactor is a closed system. The kinetic parameters
determined for the three-lump model reproduced the experimental data with a good fit. These
parameters, determined using short reaction times (s: 10 seconds) fall in the range of reported
values obtained in pilot scale riser units stressing the importance of evaluating cat-cracking
reactions under appropriate conditions. The small value of the gasoline cracking rate constant
indicated little over-cracking for short contact times. The model also verified the feed molecular
type dependence of the kinetic constants suggesting the use of higher lumped models.
The three catalyst activity decay functions evaluated (exponential decay, power law decay and
a Froment-Bischofftype decay) showed that no one particular function predicted the experimental
data better than the others for the range of experimental conditions used. It is concluded that for
short reaction times (below 10 seconds) the simple exponential decay law may be used to
effectively predict the data. It was also observed that the deactivation constant (k.t or a) was not
120
strongly influenced by temperature.

The evaluation of the eight-lump model provides data for cat-cracking kinetics which is lacking
in the open literature. This model furnishes kinetic parameters which account for chemistry of
the feedstock and are applicabl~ to fast reaction times. The model fit the data with reasonable
success with predictions of product yields to within ± 3 wt %. The model also provides insights
to the relative cracking rates of molecular types. The paraffinic groups exhibited higher cracking
rates than the naphthenic and the aromatic groups which suggests that the bulkier molecules
encounter diffusional limitations in the zeolite. Also, kinetic values obtained from pure light oil
mixture data were higher than values obtained from the eight-lump model indicating that
interaction effects may be important.
It is concluded that the Riser Simulator is a suitable system for kinetic modelling of riser
cracking and can also be used as a quick and reliable method for the screening of FCC catalysts.
It is our view that the use of the Riser Simulator could contribute significantly to the development
of novel catalysts required for the production of environmentally acceptable gasolines.
Nomenclature
A Symbol for gas oil in the three lump model, aromatic compounds in the 8-lump model
B Symbol for gasoline lump in the three lump model
C Symbol for light gases plus coke lump
CA Concentration of gas oil (gmol/cm3)
CD Concentration of gasoline (gmol/cm3)
Cc Coke concentration (gcok.lg""talytJ
Ci Concentration of component i (gmol/mL)
Ct Total active sites (gmol sites/g catalyst).
D Constant involved in power law decay = [(n-l)kJ-N (SN)
EA Energy of activation (kcal/gmol)
G Symbol for gasoline lump in the 8-lump model
ta Overall gas oil cracking rate constant in the 3-lump model (cm6/gcat.s.gmolo~
ta' Overall gas oil cracking rate constant in the 3-lump model using power law decay
(cm6/g""t"sl-N.gmolo~
kl Gasoline formation rate constant in the 3-lump model (cm6/g""t.s.gmolo~
kz Gasoiine cracking rate constant in the 3-lump model (cm3/gcat .s)
k3 C-Iump formation rate constant from gas oil in the 3-lump model (cm6/g""t.s.gmol~
kd Deactivation rate constant (1/s)
k/ Deactivation rate constant (cm6/gmoF.s)
koc Rate constant for gasoline cracking to C-Iump (cm3/g""tos)
kih Overall rate constant for the cracking of heavy lumps (cm3/gcat.s)
kmc Rate constant for heavy lump cracking to C-Iump (cm3/gcat .s)
kmo Rate constant for heavy lump cracking to gasoline (cm3/gcat .s)
ku.u Rate constant for heavy lump cracking to light lump (cm3/gcat .s)
~l Overall rate constant for the cracking of light lumps (cm3/g""t.s)
~c Rate constant for light lump cracking to C-Iump (cm3/g cat .s)
~o Rate constant for light lump cracking to gasoline (cm3/gcat.s)
m Constant related to coke formation (equation 1.3)
me Mass of catalyst (g)
M.vg Average molecular weight of vapours in the reactor
121
Mi Molecular weight of component i (g/gmol)

n Order of catalyst activity decay
N Function of the order of decay ( = lI(n-l»
Ni Moles of component i (gmol)
Pi Partial pressure of component i (atm)
rA Rate of gas oil cracking (gmoloil/gcat.s)
rD Rate of gasoline formation (gmolfgcat.s)
S Symbol for aromatic substituent groups in the to-lump model
Catalyst time on stream (s)
T, Sample loop temperature (OK)
VI Stoichiometric coefficient for gasoline formation from gas oil (- MA/M D)
Wi Mass of component i (g)
Wo Mass of oil injected minus coke (g)
WT Total mass of gases in the reactor (g)
W Oil refractoriness
XHC Mass fraction of hydrocarbons (gHC/g..,.J
Yi Mole fraction of component i (gmol/gmol..,.J
Yi Weight fraction of component i (g/g..,.J
Yio Initial weight fraction of component i
Greek Symbols
Ci Alternate symbol for kd (lis)
o Constant related to coke formation (equation 1.4)
 Deactivation function
E Constant related to coke formation (equation 1.3)
(J Proportionality factor (gmol sites/gmol coke)
Subscripts
A Refers to aromatic compounds in the 8-lump model, gas oil in the 3-lump model
B Refers to gasoline in the 3-lump model
C Symbol for light gases plus coke lump
G Refers to gasoline lump in the 8-lump model
h Refers to heavy lumps
i P, N, or A
I Refers to light lumps
N Refers to naphthenic compounds
P Refers to paraffinic compounds
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MIXING PATTERNS IN A NOVEL RISER SIMULATOR
A. Pekediz!, D.W. Kraemer2 , J. Chabot!, and H.I. de Lasa!

1 Chemical Reactor Engineering Centre
Faculty of Engineering Science
The University of Western Ontario
London, Ontario, Canada N6A 5B9
2 Imperial Oil Laboratories, Sarnia, Ontario, Canada
ABSTRACT. Characteristics and fluid dynamics of gas phase recirculation in a novel Riser Simulator
Reactor have been investigated using constant temperature hot wire anemometry. In situ concentration and
velocity measurements enabled to evaluate the mixing time and the inner recirculation ratio of the gas
phase. In addition, fibre optic techniques allowed to characterize the degree of fluidization of the catalyst
particles and the effect of gas phase density changes. By combining the anemometry and the fibre optic
techniques, mixing patterns in the Riser Simulator have been evaluated. The importance of the study can
be realized in the context of the potential use of the Riser Simulator for gas-solid reaction kinetics.
1. Introduction
Novel "bench scale" reactors to adequately test novel catalysts and to investigate the reaction
kinetics of systems of high industrial interest such as FCC and oxidative coupling of methane are
crucial. In this context, the novel Riser Simulator reactor, an internal "upflow" recycle fluidized
batch reactor, was recently developed. Mixing in laboratory as well as industrial scale reactors
is an important issue, providing uniform temperature and concentration necessary for the clear
understanding of the reaction kinetics. Consequently, in order to validate the "ideal" nature of
the mixing in the Riser Simulator Reactor, an extensive fluid dynamics study was undertaken.
Gas mixing and catalyst bed dynamics have been studied in order to assess "perfect" mixing and
particle fluidization conditions in this novel reactor.
Gas mixing in laboratory internal recycle reactors used for gas-solid catalytic studies may be
assessed from pressure drop (Berty, 1974; Berty, 1979), temperature drop measurements across
the bed (Mahoney, 1984), or from mass transfer coefficient estimations (Caldwell, 1983). For
a given impeller speed, the first method involves comparing the bed pressure drop of the recycle
reactor with pressure drop of a calibrated fixed catalyst bed conducted in a separate unit. Then
knowing the fluid velocity versus pressure drop for the calibrated bed, the impeller speed versus
fluid velocity can be drawn. The recycle rate can also be determined from thermodynamics
based on the ratio of the adiabatic temperature change and the measured temperature difference.
This method requires the measurements of temperatures across the bed and the mass flow rate.
The second method involves the evaporation of solid pellets, such as naphthalene, into the gas
133
H.l. de Lasa et al. (eds.). Chemical Reactor Technology for Ellvirol1mel1tally Safe Reactors and Products. 133-146.
© 1993 Klllwer Academic Publishers.
134
phase. From mass transfer data, the gas superficial velocity may be related to the mass transfer
coefficient. This technique is described in detail in Caldwell (1983).
Furthermore, for a well mixed continuous system, transient response techniques may also be
employed to assess the degree of mixing in absence of chemical reaction. A disturbance is added
to the system inlet. Then the response at the outlet may give the "fingerprint" of the flow inside
the reactor, regarding dead volume, short circuiting or channelling. In this case, the recycle gas
velocity may be estimated from the flow model of the system. Wen and Fan (1975) gives an
extensive review on flow modeIling including selection of tracers to be used as disturbances for
continuous systems.
It has to be noted that in the above mentioned methods, the gas superficial velocity generated
by the impeller was not measured directly in the reactor and this introduces a significant degree
of uncertainty on the actual gas flows.
In the present study, direct measurement of gas velocity with respect to a given impeller
rotational speed was preferred to asses, with improved confidence, gas recirculating rates. This
was achieved by placing a hot-film anemometer sensor inside the Riser Simulator Reactor.
Because the Riser Simulator operates as a batch system, in-situ measurements represent the actual
flow created by the impeller. There is in this case no influence of incoming and outcoming
streams, as in continuous well mixed reactors. In addition to gas mixing, it was required to
investigate the catalyst dynamics to confirm intense fluidization of the solid particles placed
between the two porous grids, at the catalyst basket. This was achieved with fibre optic
measurements allowing to follow the intensity of particle fluidization inside the catalyst basket.
Then, mixing patterns in the Riser Simulator Reactor were investigated by following the gas
phase using hot wire anemometry and by observing the catalyst particles applying fibre optic
techniques.
2. The Riser Simulator
The Riser Simulator Reactor is an internal recycle fluidized batch reactor. This patented novel
device (de Lasa 1989; de Lasa, 1991), has been developed and successfully tested for the
estimation of kinetic parameters of catalytic cracking of heavy oils (Kraemer and de Lasa, 1988).
The details of the unit are given in the section entitled "Novel Techniques For FCC Catalyst
Selection and Kinetic Modelling" by de Lasa and Kraemer in this NATO-AS I Proceedings.
A schematic diagram of the Riser Simulator with the associated instrumentations used in the
context of this study is shown in Figure 1. Two outer shells, lower section and upper section,
permit to load or unload the catalyst. A metallic flexicarb gasket seals the two chambers. The
other main components of the reactor are a catalyst basket placed in the lower chamber, an
impeller located in the upper section, and a packing gland assembly and a cooling jacket
surrounding the shaft that support the impeller.
The reactor is designed in such a way that an annular space is created between the outer
portion of the basket and the inner part of the reactor shell. The unit differs from the
conventional internal recycle reactors (Doraiswamy and Tajbl, 1974; Christoffel, 1982; Berty,
1984) by the important fact that the catalyst bed is fluidized inside the catalyst basket between
two 20 micron porous grids. This condition is achieved by locating the impeller in the upper
region of the reactor, above the catalyst basket. Upon rotation of the shaft, gas is forced outward
from the centre of the impeller towards the walls. This creates a lower pressure in the centre
region of the impeller thus inducing flow of gas upwards through the catalyst chamber from the
135
bottom of the reactor annular region where the pressure is slightly higher than inside the bed.
The overall direction of gas flow is indicated by the arrows in Figure 1, where gas is forced to
swirl downwards in the annular region and then upwards through the catalyst bed, generating a
re-circulating pattern. The impeller provides a fluidized bed of solids as well as intense gas
mixing inside the reactor.
Intense mixing in the upper section is secured by the impeller itself while mixing in the lower
chamber depends on gas recirculation rates. Furthermore, gas and particle mixing in the lower
section are proportional to the impeller rotational speed. The Riser Simulator has been designed
to operate at a maximum impeller rotational speed of 12000 revolutions per minute (RPM).
However, from a practical view point it appears that only 76 per cent of the total spinning rate
of the impeller (0-8000 RPM) is required for proper fluidization conditions. Then this study was
essentially addressed to gain a better understanding of the fluid and particle mixing patterns under
this range of conditions.
RISER SIMULA TOR
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Figure 1. Schematics of the experimental system; fibre optic system and hot wire anemometer
are described as connected to the Riser Simulator Reactor.
3. Gas Mixing Experiments
Temperature compensated anemometry was used for the gas velocity measurements. By sensing
the changes in heat transfer from a heated sensor exposed to the fluid motion, thermal
anemometers measure fluid velocity in terms of voltage. Measurement at conditions should be
such that fluid temperature and composition are constant. The system consists of a sensor and
a control box which supplies current to keep the temperature constant around the sensing
136
element. The principles of the operation of this gas velocity sensor are given elsewhere
(Goldstein, 1983).
For the present study, a general purpose, hot film sensor was purchased from TSI Incorporated
(model no 1210-20). The manufacturer certified the probe for single component air velocity
measurements at ambient temperatures up to 150°C with a recommended minimum velocity of
0.15 mls and a maximum velocity of 350 m/s.
In order to measure the gas velocities generated by the impeller, the sensor of the anemometer
was inserted in the annulus region between the catalyst basket and the wall of the reactor. Figure
1 shows the location of the hot film sensor inside the reactor. The sensor was inserted from the
bottom of the reactor through 114 inch Swagelok fitting. Then the direction of flow generated
by the impeller was parallel to the supporting sensor tube and transverse to the hot film as it is
shown in Figure 1. The elevation of the sensor was adjusted by sliding the sensor back and forth
inside the probe. Only the needles that support the hot-film were inserted inside the reactor and
were in contact with the gas.
For gas mixing experiments, sand particles with an average diameter of 73 JLm were inserted
in the catalyst chamber (between the two 20 JLm porous grids).
3.l. METHODOLOGY
The readings from the sensing element were collected in two different operating modes, namely,
velocity and concentration. Argon was used as a carrier gas to fill the reactor and as a medium
to measure the velocity generated by the impeller. Then upon spinning the impeller, the response
from the anemometer was due to the velocity variation effects given temperature, pressure, and
concentration were kept constant. After the velocity was stabilized at a desired impeller spinning
rate, hydrogen was injected as a tracer to measure the response of the sensor due to the
concentration changes and hence to follow the mixing characteristics of the gas phase. During
the operation the reactor was kept under batch and isothermal conditions.
The injection of the tracer gas to the reactor was made by an automatic injection system,
specially designed and controlled precisely by a personal computer. The readings from the
anemometer were digitized and interfaced to the computer by a 12-bit data acquisition card. The
PCLMP16 model card was purchased from The National Instruments Corporation.
3.2. GAS VELOCITY MEASUREMENTS
The response of the anemometer due to the velocity or concentration changes inside the reactor
was recorded for various impeller speeds. Gas mixing at the various impeller rotational speeds
can be seen in Figure 2, Figure 3, Figure 4, and Figure 5. The percentages shown on the top
of the figures correspond to the percent of the motor rate, marked on the speed controller.
Figure 2 indicates the response of the sensor at the total spinning rate of 10%. The tracer
injection was made after 4 seconds from the starting point which is zero time. It has to be noted
that the anemometer readings up to the point of injection is due to the velocity changes inside the
reactor resulting in a horizontal line. After the injection, the curve as shown in Figure 2 rises
up to a maximum point and then decreases slowly until it reaches a new horizontal line position.
The transition time from the lower horizontal line to the upper one determines the mixing time
inside the reactor and will be discussed in the following section. Because the anemometer
measures the response in terms of voltages, it was required to calibrate the hot film sensor.
In order to convert the anemometer readings to velocity values, a commercial probe calibrator
137
purchased from TSI Incorporated was used. The Model 1125 Calibrator provides a calibrated
chamber-flow based on the Bernoulli equation. The results of the mixing experiments are
summarized in Table 1.
As seen in Table 1, when the impeller speed was elevated from 10% to 70%, higher velocity
values were obtained. For example, in Figure 3 and Figure 4, the impeller rotational speed was
changed from 20%(2100 RPM) to 70%(7350 RPM) respectively. It can be seen that the lower
curves (before 4 seconds) which represent the velocity measurements are gradually shifted from
2 Volts to 2.7 Volts. The velocity reported represents an averaged value during a 4 second period
before tracer injection to the reactor. Intensity of mixing in the gas phase can also be assessed
in Figure 3 and Figure 4 by considering the velocity components or the range of the band. The
range of the band can be approximated as proportional to the standard deviation. The standard
deviation at 10% and 70% was 0.004 volts and 0.147 volts respectively. Thus, the intensity of
mixing was increased 36 times from the lower mixing range to the 70% range.
The gas volumetric flow rate inside the annulus can also be calculated by multiplying the
measured velocity by the cross sectional area of the annulus, which is 4.38 cm2 (refer to the
column volumetric flow in Table 1), and assuming a flat velocity profile along the annulus
section. For instance, knowing the volume of the lower chamber, which is approximately 20
cm3 , then the gas can be recirculated through the lower chamber 1000 I 20 = 50 times in one
second at the impeller speed of 7350 RPM (70%). It has to be mentioned that the reactor is
normally operated at 7875 RPM (75%). Then a recycle rate above 50 in one second could be
expected in this novel Riser Simulator Reactor.
TABLE 1. Gas mixing results from the Riser Simulator Reactor

Impeller Velocity Volumetric Estimated
% Speed (RPM) (cm/s) Flow (cc/s) mixing time(s)
10 1050 0.11 0.5 1.50
20 2100 16.20 71.0 1.00
30 3150 56.80 249.0 0.50
40 4200 90.63 397.3 0.33
50 5250 138.58 607.5 0.10
60 6300 206.22 904.0 0.04
70 7350 253.86 1112.9 0.02
The consistency of the method of evaluation of velocity is illustrated in Figure 6 where the
results of two repeat independent experiments with only the grids installed on the catalyst
chamber (hollow and filled circles) and one run with 73flm sand particles (hollow triangles) are
given. It could be seen that typical velocity deviations at 7370 RPM are not more than ± 14%.
There is no significant effect of particles in the recirculation rates and this seems to be an
expected result considering higher pressure drops in the grids than in the bed itself.
3.3. MIXING TIME
Mixing time was evaluated from the time the tracer gas was injected to the state of uniform tracer
concentration inside the reactor. In other words, the mixing time is the period spent between the
injection point to the new steady state or uniform conditions achieved. The faster the mixing,
the shorter the transition time would be expected. At the impeller speed of 1050 RPM, the
138
mixing time was about 1.5 seconds. It was observed that above 2100 RPM, a rapid mixing
having mixing times below 1 second was achieved. At 7350 RPM as shown in Figure 4, it was
10% 20%
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2.0 2.0
1. 5 1.5 '------'_-1.._-'-_-'------''-------'-_--'----'
o 250 500 750 1000 1250 1500 1750 2000 0 250 500 750 1000 1250 1500 1750 2000
Time x 100 (s) Time x 100 (s)
Figure 2 Gas mixing at the impeller Figure 3 Gas mixing at the impeller
rotational speed of 10%(1050 RPM). rotational speed of 20%(2100 RPM).
70% 70%
3.5 ,..--,--,---,--,---,---r---,----. 4.0 , . . - - - - , , - - - , - - - , - - - - , - - - - - - ,
3.0 3.5
i'" 2.5 3.0

'0
c:
en'"
2.0 2.5
1.5 2.0 '--_----''---_----L_ _-1.._ _- - ' - _ - - '

o 250 500 750 1000 1 250 1500 1750 2000 1 .00 1.02 1.04 1.06 1.08 1.10
Time x 100 (s) Time (second)
Figure 4 Gas mixing at the impeller Figure 5 The mixing time for the
rotational speed of 70%(7350 RPM). spinning rate of 70%(7350 RPM).
139
not possible to estimate the mixing time because the transition time was occurring in a very short
time interval. In order to estimate the transition time precisely, the data sampling rate was
increased to 10 kHz and the experiment was repeated. Figure 5 indicates the zoomed report
around the injection point for this repeat experiment. Because it was intended to estimate the
mixing time not to measure the velocity for this experimental run, then the injection was made
at the one second time mark instead of the 4 second mark. From Figure 5, it was noted that the
first 16 milliseconds are essentially the delay for the injection system. Following this, the actual
mixing time is less than 20 milliseconds. On the basis of similar analysis, mixing times were
estimated for other impeller speeds and the results obtained are given in Table 1.
Mixing times were also confirmed from velocity measurements. At 70% of the total impeller
speed which corresponds to 7350 RPM, the volumetric flow rate generated inside the annulus
was 1112.9 cm3 /s. Then the residence time for one pass of gases throughout the lower reactor
zone was about 18 milliseconds which is consistent with the estimated mixing time of 20
mill iseconds.
RISER SIMULATOR PERFORMANCE
300
250 'V
/0
v/ e
#
-;;- 200
"-
E
3 150
..
~
g
> ~.
.
lOa
/;f!'
v'/
(
50
a ......... ~
a 2000 4000 6000 8000
Impel/er Speed (RPM)
Figure 6. Velocity versus impeller speed.

(v 73 Jtm sand particles; 0 and. empty basket
with grids).
4. Particle Fluidization Experiments
To further evaluate the fluid-solid mixing characteristics taking place in the catalyst bed a fibre
optic probe technique was used. The fibre optic probe was inserted from the side of the reactor
through the basket where the probe contacts with catalyst particles. A schematic of the system
is shown in Figure 1. It has to be noted that two models, cold and hot model, were constructed
to apply the fibre optic technique (Kraemer, 1990). The cold model was made of plexiglass
material and had the same internal dimensions as the hot model or the Riser Simulator Reactor
made of inconel.
The fibre optic technique was previously developed for measuring hydrodynamic parameters
in a gas-solid fluidized bed (Huskey, 1990) and in three-phase fluidized beds (Lee, 1986; Chabot,
140
1989). In the present application, the approach was to measure light signals reflected by the
particles as the impeller speed was varied under different conditions of pressure and inert gases.
Details of the fibre optic probe system used can be found in the works by Lee (1986) and
Chabot et.al. (1992) thus a brief description will be given here. The main components of the
photometric measuring system are shown in Figure 1 and include a light source, light guides and
photo detectors. The light source used was a Spectra Physics helium-neon laser (35 mW) model
no. 124B-255 which provided a stable red light (wavelength of 632.8 nm). To carry the laser
signal, pure silica single core 400 JLm optical fibres were used. The reflected light intensity was
measured by two EG&G photodetectors model no. 460-1A. The analog signals were digitized
using an HP-lOOO model A600+ computer system.
To construct the fibre optic probe measuring device two 400 JLm optical fibres were inserted
inside a 1/8" O.D. tube which was approximately 30 cm in length. One fibre was used for
transmitting the light signal to the bed, the other to catch the reflected signal. The fibres
consisted of 3 layers : an inner silica core, a cladding layer (to maintain light in central silica
core) and an external coating for protection and flexibility. The ends of the fibres were polished
using micro sand paper to ensure good light transmittance. The tips of the two fibres were
extended 2mm past the end of the tube sheath. A high temperature cement was used to fix the
fibres in this position.
The probe was then inserted in the reactor from the side of the lower shell. Figure 1 shows
the placement of the probe which was just above the bottom grid with the fibres protruding into
the bed approximately 2 mm. A Swagelok fitting was used to hold the probe in place and to seal
the device from gas leakage between the tube and probe cavity. With the fibre optic probe, FCC
catalyst was used to perform the experiments. The particle size for this commercial FCC catalyst
was 60 JLm. The weight of catalyst used in all experiments was constant to maintain a constant
bed height (0.8 grams).
4.1. EXPERIMENTAL CONDITIONS USED
For the state of the catalyst bed during operation of the reactor, two extreme conditions could
exist. The first would be a fixed bed of catalyst corresponding to a low gas velocity through the
bed (i.e. low re-circulation rate) which would be detrimental to the objective of this unit (low
degree of mixing, insufficient gas-solid contacting). The second extreme would be the case of
over-revving of the impeller causing a high velocity through the bed (pneumatic transport range)
resulting in a fixed bed of catalyst stuck at the top grid. This case would also be undesirable
since the idea is to mix the particles for uniform catalyst activity. Therefore it was necessary to
test the type of signal spectrum that would be obtained using the fibre optic probe if these two
situations were to exist.
The spectrum for the first case (fixed bed) was obtained by simply leaving the impeller at zero
RPM so that no flow was sent through the catalyst chamber. The resulting spectrum indicated
no peaks because the catalyst was covering the emitting fibre thus no light could be reflected.
The spectrum for the second case was obtained by using no catalyst in the bed (i.e. probe located
at bottom of bed) and running the impeller at operational speed. Again no peaks were recorded
since there were no catalyst particles to reflect the emitted light. Thus, if over-revving were to
occur during operation, the recorded spectrum would be blank. It is noted that no such condition
was observed.
The experiments done in the transparent model of the Reactor made of plexiglass allowed
visual observation of the phenomena taking place. Observing the bed with the laser signal on
141
and the impeller at rest only a small amount of red light was visible. As the RPM was increased
the light became more intense. When the bed was fluidized the light from the laser was clearly
visible and appeared to be glowing resembling a flickering flame. This behaviour is the result
of catalyst particles or groups of particles that pass through the path of the emitted light and
reflect it in different directions.
As the bed agitation was increased by using higher impeller speeds the flickering light became
more intense. This relationship was quantified by recording the reflected light spectrum at
various impeller RPM's. Figure 7 shows two signal spectrums using N z at room conditions with
catalyst present. Spectrum 1 was obtained using an impeller speed of 6300 RPM and spectrum
2 was measured at an RPM of 7875. It can be seen that there is an obvious correlation between
impeller speed and signal intensity. In the initial part of each spectrum (less than 10 seconds)
the impeller is at 0 RPM showing that no light is reflected. When the impeller is brought to
6300 RPM (spectrum 1) reflected light peaks are observed with intensity levels smaller than 0.1
volts. At the higher RPM indicated by spectrum 2 the intensity of reflected peaks is much higher
with values reaching above 0.4 volts. The interpretation of this behaviour is that as soon as the
impeller rotational speed is increased more fluid passes through the bed resulting in additional
bed expansion. With this expansion more light is able to pass into the bed from the emitting
fibre and subsequently more light may be reflected back to the receiving fibre. Furthermore,
with higher re-circulation rates the bed becomes increasingly agitated resulting in an increase in
the number of reflections of light (signal frequency). This suggests the possibility of correlating
average signal intensity and/or average signal frequency with bed pressure drop through the
corresponding RPM value, since both can be measured under the same conditions (nitrogen at
room conditions).
Spectrum 1: RPM=63oo, 1 atm N2 , 25°C Spectrum 2: RPM=7875, 1 atm N z, 25°C
Signal Signal
0.40 Intensity, o. 40 Intensity,
(Volt) (Volt)
0.30 0.30
0.20 0.20
0.10 0.10
0.00 b=~~~~b=
o 5 10 15 20 25 30
Time (Second) Time (Second)
Figure 7. Signal spectrums obtained from the optical probe at two different impeller speeds.
Knowing the average signal frequency versus RPM curve and the pressure drop versus RPM
curve for the same fluid could provide information on the bed density and consequently on the
state of the bed (fluidized/not fluidized) for a certain reactor environment. Thus runs were
142
performed under several different impeller speeds. The results for the average signal intensity
measured at the various RPM's are plotted in Figure 8. The results were obtained using nitrogen
gas at room conditions. Referring to Figure 8 it can be observed that at low RPM's (less than
6000) there is very little motion in the bed with average signal intensity being close to zero. As
the RPM's are increased to about 6300, minimum fluidization occurs and the average intensity
significantly increases. The value of the impeller speed for minimum fluidization was determined
by visual observation and by the pressure drop versus RPM curve (Figure 9) and are quite close
in agreement. Beyond minimum fluidization the number of signal reflections increases rapidly
with further increases in RPM and then starts to level off. Presumably if the curve were
extended to higher RPM's a drop in the average signal intensity would eventually occur as the
regime of fluidization changed from aggregative to pneumatic transport. In this extreme case one
would expect solids to be stuck at the top grid and no light would be reflected back to the probe
as mentioned previously.
200
Operating
Speed
>
E 150
~
-00
c
ClJ
E fir'
, , ,'
Minimum
Cii 100 FluidizatIon
c p'
Ol
Ui
Ol
«>
50
Cold Model Hal Model
[3- -- --e-- ---8--·
N2 @ I aim, 2S'C
o ~--~--~--~--~--~--~--~--~--~----~--~~
5 6 7 a 9 10 11
Impeller Speed, APM/l000
Figure 8. Average signal intensity versus impeller speed.
The signal intensity versus RPM curve obtained from the hot model runs (dotted line in Figure
8) follows the same path as that for the cold model with nearly similar shape. This is not too
surprising since both reactors are of identical internal dimensions.
In general the information obtained in Figures 8 and 9 provides a guideline for the operational
speeds of the impeller indicating when the bed is in a fluidized condition. Below 6300 RPM the
bed will not be fluidized and somewhere above 10,000 RPM pneumatic transport will occur. It
has to be mentioned that a run was done in the cold model using an air driven impeller which
had a maximum speed of 20,000 RPM. Using ambient air it was observed that at speeds in
excess of 12,000 RPM bed agitation was violent with solids hitting the top grid and falling back
down, Eventually at higher speeds catalyst became stuck at the upper grid. The exact value of
143
0.5 , - - - - - - - - - - - - - - - - - - - - - , - - - - - - ,
Bed pressure drop
--e--
Grid pressure drop
--.0--
0.4 (N2@ 1 aim, 2S'C)
6'
C\J
I
2- 0.3
0..
0
0 " ,'0
OJ
:; 0.2 ",ti
U1 , -0'
U1
OJ ,0- '
d: ~"
0.1 ,0
. . . r....
..a"" 0: Min. Fluidization RPM
0
4 6 B 10 12 14
Impeller Speed (RPM/l 000)
Figure 9. Pressure drop versus impeller speed.
impeller speed at this condition was difficult to assess because of the instability of the motor at
this speed. Thus it was concluded that the impeller speed should not exceed 12,000 RPM to
achieve satisfactory operation.
The operating impeller speed used in the actual experiments was chosen based on a
combination of the fluidization regimes attainable according to Figures 8 and 9 and on the
physical constraints of the mechanical system. Above 8000 RPM the shaft-sealing system in the
hot model became unstable causing mechanical failure of the seal which also aided in shaft
alignment. In some instances grinding of the impeller blades against the inner reactor walls and
top catalyst basket surface occurred. This was certainly an unpleasant noise and more
importantly caused the shaft to go out of alignment. Therefore 8000 RPM was taken as the
maximum value for the impeller speed and falls in the well fluidized regime. The actual value
used was 7875 RPM which corresponds to 75% of the motor speed on the speed controller
(maximum motor speed is 1750 RPM with a 6: 1 pulley gear ratio). Markings on the controller
were made for every 5% thus the value of 75% was the closest to 8000 RPM without exceeding
it.
4.2. THE EFFECT OF BATCH OPERATING CONDITIONS ON BED DYNAMICS
The effect of injection and purging on the bed dynamics can be seen in Figure 10 which is the
spectrum obtained for an injection of 50 mL of air into an initial mixture of N2 and air at 1 atm
and 25°C. The procedure for this experiment involved initially filling the reactor under vacuum
with nitrogen and then adding air to bring the reactor to 1 atm pressure. The impeller was
brought to operational speed (7875 RPM) and then the laser signal was turned on (data
acquisition simultaneously started). Approximately 15 seconds later 50 mL of air was injected.
144
Then, roughly 10 seconds after this the reactor was evacuated to purge the gases.
Signal
illtensity
(Volt)
0.40
0.30
0.20
PURGE
0.10
o. 00 L~~,--:::;::======:::::::;:======::;:==
o 5 10 15 20 25 30 35 40
Time (Second)
IN.JEC"rrON
Figure 10. Effect of density changes on the bed dynamics.
It is interesting to see from Figure 10 that the signal intensity jumps almost instantaneously
to a higher value upon injection of the air due to the increased fluid mixture density. This
indicates bed expansion with increased agitation of the catalyst. This takes place at
approximately the 7.5 seconds which was the time of injection from the start of the signal. Also,
when purging takes place, 10 seconds later, the signal intensity drops sharply to the baseline
value indicating bed collapse due to the loss in pressure. This result shows that purging of the
reactor effectively stops the flow going through the bed and only the fluid occupying the catalyst
volume can undergo further reaction (about 2 % of the total volume).
In summary, the above analysis shows that under initial conditions before the reactant injection
the bed is in a state of fluidization somewhat above minimum fluidization. Upon injection the
resulting gas pressure increase (or gas density increase) causes an increase in the impeller
pumping rate vaulting the bed into a state of intense fluidization, with a smaller catalyst bed
density (or increased solids hold-up). The overall effect is a high degree of agitation and solid
mixing. Since the gas density remains constant and the viscosity of the reaction mixture changes
only slightly during the reaction, for example cracking of heavy oil, then this bed condition is
maintained until purging. The rapid decrease in pressure causes quick bed collapse with gas flow
being diverted to the outlet line.
s. Conclusions
By applying hot-wire anemometry, in-situ velocity and concentration measurements enabled to
evaluate the mixing time and the inner recirculation ratio of the gas phase, and to describe the
mixing patterns in this novel unit. Mixing time was evaluated from the time the tracer gas
injected to the state of uniform tracer concentration inside the reactor. At the impeller speed of
1200 revolution per minute (RPM), the mixing time was about 1.5 seconds. It was observed that
145
above 2100 RPM, a rapid mixing having mixing times below 1 second was achieved. At the
impeller operational speed of 7350 RPM the gas mixing time was estimated to be less than 20
milliseconds. At this condition, the gas velocity was 250 cm/s resulting in a volumetric gas flow
rate of approximately 1000 cm3 /s (see Table 1). Since the volume of the lower chamber is 20
cml, then the gas could be circulated more than 50 times in one second around the catalyst
chamber.
From the fibre optic technique and pressure drop measurement it was proven that the FCC
catalyst was fluidized at the impeller rotational speed of above 6300 RPM and somewhere above
10,000 RPM pneumatic transport could occur. The condition that favours the pneumatic
transport was not desired because the catalyst could eventually become stuck at the upper grid.
Therefore 7875 RPM, which corresponds to 75% of the motor speed on the speed controller, was
taken as the normal operational speed of the impeller and falls in the well fluidized regime (see
Figure 8 and 9).
Thus, at the operational speed of 7875 RPM, the catalyst was intensively fluidized and gas was
completely well mixed in the range of reaction times (1-10 seconds) expected for novel downflow
reactors or riser units. In summary, this study proves the excellent ability of the Riser Simulator
for catalyst testing and kinetic modelling of catalytic reactions to be conducted under short
contact times.
ACKNOWLEDGEMENTS
Mixing experiments have been conducted with the financial support provided by The Institute
for Chemical Science and Technology (lCST) and NSERC-Canada under Industrially Oriented
Research Grant. This support is gratefully acknowledged. In addition, a partial support from
Gazi University to A. Pekediz is gratefully acknowledged.
REFERENCES
Berty, J.M. (1984) "20 years in Recycle Reactors in Reaction Engineering," Plant/Operations
Progress, 3, 3, 163.
Berty, J.M. (1974) "Reactor for Vapor-Phase Catalytic Studies," Chemical Engineering
Progress, 70, 5, 78.
Berty, J .M. (1979) "Testing Commercial Catalysts in Recycle Reactors," Catal.Rev.Sci.Eng.,
20 (1), 75.
Caldwell, L. (1983) "An Improved Internal Gas Recirculating Reactor For Catalytic Studies,"
Applied Catalysis, 8, 199.
Chabot, J. (1989) "Fibre Optic Sensors for Studies in Multiphase Reactors," M.Sc. Thesis,
The University of Western Ontario, London, Ontario, Canada.
Chabot, J., Lee, S.L.P., Soria, A., de Lasa, H.I. (1992) "Interaction Between Bubbles and
Fibre Optic Probes in a Bubble Column," Can.J.Chem.Eng., 70, 2, 61-68.
Christoffel, E.G. (1982) "Laboratory Reactors and Heterogeneous Catalytic Processes,"
Catl.Rev.Sci.Eng., 24, 2, 159.
de Lasa, H.I., (1991), Canadian Patent 1,284,017.
de Lasa, H.I., (1989), US Patent 4,929,798.
146
Doraiswamy, L.K., Tajbl, D.G. (1974) "Laboratory Catalytic Reactors," Cat.Rev.Sci.Eng.,

10, 2, 177.
Goldstein, R.I., ed. (1983) Fluid Mechanics Measurements, Hemisphere Pub. Corp., New
York.
Huskey, D., (1990) "Evaluation of a Multitubular-Cracker-Exchanger FCC Unit," M.E.Sc.
Thesis, The University of Western Ontario, London, Ontario, Canada.
Kraemer, D.W., and de Lasa, H.I. (1988) "Catalytic Cracking of Hydrocarbons in a Riser
Simulator," Ind. Eng. Chem., 27(11), 2002-2008.
Kraemer, D.W. (1990) "Modelling Catalytic Cracking in a Novel Riser Simulator," Ph. D.
Thesis, The University of Western Ontario, London, Ontario, Canada.
Mahoney, I.A. (1974) "The Use of Gradientless Reactor in Petroleum Reaction Engineering
Studies," I.Catal., 32, 247.
Wen, C.Y., Fan, L.T. (1975) Models For Flow Systems and Chemical Reactors, Marcel
Dekker Inc., New York.
CHEMICAL ASPECTS OF CLEAN FUELS PRODUCTION
P.H. SCHIPPER. A.V. SAPRE AND Q.N. LE

Mobil Research & Development Corporation
Paulsboro & Princeton, New Jersey 08066
ABSTRACT. The passage of the revised Clean Air Act Amendments on November 15, 1990 and recent
EPA regulations will result in landmark changes in the major transportation fuels in the United States.
There could be significant changes in the compositions of both gasoline and diesel fuels based on recipe
formulation or performance standards designed to meet both environmental considerations and quality
requirements. For gasoline, the major changes might include adding oxygenates, reducing total aromatic
as well as benzene concentration, and lowering the Reid vapor pressure (RVP). The next-generation diesel
fuel must conform to the lower sulfur content and possibly higher cetane index specifications. This paper
discusses various process technologies and refinery configurations that could be required to produce
tomorrow's fuels.
1. Introduction
Preliminary results from the first phase of the Auto/Oil Air Quality Improvement Research
Program have already revealed the benefits of oxygenates in reformulated gasolines for reducing
CO and to a lesser extent hydrocarbon exhaust emissions (Collucci and Wise, 1991). However,
recent air modelling studies indicate oxygenates have no clear effect on smog. In view of the
Clean Air Act Amendments and recent findings of the Auto/Oil program, various process
technologies and refinery configurations could be required to produce the transportation fuels for
tomorrow.
Prior to discussing the refinery of the future, we will refer to the proposed requirements of the
Clean Air Act Amendments, and the objective and initial results of the Auto/Oil study.
1.1. U.S. GASOLINE POOL
Total refinery capacity in the United States is currently estimated to be around 15-16 million
barrels per day(M BID). The U. S. product demand is about 17 M BID. Table 1 shows the
current and projected distribution of product demand in the U. S. in which over 50% demand is
gasoline related product (Unzelmann, 1991). The projected demand for gasoline in the year
2,000 is about 7.1 M B/D, reflecting about 0.7% average annual growth. Most of the gasoline
is produced in refinery units such as fluid catalytic crackers (FCC), reformer and alkylation units.
The current average U.S. gasoline composition as shown in Table 2 is made up primarily from
the combination of FCC gasoline (35.5%) and reformate (34%) (Unzelman, 1991). The
remaining gasoline components are made of alkylate, light straight run naphtha, butanes,
isomerate and methyl tertiary butyl ether (MTBE). The average U.S. gasoline pool has about
88.4 road octane and contains about 32 % aromatics.
147
H.l. de Lasa et al. (eds.). Chemical Reactor Technology for EnVironmentally Safe Reactors and Products. 147-182.
148
TABLE 1
U. S. Pe!rolewn Product Demand/Forecast
Million Barrels Per Day
1985 1990 1995 2000
Gasoline 6.85 7.21 7.4 7.1

Distillate 2.87 3.05 3.4 3.7
Fuel Jet 1.22 1.45 1.6 1.7
Residual Oil 1.20 1.22 1.4 1.8
Others 3.61 4.03 4.2 4.4
Total 15.53 16.96 IS.0 IS.7
(Unzelmall,l991)
Table 2
Approximate Composition oC 1989 U. S. Gasoline Pool
Vol j!i Octane Aromatics
Butanes 7.0 91·92

Light Straightrun 3.3 55·75 0.4
lsomerate 5.0 80·88
FCC Gasoline 35.5 84·89 23·33
Hydrocracked Gasoline 2.0 85·87 2-6
Coker Gasoline 0.6 60·70 4·8
Alkylale 11.2 90·94
Reformale 34.0 86·96 50·80
MTBE 1.4 106·110
Average 88.4 32.1

(Unulman. 1991)
1.2. CLEAN AIR ACT
In an effort to further reduce the air pollution in U.S. cities that do not consistently meet the
standards for national ambient air quality, the Clean Air Act (CAA) Amendments which passed
on November 15, 1990 not only call for a definition of reformulated gasoline but also set specific
requirements for emissions reductions and performance standards. These regulations mandate
refiners to market only cleaner-burning reformulated gasoline in the nine major cities with the
most severe ozone pollution beginning January 1, 1995. The current list of severe ozone
nonattainment cities includes Los Angeles, Baltimore, New York, Chicago, Houston, Milwaukee,
Hartford, Philadelphia and San Diego, representing about 25 vol% of total U. S. gasoline.
Summarized below are the recipe or the performance standards requirements for future
reformulated gasoline outlined by the CAAA:
SPECIFICATION FOR REFORMULATED GASOLINE
FORMULA
o Benzene concentration of 1.0 vol % maximum

o Minimum oxygen content of 2.0 wt%
o Aromatics concentration of 25 vol % maximum
o No heavy metals, specifically lead and manganese
o Detergent additives for deposit prevention
149
PERFORMANCE STANDARDS
o Reduction of VOC and air toxics by 15% effective in 1995

o Reduction of VOC and air toxics by 25% effective in 2000
o VOC standard applicable only in summer months
Reductions of volatile organic compounds (VOCs) which are ozone-forming constituents, must
only be met in the summertime. However, the emission requirements for air toxics applies
year-round. The definition of air toxics includes benzene, 1,3 butadiene, polycyclic organic
matter (POM), formaldehyde and acetaldehyde.
The Clean Air Act Amendments define the important role of oxygenates in future gasolines
with the requirement of2.0 wt% oxygen content in nonattainment ozone areas, unless the refiner
can demonstrate that his formulation reduces VOC and air toxies by more than 15 %. In addition,
beginning in November 1992, gasoline sold in the 44 CO non attainment cities must contain a
minimum of 2.7 wt% oxygen concentration during the winter months. Based on the current
estimation, the reformulated gasoline demand for the CO nonattainment areas accounts for about
1/3 of the total U.S. gasoline consumption (Lichtblau, 1991). One way to achieve the oxygen
specification would be to add about 640 K BID MTBE equivalent (ethanol included) into the
gasoline by 1995 (Davis, 1991). Compared to the estimated domestic supply scenario of 500
K B/D in 1995, a short-fall of about 140 K BID MTBE equivalent is anticipated when the CAAA
ruling becomes effective in 1995. To alleviate the constraint on insufficient domestic supply
based on capacity or distribution, EPA has an option, if warranted, to provide a waiver extending
the deadline of a year for oxygen requirements in the CO nonattainment areas.
In addition to reformulated gasoline, next-generation diesel fuels have also been targeted by the
CAAA ruling. Effective October 1, 1993, highway diesel fuel must have a maximum sulfur
content of 0.05 wt% and a minimum cetane index of 40. New diesel fuels will mean deeper
hydrodesulfurization and more severe hydroprocessing to reduce aromatics content and
consequently increase the cetane number.
1.3. AUTO/OIL RESEARCH PROGRAM
The Auto/Oil Air Quality Improvement Research Program (AQIRP) is a cooperative research
program in which three U.S. auto companies and fourteen oil companies are participating. The
program's objective is to conduct comprehensive research and testing to assess the potential
reductions in vehicle emissions and improvements in air quality, especially ozone, achievable with
reformulated gasoline, alternative fuels and/or engine technology. J .M. Collucci of General
Motors Research Laboratories and J.J. Wise of Mobil Research and Development Corporation
are co-chairmen of the program task force.
The program involves two phases. Phase I is a $ IS-million study, which will be completed at
the end of 1991. It focuses on the potential air pollution reduction from both reformulated
gasolines which mayor may not be produced in volume from existing refineries and from
methanol fuels. Future vehicle emissions from these fuels will be compared to today's average
gasoline in existing vehicles. Phase II, which will cost about $25 million, extends Phase I to
future gasoline formulations based on the findings from Phase I studies and prototype vehicles
having advanced emission control systems.
The program's Phase I consists of (a) measuring emissions for a number of fuels and vehicles;
(b) modelling to predict the ozone impact from these emissions; and (c) conducting an economic
analysis for the fuel/vehicle options to provide a range of potential costs to reach the air quality
150
goals. Specifically, Phase I involves comprehensive emissions testing including 53 vehicles; a

combination of 20 current and 14 older vehicles and 19 prototype flexible and variable fuel
vehicles; 30 different fuel compositions, consisting of more than 2,200 emission measurements.
Testing involves determining the emissions from tailpipe, both evaporative and running losses
including the concentration of about 150 hydrocarbons, carbon monoxide, nitrogen oxides,
methanol, formaldehyde and other oxygenates. These measurements will be used to correlate fuel
composition to emission composition and air qUality. Large scale computations representing air
modelling of 3 cities are being undertaken to determine the effects of different fuels on ozone.
1.3.1. Fuel Blending. All 30 test fuels in Phase I were blended by Phillips 66 Company with the
assistance of the participating companies (pall and McNally, 1990). Four different test fuel
matrices with target fuel composition variables are shown below:
Fuel Matrix Fuel Variables

o Reformulated Gasoline Aromatics, MTBE, OIefins, T90
o RVP and Oxygenates RVP, Ethanol, ETBE, MTBE
o Methanol Fuels Methanol/Gasoline Mixtures
o Sulfur Fuels Sulfur
Sixteen different reformulated gasoline blends were tested with the current and older vehicles.
Key reformulated gasoline properties were set at two levels. These properties included aromatics
content, MTBE concentration, olefins level and 90% evaporation temperature, a measure of fuel
boiling range.
Fuel Composition Industry Avg.
Low High
Aromatics, vol % 20 45 32
MTBE, vol % 0 15* 0
Olefins, vol % 5 20 12
T90, F 280-300 350-360 335
*Note: 15 vol% MTBE corresponds to 2.7 wt% oxygen content
All of these gasolines were blended to constant properties according to the guidelines below:
RVP, psi 8.7

Sulfur, ppm 300*
Benzene, vol % 1.6*
Road Octane, R + M!2 87 min.
T50, F 240 max.
Additive Package EPA Certification Fuel Package
Note: * Industry Average
The key fuel being tested in the methanol portion of the program is M85, a mixture of 85%
methanol with 15% industry average gasoline, adjusted to a RVP of 9 psi. These fuels are being
tested in flexible and variable fuel vehicles together with MO, (zero% methanol) the industry
average gasoline, and M10 (a 10% methanol blend with industry average gasoline).
RVP and oxygenated fuels were designed to evaluate the impact of RVP and oxygenate type
on vehicle emissions. Reformulated gasoline blends that contain various oxygenates, either
ethanol (10 vol%), ETBE (17.2 vol%) or MTBE (15 vol%) have 20 vol% aromatics, 5 vol%
lSI
olefins and T90 of 280 F. Data will also be developed on the effect of varying the RVP from
7.7 to 8.7 psi. The impact of sulfur content on exhaust emissions was evaluated at low (50 ppm)
and high (500 ppm) sulfur fuels.
Blending components used in the Auto/Oil Study were obtained from various streams from
current refinery configurations. They include FCC gasolines, reformates, straight run naphtha,
alkylates and isomerate. Table 3 shows the compositional analysis and physical properties of
these blending stocks.
TABLE 3
ANALYSES OF BLENDINC COMPONENTS'
Blendi", Cat Cracked light light Heavy Full light C6

Component Naphtha Cat Cracked Alkylate Alkylate Ranle 51. Run lsomerate
Naphtha Reformat. Naphtha
Cra.ity, API 52.1 66.& 72.3 55.& 44.2 81.8 83.0

Aromatics, vol" 35.2 17.6 0.5 1.0 61.1 2.2 1.6
Olefin., vol .. 32.6 44.9 0.2 0.9 1.0 0.9 0.1
Saturates, vol.. 32.2 37.4 99.3 95.1 37.9 96.9 98.3
Benzene, vol., 1.06 1.24 0.00 0.01 1.17 0.73 0.00
RVP, pal 4.3 8.7 4.6 0.3 3.2 10.8 8.0
Distillation, DOSreeo of
RON 93.2 93.6 93.2 65.9 97.3 63.7 78.6
MON 81 79.4 91.2 74.5 86.7 61.2 80.5
(R+M)/2 87.1 86.5 92.2 70.2 92.0 62.4 79.5
Sulfur, ppmw 321 0 IS IS 9 325 10
(Pahl and McNally, 1990)

• Preliminary Results -IiaUstical analysis not complete
1.3.2. Initial Results of Auto Oil Study. Initial results from Auto/Oil Study released first in
December 1990 and later at the March 1991 National Petroleum Refiners Association meeting,
revealed the effect of reformulated gasoline composition on exhaust mass emissions including
hydrocarbons (HC), carbon monoxide (CO), and oxides of nitrogen (NO,.) from both current and
older vehicles (Colucci and Wise, 1991). Emission data suggest the complexity of the study and
imply that changes in gasoline compositions do not apply equally to all vehicles. Five major
findings are summarized as follows (Colucci and Wise, 1991):
o Changing the level of olefins in gasoline does not have much of an impact on mass vehicle
exhaust emissions.
o Reducing aromatics can - depending upon vehicle type - either reduce or increase mass
exhaust emissions.
o Adding oxygenates decreases the amount of mass exhaust emissions by 5 to 7%.
o Reducing the boiling range of gasoline (T90) reduced exhaust hydrocarbon emissions
substantially more in the current vehicles than in older vehicles.
o Reducing sulfur from 450ppm to 50ppm significantly reduced mass exhaust emissions.
Fuel effects on auto exhaust emission on older vehicles (1983-1985) and current vehicles (1989)
are shown in Figure 1 and 2, respectively. Specifically, the data indicate that:
o Aromatics Effect: Decreasing aromatics content from 45 to 20% reduced exhaust
hydrocarbon by 6% for current vehicles, but led to about 10% increase in hydrocarbon emissions
152
1('"
~...
-15'1t [;JHC
111 co
miN""
-25"
Arornoatia MTSE TOO
)60-> 260'F
Figure 1. Fuel Effects On Auto Exhaust Emissions (Current Vehicles - 1990)
Arornatia M1BE Olefins TOO

"""Co>Iu:rlandWi>eI991 -45-->20" 0->15" 2().>S," 360->280°F
Figure 2. Fuel Effects On Auto Exhaust Emissions (Older Vehicles - 1983-85)
0%
HC CO NOx
-2% f-- -
'"c0
-4% r---- r--
'in
'E'" -6% r---- r--
c..J
'"'"
0 -8% r--
~
.5
~-10%
c
-
0
-'"
u
-12% -
-14% -
-16%
from Colucci and Wise, 1991 Sulfur 466 -> 49ppm
Figure 3. Fuel Sulfur Effects On Exhaust Emissions (Current Vehicles - 1989)

153
for the older vehicles. Cutting aromatics in gasoline lowered carbon monoxide level for all
vehicles while having little effect on NOx emission.
o MTBE Effect: Blending of 15 vol% MTBE in gasoline (2.7% OZ) decreased exhaust
hydrocarbons in both the current and older vehicles by 5 and 7%, respectively. The presence
of MTBE in gasolines reduced CO emissions for both types of vehicles.
o Olefins Content: Reducing olefins concentration from 20 to 5% increased exhaust
hydrocarbon by 6% for all vehicles, but decreased the NOx formation without affecting CO
emissions.
o T90 Effect: Lowering the T90 boiling point from 360 to 280 F significantly decreased the
exhaust hydrocarbon by 22 % for the current vehicles and only about 5% for older vehicles. NOx
emissions increased about 5% for reducing T90. About 12% increase in CO emission was
observed with older vehicles with T90 reduction.
o Sulfur Effect: Decreasing the sulfur content in gasoline from 466 to 49 ppm has significant
benefits in reducing mass exhaust emissions for current vehicles. Figure 3 shows that exhaust
hydrocarbon, CO and NOx were reduced by 16, 13 and 9%, respectively. The emission
improvement is likely due to the enhanced activity of the catalyst in the exhaust converter due
to less catalyst deactivation. The effect appears to be reversible when switching from the low
to high sulfur fuels and vice versa.
It is likely that many of the reported differences of the effect of fuel compositions on exhaust
emissions result from different vehicle technology such as, the use of fuel injection in newer
vehicles versus carburetor in the older ones (Octane Week, 1990).
The preliminary results reported are based only on exhaust emissions and do not include the
evaporative emissions which are a major source of vehicle emissions. The results from
evaporative emissions and from the flexible and variable fuels vehicles testing with
methanol-containing fuels will be released sometime this year.
2. Refinery Processing To Meet The Proposed Specifications
2.1. INTRODUCTION
The requirements to meet the specifications and performance criteria for reformulated gasoline
will push refineries to their limits. Not only are modifications and optimization of current
refinery process configurations necessary, but also incorporation of new processes may be
needed to produce or to remove various gasoline components in order to meet the reformulated
gasoline specifications or achieve greater than 15% reduction in emissions.
The regulatory demands are going to significantly alter the landscape of modern refineries.
Since both gasolines and diesel fuels are produced to a large extent by catalytic processes,
significant opportunities exist to develop novel catalysts which can specifically produce the
hydrocarbons of interest. Although a large number of catalytic process technologies can meet
the future challenges, we will focus on a typical refinery today and highlight potential changes
to existing processes and addition of new processes to meet tomorrow's challenges. We believe,
increasing olefin production from existing processes as intermediates for further processing such
as etherification and oligomerization will playa critical role.
Gasoline components that are consistent with the Auto/Oil program and the CAA standards are:
o Isomerate - (from CS-C6 fraction)
o Alkylate
o MTBE/TAME (methyl tertiary amyl ether) as oxygenate and for octane enhancement
154
These combined components have high octanes with zero aromatics and significant oxygenates.
The refinery of tomorrow could evolve to produce a higher percentage of these 3 components.
However, there is also a significant amount of optimization of our existing refinery processes
(reforming, FCC) which can lead to increases in the production of reformulated fuels. For
example, two of the three components, alkylate and MTBE, depend on availability of light olefin
feedstocks; thus, increasing olefin production is crucial. The FCC unit is a significant producer
of light olefins and will playa major role in modern refineries. Reformers will also playa key
role because of the need for hydrogen, but their severities will be reduced to reduce aromatics.
This will reduce the hydrogen production in the refinery somewhat. However, hydroprocessing
will play an increasing role to reduce the sulfur and nitrogen emissions and increase the hydrogen
content of the fuel. Other processes, such as dehydrogenation of light paraffins to olefins (further
increasing alkylate and ethers) and coke gasification may be used to supplement the hydrogen
production. The gasification will produce syngas for downstream methanol production. This is
a key component for MTBE production.
The current trends for distillate are to significantly reduce the sulfur and aromatic content.
High concentrations of aromatics in the distillate are undesirable. Naphthenes are better than
aromatics, however, we do not have sufficient information on how easily the naphthenes get
converted to aromatics in a flame. The best diesel fuel is perhaps that based on slightly branched
isoparaffins. This fuel will result in low sulfur and nitrogen oxide emissions and high cetane
numbers. Producing this type of fuel from light olefin building blocks such as using Mobil's
MOGD (Mobil Olefin to Gasoline Plus Distillate) process is well known.
Figure 4 shows an example process flow configuration of a future refinery which is based on
increasing light olefin production (C3 = to C6 =) (Chen and Weekman, 1991). This figure
highlights ways to increase light olefins production and their conversion to environmentally
acceptable gasoline and distillate blending components. Figure 4 also illustrates the role
conventional technology will play in the production of reformulated gasoline and distillate. It also
shows coke gasification and dehydrogenation as processes which supply additional hydrogen and
also increase clean fuels production.
In the following sections, we will briefly review the chemistry of each new and existing process
in the refinery, and highlight process modifications or innovations to increase the production of
clean fuels, i.e. reduce benzene and aromatics and increase oxygenates.
2.2. REFORMING PROCESS - OPTIONS TO REDUCE AROMATICS AND BENZENE
The reformer converts naphthenes and paraffins to high octane aromatics and branched paraffins
(Table 4). In addition, low-carbon-number paraffins (Cd outside the gasoline boiling range are
produced and there is a net generation ofH 2. These transformations take place through a complex
set of chemical reactions which involve over 300 chemical species. In general, reactions can be
classified by type as shown here.
Paraffin Ring Closure Paraffin Isomerization
a CH,CH,
'"
IIe,H,. = +H, c-c-c-c-c-c-c
IIe,H,. = ~'+H' ~
c-c-c-c-c
I
c
155
o
Naphthene Isomerization Naphthene Dehydrogenation
a-CH,CH. = OCH. C-C

===0
cA(C-C
+3H,
Paraffin Hydrocracking Aromatic Hydrodealkylation
LPG
I----.--~ LPG
L-=====~~_..., LlOlelin •
...rr------i---:--:--100- G.lollne
CS·C6
Reformal.
1--;--:--100- Gasoline
l
I------;--;----l... Gasoline
Crude
Fuel Ga.
1--:--;--100- Sulfur
D> Ammonia
!
C
1--r-:-'-100- Gasoline
1+_ _ _ _ _ _ _-'--'-'-100- Premium

Distillate
LPG
Case.
_c..:..:. _ _ _ _.;-;.........~ r rG
S~~ur .s
Ammonia
Gasoline
Olenn
.~I----
Methanot Upgrading
8'" c
Ji
Premium
Distillate
.
'0
c Alkylallon
~ ~ Oimerlzatlon
Ollgomerlzallon
~ Syngas ::e Etherification
Hydralion
[rom Chen and Weekman. 1991
Figure 4. A Proposed Refinery Configuration for Refinery Fuels
Reaction parameters for the classes of reactions vary widely, as shown in Table 5 (Ramage et.
al, 1987). The dehydrogenation reactions are very rapid and quickly approach equilibrium
concentration, resulting in an initial rapid increase of aromatics. Cyclopentanes are isomerized
to cyclohexanes, which are in turn rapidly dehydrogenated to aromatics. Also, paraffins are
isomerized to higher branched paraffins. Ring closure and paraffin cracking are slow steps in
the reaction sequence. Paraffin reactions are critical in the reforming process. Paraffins are
156
TABLE 4
REFORMING CHARGE AND PRODUCT COMPOSmONS
Mid-OlntiDem Anbian l...i&ht
CS + Composition (WI. %) Ow:IO Product Ow:ao Product
i-Paraffino 27.2 21.4 33.1 26.0

n-Paraffino 28.0 10.0 34.3 12.4
NaphtbcDeo 32.9 0.1 18.3 0.8
Aromatica 11.9 67.8 14.3 60.8
CS+RON 64.2 99.1 <60 97.1
Rebd..
RetdiondUl ruction rate AH.. (\I/mol
Dehldroienltioo
O==OUHI VU}rap\l(SII @
Rin&/p&r>IIIn Isomerlutloa
O==cr c Rapid (2) -21
== C1'
Rin&d"",.. C
C-C-C-C-C-C VeT)' slow (0.011 120
r.,.lIInmciiD,
C-C-C-C-C-C ~ C-C-C-C + C-C Slow(O.Ol) -31
from Ramage et al .. 1987
converted through three reactions; ring closure to five- and six-carbon-member naphthenes
[cyclohexanes], isomerization to branched paraffins, and cracking to lower-carbon-number
paraffins. The ring closure reaction will increase aromatics and octane the most since
naphthenes, in turn, rapidly convert to aromatics. However, the ring closure rate is slow and
approaches that of paraffin cracking. The similarity of these two reaction rates causes a
significant gasoline yield loss when the reformer severity is "pushed" to make high octane (high
aromatic yield). Also, thermodynamics has a pronounced effect on the benzene yields. Its
concentration drops after being formed initially since the reaction sequence is reversible.
Benzene, after being formed is hydrogenated to naphthenes which ring open to paraffins.
Paraffins can then ultimately crack to Cs- light gas. Therefore, in general, process conditions
which favor cracking and ring opening over ring closure will decrease aromatics. Such
conditions are, for example, high pressure, low temperature, and decreased paraffin carbon
number. Aromatization selectivities for paraffins as a function of pressure and carbon number
are listed in Table 6 (Ramage, et al, 1987). Most reforming reactions are reversible. Thus,
thermodynamic constraints play an important role in understanding the reforming chemistry and
in model development. Aromatics formation as a function of pressure and temperature, from a
C6- 370K Mid-Continent naphtha is shown in Fig.5. Low yields of aromatics are favored by high
157
pressures and low temperatures. Conditions which favor low aromatic yields also give low
overall gasoline yield because the side reaction to C5- paraffins is increased.
Table 6
Aromatization Selectivities of Paraffins
Carbon Number 1241 kPa 3103 kPa

6 0.26 0.04
7 0.41 0.19
8+ 0.63 0.54
Weight of aromatic produced divided by weight of paraffin converted at 783 K

from Ramage et al. 1987
~ 8or-------------------------------~
~ CS- 370 K Mid-Continent Naphtha
=
.2
so
690 kPa
~ 1380 kPa
;::
(1)
"co
.
o
c
40 _ - r - - 2760 kPa
"" 4140 kPa

~ 20
=~~-
+
"
c
~
_ - - - - - - - - 5500 kPa
c
(1)
~OLO----6~50-----70LO----7~50----8~O-O----85~0----~
'"
Temperature, K
Figure 5. Effect of Operating Conditions on Aromatics Formation
The reformate stream also contains the largest concentration of benzene found in the gasoline
pool (Table 7 Keesom 1991). Since light reformate is a major source of benzene in the gasoline
pool the reduction in benzene requires not only a reduction in reformer severity but also feedstock
shifts and additional downstream processing. Some of these processing steps include:
o Separation of C6- straight run naphtha prior to reforming followed by isomerization of the
C51C 6 normal paraffins to high-octane isoparaffin components.
o Splitting the light reformate followed by benzene extraction for chemical grade benzene or
saturation to the corresponding cycloparaffins.
o Splitting the light reformate followed by benzene alkylation with light olefins from the FCC
off-gas.
o Selectively cracking paraffins to light olefins in the reformate which subsequently react with
benzene and toluene in the feed (M-forming).
We will concentrate in this paper on the isomerization, benzene alkylation and M-forming
processes. The isomerization process focuses on the removal of benzene precursors in the
reformer while other technologies upgrade the reformate products.
158
TABLE 7
Benzene Distribution and Contribution in Gasoline Pool

Benzene Benzene
Gasoline Component Volume % Cone .. vol% Distribution. %
Light Reformate 40.5 4.0 78.2

Light Hydroeraekate 7.4 3.0 10.9
FCC Gasoline 26.4 0.8 10.2
from Keesom, 1991
2.3. ISOMERIZATION
Highly branched light paraffins have much higher octane numbers than the straight chain
hydrocarbons (See Table 8). The isomerization of Cs and C6 paraffins is an equilibrium reaction
which is slightly exothermic and occurs in the vapor phase at a temperature range of between
lOOC and 300C. The concentration of branched Cs and C6 isomers increases as the temperature
decreases (See Table 9). With the increased branching comes increased octane number and
therefore the isomerization reaction realizes a greater product octane gain at lower temperatures.
At the reaction temperatures of interest, a single pass isomerization reactor will only partially
convert the normal paraffins into iso-paraffins. Since the n-paraffins in the effluent have a
negative impact on the octane for single pass operation, separating and recycling these normal
paraffins back to the isomerization reactor will further increase the octane of the product (Maier
et. al, 1991).
I&hItl
TABLE 9
Oclan. Numbec of CSIC6 Panaffina
Component C5 Paraffin Equilibrium

CS RON MaN
n..cs 61.7 62.6
i..cs 92.3 90.3
T,C i-C5, %
C6
150 82.0
n-C6 24.8 26.0 200 79.5
2·2 Dimelhyl-Ol 91.8 93.4 250 75.0
2.3 Dimelhy-Ol 103.5 94.3
2 Methyl CS 73.4 73.S 300 72.0
3 Methyl CS 74.S 74.3
Table 10 illustrates the respective product octane as a function of reaction temperature for both
single pass and recycle operation. Therefore, separation of the products is beneficial. This
separation can be done using either distillation or molecular sieves to separate the n-paraffins
from the iso-paraffins (Schieferli et. aI, 1991). The isomerization reaction occurs in a fixed bed
159
reactor in a hydrogen atmosphere. Since the reaction is exothermic, multiple beds can be used
with reactor inter-cooling. Benzene in the feed can be saturated to cyclohexane with significant
ring opening to iso-hexane (Keesom et ai, 1991).
Table 10. C51C6 ISOM Octanes
T= 200 C
Feed, C5 P = 60%
C6 = 30%
C6 Cyclics 10%
Configuration Octane
Single Pass 84
Recycle 91
Because the isomerization reaction is favored at low temperature, it requires high activity
catalysts. Two catalysts that are currently being used commercially include 1) Pt on chlorinated
alumina and 2) Pt on mordenite (Maier et. ai, 1991). The mordenite based catalysts are much
less sensitive to poisons in the feed but are less active requiring a higher temperature that results
in considerably lower octane than the chlorinated alumina based catalysts. Currently, work is
in progress to produce more stable/highly selective isomerization catalysts (Travers et. ai, 1991).
2.4. BENZENE ALKYLATION
Another method to remove benzene is to react it with propylene or ethylene (benzene alkylation)
to produce propylbenzene (cumene) or ethylbenzene. Commercial benzene alkylation processes
in the chemical industry have been known for many years. Typically these processes require
fairly pure benzene and ethylene feed. The shape selective ZMS-5 catalyst is used as a basis for
ethylbenzene synthesis in the Mobil-Badger process (Chen et. ai, 1989). ZSM-5 is very selective
in this process; as a result this process is currently used in the chemical industry to produce about
25% of world's ethylbenzene. Currently there are 12 operating Mobil-Badger EB units including
a recent Shell Chemical unit which uses FCC off-gas as the ethylene feedstock source.
Recently, several processes have been announced which can alkylate the benzene in a dilute
light reformate stream with FCC off-gas. UOP has recently announced a process called
ALKYMAX which can alkylate the benzene in the light reformate with a dilute propylene stream
(C3 LPG from an FCC unit) in a fixed bed reactor (Kessom et. ai, 1991). Alkylating the light
reformate will result in a reduction in the gasoline RVP as a result of the increase in the
molecular weight of the light reformate stream. Benzene alkylation is a very attractive
technology not only to reduce benzene but also to upgrade reformate by increasing the volumetric
yield of gasoline and octane number. For example, the blending research octane number of
propylbenzene is in the range of 127-132 compared to 99 obtained with benzene. The process
also upgrades propylene to high octane gasoline. Since it uses propylene, there is a tradeoff for
the propylene feedstock between conventional alkylation vs. benzene alkylation.
A similar benzene alkylation process is being used by CDTECH in a catalytic distillation
column (Called Catstill) (Dixon, 1989). In this case, the reformate does not have to be split
prior to the reaction. Rather the entire reformate is sent to the bottom of the tower (Figure 6)
where it is fractionated. FCC off-gas is then added further up the column where it is reacted
160
over a zeolite catalyst to over 90% conversion of the olefins in a single pass. Since the reaction
is exothermic it is used to aid in the fractionation of the product.
--
-
'------<-
Figure 6. CATSTILL PROCESS sM Reactor/Column System
2.5. M-FORMING
Mobil's M-Forming process, based on the ZSM-5 catalyst, is another alternative to reduce the
concentration of benzene and toluene in the reformate (Chen et. aI, 1987, Chen and Garwood,
1973). The M-Forming process upgrades reformate by selectively cracking paraffins to light
olefins which subsequently react with benzene and toluene in the reformate product. By
integrating with the upstream reformer, M-Forming not only can reduce benzene but also increase
the reformate yield as shown in Fig. 7. The compositional change with M-Forming severity
indicates that at least 12 % benzene reduction was achieved via M-Forming. Further benzene
reduction is possible if low-severity reforming is coupled with high-severity M-Forming.
Compared to conventional reformates at the same octane rating, the products from the
combination of reforming/M-Forming process are lower in aromatics and higher in isoparaffins.
Table 11 shows a typical example using a C6-80 C Mid Continent naphtha. This data clearly
show a reduction in benzene and toluene with M-Forming reaction severity. The product of
M-Forming was made after reforming the naphtha to 84 clear octane and continued with
M-Forming to 96.8 R+O.
2.6. FCC PROCESSING OPTIONS FOR REFORMULATED FUELS
As with the reformer, the properties of the FCC gasoline are affected by the operating conditions,
feedstoc!c, catalyst selection, additives and new hardware technology. In addition, the FCC
produces light olefins which are the building blocks for the major new clean fuel processes such
as etherification and alkylation.
161
..
'v
\\
70
,
\
80 90 100
c,· Octan., • .0
Figure 7. Reforming vs. M-Forming. (From Chen et aI., 1987)
TABLE 11
Benzene Reduction Via Mobil M-Formlng Process
Effect of M-Forming on Reformate Composition
C6-80°C Mid-Continent Naphtha @ 28 Atm
Feed ~
CS+, R+O 84.5 92.7
Composition, Wt. %
Aromatics (Tolal) 42.7 46.8 (+4.1)
Benzene 18.5 16.3 (-2.2)
Toluene 23.4 21.7 (-1.7)
Xylenes 0.6 1.5 (+0.9)
C9 0.2 3.7 (+3.5)
Cl0 0.0 3.3 (+3.3)
C11 0.0 0.4 (+0.4)
Paraffins (Total) 44.0 32.4 (-11.6)
C6 30.9 23.4 (-7.5)
C7 12.9 8.7 (-4.2)
C8 0.2 0.3 (+0.1)
Naphthenes 1.4 1.1 (-0.3)
Pentanes 8.0 9.0 (+1.0)
Butanes and Ughters 3.9 10.7 (+6.8)
Chen fit al, 198?
2.6.1. Reaction Mechanisms. In catalytic cracking, the basic reaction mechanisms involve the
formation of carbonium ions and include beta scission cracking, olefin isomerization,
dealkylation, transalkylation and hydrogen transfer (Venuto and Habib, 1979). The rate of
cracking of paraffins increases with increasing carbon number; although the olefins (formed from
162
the primary cracking reactions) react at a much faster rate than the paraffins. Naphthenes crack
more rapidly than straight chain hydrocarbons, whereas the aromatics in the feed are primarily
dealkylated.
A secondary reaction that occurs is the hydrogen transfer reaction. Here hydrogen is
transferred to olefins from other reactants (naphthenes).
3Cn H2o + CmHzm = > 3Cn H2o+z + CmHZm.6

Olefins + naphthenes = > paraffins + aromatics
In the example above, hydrogen is transferred from the naphthenes to the olefins to form
paraffins and aromatics.
Based on this chemistry, the major causes of aromatics in the FCC gasoline are the dealkylation
of aromatics in the feed and the hydrogen transfer reactions. The major cause of olefins in the
gasoline is the trade-off between the rate of secondary cracking reactions and the rate of hydrogen
transfer reactions. Operating conditions, catalysts and FCC hardware modifications can alter the
ratio of cracking to hydrogen transfer.
2.6.2. Impact of operating conditions. Stokes et. al (1990) show that increasing riser top
temperature increases the olefin content significantly at the expense of the paraffin and naphthene
yield. This is primarily due to an increase in the ratio of the rate of cracking (beta-scission)/
hydrogen transfer rate (Voge, 1958). Octanes increase along with an increase in the light olefins
and fuel gas (Table 12). Gasoline selectivity has decreased slightly due to the increase in
secondary cracking reactions. This results in a slight increase in gasoline aromatic content.
Increasing C/O ratio by decreasing preheat will only slightly change the composition; the gasoline
olefin content will decrease slightly and the aromatics will slightly increase.
The aromatics in the FCC gasoline are concentrated in the back end of the gasoline. Yepsen
and Witsoshkim (1991) show that the heaviest 10 % fraction of the FCC gasoline contains almost
80-100% aromatics. Thus, undercutting the gasoline will significantly reduce the gasoline
aromatics at the expense of a significant reduction in the gasoline pool. However, the heavy end
of the FCC gasoline would then need to be blended into LCO which, if it is to be used as a
valuable product, would have to be severely hydrotreated. The front end of the gasoline contains
significant olefins which can be used as Cj alkylate or TAME ether feed.
Changing feedstock from a paraffinic to an aromatic stock (such as adding resid) has been
shown to increase the aromatics in the gasoline (Stokes, et. ai, 1990; Yepsen et. ai, 1991)
because of the increase in the aromatic dealkylation reactions.
2.6.3. FCC Catalyst. The FCC catalyst can also playa major role in the shifting of the FCC
gasoline composition, particularly the olefins. A key parameter in FCC catalyst manufacturing
is the faujasite "Y" zeolite catalyst unit cell size which relates to the silica/alumina ratio of the
zeolite. Different unit cell sizes in the FCC unit can be achieved by either dealuminating the
fresh zeolite during manufacturing (either by use of steaming or chemical dealumination) and/or
by adding different amounts of rare earth during the dealumination process. Young et aI (1991)
show that as the unit cell size of the catalyst decreases, the FCC gasoline composition shifts to
more olefins and less aromatics. This is due to a decrease in the bi-molecular hydrogen transfer
reaction which occurs with low unit cell size catalysts.
At constant coke, the olefin content of the FCC gasoline increases from 27.3 to 36.9% as the
unit cell size of the catalyst drops from 24.4 to 24.26A (Table 13).
163
TABLE 13
Table U Impact of FCC Unit Cell Size on Gasoline Composition
Impact of Riser Temperature on FCC Gasofine Composition
4.1% Coke
Constant Conversion Comparison
c.taIyot
UCS,A 24.40 24.29 24.26
Reactor Temperatu~, F 960 1000 Conversion 62.6 66.2 70.0

Gasoline 53.0 56.4 59.0
LCO 21.2 21.2 19.2
Yields. % Feed
MCB 16.2 12.6 10.8
H2 ,Wt$ 0.04 0.06
C3- 5.7 6.4 6.9
C2- ,Wt$ 2.3 2.8 nC4= 4.2 4.6 4.7
C3~ ,V" 6.8 7.2 iC4= 1.3 1.8 2.3
C3 ,V$ 2.0 2.0
C4= ,V$ 6.1 7.1 Gasoline Composition
3.9 n-Paraffins 4.4 3.8 3.6
iC4 ,V$ 4.2
iso-Paraffins 32.5 29.0 25.8
nC4 ,V$ 1.1 0.9
Aromatics 24.5 24.7 23.6
Napthta, 450 F TBP EP, V" 57.6 56.8 Naphthenes 11.3 10.9 10.1
LCO ,V" 18.0 17.6 OJefins 27.3 31.6 36.9
Bottollll 14.0 14.4 Iso-amylene 4.5 5.4 6.S
Cnke ,V$ 3.9 3.6
l'iBl!hl!!I
Paraffins ,V" 40.0 34.4 FCC + ALKP + ETHER'''COMPOSITION
OlefinJ ,V$ 29.7 35.0 Total Gasoline 74.8 81.4 86.S
Naphthenea ,V$ 10.4 10.0 Total Ammatics 11.4 l1.1 16.1
Aromatics ,V" 19.9 20.6
(Young el 11,1991)
RON 90.2 91.6

MON 79.2 79.6
(R+M)f2 84.7 85.6
...AIky Produced from C3 = and nC4 =
(Stok.el etll, 1990) **Ether= MTBE + TAME
This comes at the expense of a drop in paraffin content. The aromatics content of the FCC
gasoline, however, does not decrease as significantly, only from 25 to 23.6. %
It is evident from the above data that little change in the FCC gasoline aromatic content can
be achieved by altering process conditions or catalysts. There is a large impact on endpoint
which can only significantly sacrifice yields, However, the FCC gasoline composition cannot be
looked at in isolation. The FCC unit must be examined not only for its gasoline production but
also for the potential gasoline production from the light olefins. A typical clean fuels process
scheme centering around the FCC unit is shown in Figure 4. In the overall process the ~= and
n-C4 = would be alkylated and the i-C 4 = and i-Cs= would be etherified to produce MTBE and
TAME. In addition the nC s = could also be alkylated. In the overall scheme, catalyst variations
or operating conditions which increase light olefins (higher riser top temperature, lower unit cell
size catalysts) will dilute the aromatics content in the FCC + Alky + MTBE/TAME complex.
Thus, considering the catalyst example illustrated in Table 13, a lower unit cell size catalyst will
increase downstream alkyl ate + ether production which will dilute the overall gasoline aromatic
concentration.
2.6.4. ZSM-5 Additive. An additional method to increase light olefins which will dilute the total
FCC complex aromatics content, is to add ZSM-5 to the FCC unit. Because ZSM-5 is shape
selective, it only cracks the low octane components in the gasoline boiling range to higher octane
components plus light olefins. Data show that the predominant reaction with ZSM-5 is the loss
of C7 + paraffins and olefins (Table 14) (Schipper, et aI, 1988). ZSM-5 is selective to cracking
164
of the single branched and linear olefins, which have very low research and motor octanes.
Figure 8 shows that the iso/normal paraffins increase in the gasoline boiling range when ZSM-S
is added to the unit, indicating its selective nature (Pappal and Schipper, 1991). Both Biswass
et al (1988) and Schipper et al (1988) have shown that ZSM-S does not produce aromatics in the
gasoline, but merely concentrates them due to a reduction in FCC gasoline yield. The product
light olefins with the addition of ZSM-S are highly branched (higher percentage of iso-butylene
and amylene) approaching that of equilibrium (Table IS) (pappal and Schipper, 1989). Sparrell
et al (1987) show that the activity of ZSM-S (ability to produce C3 and C4 olefins) is a function
of the amount of ZSM-S in the inventory and the regeneration conditions (temperature and steam
partial pressure).
Table 14
Yield Shins With ZSM-5
Delta Yield, vol"

CS+GuoliDe -3.7
ParaffiDI
C6- -0.6
C7+ -0.8
OIolina
C6- +0.5
C7+ -2.5
::~
Naphtben.. -0.2
Alomari.,. -0.1
LCO 0
MCB 0
iC4 +0.3
+l.S --------=::
6~
f
C4~
nC4 0 I I ,
•
C3
C3=
+0.5
+2.6 2'__
t~ o Catalyst A
a Catalyst A
0 C... ty.! B
+ ZSM·5
C2-,WI" 0 q Catalyst B + ZSM-S

0 - Equmbrium
Cob,WI"
Alkylate +6.9
RON +l.S Carbon Number
MON '+0.5 Pappa!. and Schipp.", ;~S1
Base Octane - RON 92.7 Figure 8. Iso/Normal Paraffins Ratio Shift with ZSM-S
MONSO.3
(5(:hippcl' cl ai, 1988)
2.6.5. FCC Hardware Modifications to Enhance Reformulated Fuel Production. Because ZSM-S
does produce light olefins, the wet gas production off the FCC unit will increase. This can be
compensated for by decreasing riser top temperature or C/O at the expense of both FCC gasoline
octane and yield. However, the recent hardware development of closed cyclones allows the
refinery to increase the olefin content of the Cs- composition without expanding the gas
compressor or debottlenecking the unsat gas plant. The closed cyclone design recognized the fact
that significant thermal cracking reactions occur in the FCC reactor vessel after the cracked
effluent is separated from the catalyst. This thermal cracking degrades the gasoline product
producing non-selective light gas (See Figure 9). By installing closed cyclones, the amount of
hydrocarbon in the reactor vessel decreases significantly essentially eliminating the thermal
165
cracking. Commercial yield shifts for closed cyclones at constant conditions are shown in
Table 16 (Avidan, et ai, 1990). In all cases, closed cyclones increase gasoline plus distillate
yields at the expense of Cz- gas. One way to take advantage of the closed cyclones is to add
ZSM-5 to the FCC unit until the wet gas compressor limit is achieved. This significantly
increases light olefin production at constant wet gas, thus increasing feed to downstream
alkylation and MTBE units. Table 17 shows the advantage of using ZSM-5 + closed cyclones
at a wet gas compressor limit on the amount of aromatics in the FCC + alky + ether pool.
Table 15
Olef"m Distribution Witb ZSM-5
Catalyst Equil REY Roy + USY USY+

965F ZSM-5 ZSM-S
IAlm
Olefins
C5's
1- 4.1 8.4 1.4 1.4 1.2
cis 2- 11.5 13.5 12.5 12.5 11.6
trans 2- 11.9 24.9 23.1 22.1 20.9
2-methyll- 23.6 16.3 16.9 17.2 11.8
3-mothyll- 5.1 2.4 2.4 2.4 2.3
2-methyI2- 43.3 34.5 31.6 37.8 40.8
(pippalloo Schipper, 1989)
Thennal Cracking Reduces G+O and Increases Gas

and HFO Yields
G+O Loss Light Gas Gain HFO Yield Gain

10 4,---------,
1050°F
o
.6G+O
-12.5
o
-15 L--'--'---'---li-...J
o 0.2 0.4 0.6 0_8 1 0.2 0.4 0.6 0.8 1 0.2 0.4 0.6 0.8 1
Relative Oil Residence Time
Avidan lit aI, 1990
Figure 9. Thermal Cracking Pilot Plant Yields.
Another new route to light olefins production is a variation of FCC, called Deep Catalytic
Cracking, what is being commercialized by the Research Institute of Petroleum Processing in
China. This process is more severe than conventional fluid catalytic cracking but less severe than
steam cracking and is optimized to increase light olefins selectivity. The catalysts are mixed
aluminum/sodium/ferric oxides. The total gaseous olefin yields are typically 40 wt%, in which
propylene constitutes 20 wt%. Furthermore, isobutylene accounts for more than 40% of the
166
butylene isomers, which is a raw material for MTBE synthesis. The naphtha produced in the
process has a high, clear octane number but further hydrotreating is necessary to meet future
gasoline quality constraints. Similarly, the light cycle oil has a low cetane number but can be
used as a source of aromatics.
TABLE 16
YIE lD IMPACT OF CLOSE D CYCLONES
Audit Estimate
Refinery .A,-
Gasoline, vol ~ +1.3 +1.9
LCO,Yol% +1.5 +1.1
C2·, wt.. ·0.9 ·0.8
Refinery -.-
Cas ollne, yol~ +1.5 +1.0
lCO,vol' +1.0 +1.0
C2-,wt... ·1.0 ·0.8
Refinery ·C·
Gasof1ne, vol", +1.7 -10.7
LCO,Yol % -10.8 +1.7
C2·,wt% .0.9 .1.8
Avidan et at, 1990
TABLEl7
Impact of Closed Cyclones Plus ZSM-S

Constant Wet Gas Production
Closed Cyclones
Della Yields, Vol. % Base + ZSM-S
C2-, WI. % 4.5 3.7

C3 3.4 3.3
C3= 7.9 9.8
C4 5.2 5.5
nC4 2.0 1.9
C4= 7.7 9.3
iC4 2.3 3.0
FCC C5+ Gasoline 54.0 51.4
Gasoline & MTBE & Pol 79.3 82.2
Alkylale
• All C3 and nC4='S are alkylaled.
2.7. ALKYLATION
Because it contains no aromatics and olefins, alkylate is an excellent blending component in the
production of reformulated gasoline. It acts as a diluent since it is a high octane, zero aromatic
gasoline. The current gasoline pool contains only 11 vol % alkylate. However, this will no
doubt increase in the 1990's. The present alkylate, a high octane, isoparaffinic gasoline, is
produced by reacting isobutane with light olefins in the presence of either hydrofluoric or
167
sulfuric acid. Alkylate is known to be produced through 3 mechanisms: 1. light olefins reacting
with a C4 cation to form C7 to C9 cations which undergo hydrogen transfer reactions to produce
these paraffins, 2. formation of higher carbon number oligomers which then fragment and
undergo hydrogen transfer to produce C5 to C9 isoparaffins and 3. formation of oligomers which
undergo hydrogen transfer reactions to produce heavy isoparaffins (Albright, 1990). Formation
of the high carbon numbers oligomers and isoparaffins results in loss of product, known as ASO
(acid soluble oil). Mechanism 1 produces the preferred product, trimethyl pentane, with less side
products. This is favored by high isobutane/olefin (I/O) ratios. Thus, a major portion of an
alkylation plant is the separation of the isobutane for recycle to the reactor and cooling due to the
high heat of reaction.
Alkylation processes are extremely exothermic and occur at low temperatures (4-10 C for 0
sulfuric and 25-45°C for HF). The key features in the different reactor designs are the intimate
contacting of the acid with the hydrocarbon, (particularly the olefin) and the control of the reactor
temperatures. Stratco, Kellogg and Exxon are a well known licensors of sulfuric acid alkylation
technology (Keefer et ai, 1991) and UOP and Phillips license HF technology (Lew et ai, 1991).
Historically, the light olefins used as feed have been a mixture of butenes and propene. HF is
more effective for alkylating propene together with butene because of increased hydrogen transfer
rates and much lower acid consumption. The HF alkylate properties for various butene isomers
are shown in Table 18. HF alkylate obtained from 2-butenes has a road octane of 96.0, about
3 numbers higher in octane over alkyalte derived from 1- butene. Sulfuric acid alkylation
provides alkyl ate with similar octane from either 1- or 2- butene feed. The difference in octane
potential between the two alkylation processes is presumably due to the relative rate of alkylation
transfer versus the rate of double bond isomerization. Both propene and isobutene are not.
desirable feedstocks for sulfuric acid alkylation because of their high acid consumption and lower
octanes.
TABLE 18
HF Alkylote Properties
trans- cis- iso- Mixed
- -----
8ulene·l Butene·2 Bulene·2 Butene C3= /C 4=
Sp. Gravity 0.709 0.707 0.707 0.702 0.699

Mol. WI. 114.5 113.5 113.5 112.1 '08.6
(R+M)/2 93.0 96.2 96.0 94.7 92.3
RVP. psi 2.7 2.2 2.2 3.6 3.8
Alky Yield
(VoI/Vol Olefin) .73 1.77 1.81 1.78 1.79
iC4 Consumption
(Vol/Vol Olefin) 1.10 1.14 1.17 1.15 1.28
In the past, there was little incentive to process Cs olefins in the alkylation unit because they
were normally included in the gasoline pool due to their acceptable octane rating and they cause
higher acid consumption in the alkylation process. However, the recent Clean Air Act
Amendment specification on RVP and potential evaporative emissions could force U.S.
refineries to back out Cs olefins from the gasoline pool and upgrade them via alkylation or
etherification. Although acid consumption will increase, both HF and sulfuric acid processes can
alkylate the Cs olefins, producing similar octanes as shown in Table 19. Table 20 compares the
properties of the Cs olefins before and after alkylation (Lew et ai, 1991).
168
TABLE 19
OCTANE POTENTIAL OF CS ALKYLATES
(5 Olefin I$omt!o Octane (RtMV2
3-Mcthyt-l·Butenc 90.7
l·Pentene 87.9
2-Methyt-l-Butenc 90.0
2·Pentene 89.9
2-Methyt·2-Butenc 90.3
TABLEla
Effect of Alkylation on Cs Olefin Properties
Mixed
nCs= iCS= Cs= Alkylate*
Sp. Gravity 0.644 0.6S4 0.650 0.703

Mol. WI. 70 70 70 , 10.9
(R+M)/2 82.S 90.5 87.4 89.7
RVP, psi 19.1 19.7 19.4 1.0
Relative Volume 1.0 1.0 1.0 1.51"
*Depentanized Amylene Alkylate

"Based on Cs Olefin Volume = 1.0
:'iiI,J fit aI, lJ!J1
Since FCC olefins contain significant amounts of contaminants, including sulfur, nitrogen as
well as diolefins, feed pretreatment is necessary to improve downstream alkylation or
etherification processes. In addition, methanol and dimethyl ether significantly increase acid
consumption. Thus, if an MTBE or TAME unit precedes an alkylation unit, the MTBE or
TAME effluent must be treated to remove the trace methanol and oxygenates.
Because of the expanding role of alkyl ate in reformulated fuels, new developments are currently
being pursued. This includes more stable, solid alkylation catalysts, improved liquid catalysts
and two stage processes which produce higher octane product (Albright, 1990).
2.8. OXYGENATE FORMATION PROCESSING OPTIONS TO PRODUCE OXYGENATES
2.8.1. Etherification Chemistry. Addition of oxygen-containing molecules such as MTBE and

TAME have been proven to be very effective in not only boosting the gasoline pool octane but
also reducing the exhaust emissions of unburned hydrocarbons and carbon monoxide. The
observed benefit is attributed to a promotion of more complete combustion of gasoline in vehicles
due to the presence of the oxygen in the MTBE or TAME. The blending octane potential and
169
RVP of various oxygenates including ethers and alcohols is compared in Table 21 (piel and
Thomas, 1990).
Table 11
Properties of Conventional Ethers and AJcobols
~ mil UMIi IDA £!.QH ~

Blendinl (R + M)12 110 III lOS 100 115 lOS"
Blendin, RVP,psi 8 4 9.5 18 >31
Max. Cone, vol ~ 15.0 12.7 12.4 16.1 10.0 9.7"

Max. OxYlen Cont, wt 2.7 2.0 2.0 3.1 3.7 3.1"
Boilinl Point, 1P HI 161 IS7 181 173 148

Density @601P, Lb/Gal 6.2 6.2 6.4 6.6 6.6 6.6
Note: "Properties of MethanollCooolvenl Blend.
PicJ and Thomu
MTBE is conventionally produced from the etherification of isobutylene with methanol over
sulfonated acidic resin catalysts under very mild conditions.
iC4 = + MeOH <= > MTBE
The reaction is exothermic and requires a reactor design (adiabatic fixed bed with recycle or
tubular) that keeps the temperature essentially constant. The equilibrium constant for this reaction
is about 100 (Voloch et al, 1986). The reaction takes place below 100°C and at a high enough
pressure to assure its occurrence in the liquid phase (about 200psig). In most commercial units,
the catalyst is a cation exchange resin which limits the MTBE reaction temperatures due to
catalyst stability constraints. The methanollisobutene ratio is kept close to I to avoid the
formation of oligomers at too low a methanol concentration or excess methanol in the C4
overhead stream. The upper limit in the methanollisobutene ratio is due to the formation of an
azeotrope with the C/s in the distillation process which is about 4% methanol in the overhead
stream. Typical yields from an MTBE unit at III methanol to isobutene ratio over a resin
catalyst are shown in Table 22 (Miller and Piel, 1989).
MTBE reactor designs include tubular, adiabatic fixed bed (upflow and downflow) and
expanded beds (Keffer et ai, 1991). The different reactor designs are primarily to control the
temperature and insure an all liquid phase reaction. This reaction is also ideal for catalytic
distillation, a process in which the catalyst is loaded directly into the distillation tower (as shown
in Figure 6) (D'Amico et al, 1990). This process continuously withdraws the highest boiling
components (MTBE) as the reaction proceeds, thus shifting the equilibrium and producing higher
conversion and ether selectivity (up to 99%). In addition, the exothermic heat of reaction is used
to fractionate the product. Thus higher single pass conversions can be achieved ( - 99 %) than
with conventional fixed bed reactor technology without increasing feed methanol concentrations
which would cause the azeotrope formation in the downstream debutanizer.
TAME is produced in essentially the same type of process as MTBE except it uses isoamylene
(C s iso-olefin) as the feed stock.
170
The reaction is also liquid phase, being carried out under somewhat more severe conditions than
MTBE. Reaction rates are slower for TAME than for MTBE and equilibrium conversion are
lower. Conventional single-stage iso-amylene conversion is - 65% (Chase, 1984). Catalytic
distillation can improve the conversion and selectivity by continuous removal of the product
TAME as it is being formed and shifting the TAME equilibrium. The combination of fixed bed
recycle process followed by a catalytic distillation is claimed to achieve yields of TAME as high
as 90% (D'Amico, 1990).
Typical MTBEITAME process schemes are shown in Figure 10. The catalyst in these reactors
typically requires feed pretreatment (usually a water wash) because the resin catalyst is sensitive
to feed poisons such as caustic, organic bases, nitrogen compounds and trace metals. Zeolite
catalyst could have an advantage here. Among many Mobil proprietary zeolites, ZSM-5 and
ZSM-11 have been shown to be selective zeolite catalysts for MTBE production (Chen and Kuhl,
1987). The zeolite catalysts could offer some potential process flexibility, including high
temperature stability and product selectivity as well as regenerability.
Fixed lied Proass

Mfth.nol Mflhanol
Reaclon Cebulan"., Extraction Rfco"ery
Table 22
t c .. R.llinal. r"
Conventional MTBFJTAME YleldsiStoichometry
MTBE
- Stoichomelly 1.27MTBEl1.0 iCC-
- iC4= Conversioo -96"
- MTBE Selectivity
99"
TAME
- Stoichomelly 1.22 TAME/1.0 iCS=
- 10 = Convenioo 50-65"
- Selectivity 90"+ Catalytic Dlstlllollon Process
Prima". Cal.lytlc Methanol
Miller.nd PioI. 1919 R••ctor Ol.mlallon ExtraeUon
.--~~~--'II-.
Figure 10. MTBE Flow Schemes.
As shown in Figure 11, the conventional MTBE process requires a methanol recovery and an
oxygenate (DME) removal section, which significantly complicates the process design and
increases the cost. One method to eliminate the methanol recovery and oxygenates removal
sections, and also upgrade the n-butenes to high octane gasoline is to install a MOG
(Mobil-olefins to gasoline) unit downstream of an MTBE reactor. This process uses ZSM-5
catalyst in a fluidized bed reactor making it highly efficient and flexible. The chemistry of MOG
is shown in Figure 12 (Harandi, et alI991). The light olefins can be oligomerized, redistributed,
hydrogen transferred, cracked and aromatized. The degree of aromatization depends on the
171
severity of the operation. Thus, the product yields and gasoline octane in the MOG process
depend on the operating severity as illustrated by the results in Table 23. The ZSM-5 catalyst
in the MOG process is capable of converting methanol to gasoline using well known MTG
(methanol to gasoline) chemistry. Thus MOG allows efficient upgrading of the unconverted
butenes and methanol in addition to other light oxygenates leaving the MTBE reactor (Harandi,
et ai, 1991). MOG can be directly integrated with MTBE reactors to remove the methanol
impurity in the C4 stream (Figure 11). The MTBE and MOG integration eliminates the need for
the expensive methanol recovery and other oxygenates removal sections. This reduces the
investment and operating costs of the MTBE unit by about 30%. The MOG unit also upgrades
the C3 and C4 olefins to high octane gasoline which can be directly blended into the gasoline pool.
Thus MOG is a cost effective alternative or complement to alkylation.
Methanol MTBE/MOG
Fuel
FCC LPG
C4'S
Figure 11. MTBE/MOG Integration.
C2' - C4'. C6', Ca' ......... Cs+ (PONAl

C3= - C6=. Cg= - - Cs+= ~ +
C4= _ Ca= _________ Light Gases
3al"andi et aI, 1991
Figure 12. Mobil OIefins to Gasoline (MOG) Reaction Pathway.
2.8.2. Dehydrogenation. One way to increase the production of oxygenates is to generate light
olefins by dehydrogenating the light paraffins. In particular, the new RVP regulations will
decrease use of butanes in gasoline and provide increased incentive for converting them to MTBE.
172
The iso-butane dehydrogenation reaction
c-c-c < = > c-c=c + Hz

I I
c c
requires high temperature (1050-1200 OF) and low pressure (5-50 psia). The reactions are highly
endothermic and conversion per pass is fairly low (- 20-60%). Thermodynamics (Table 24)
(Happel and Mezaki, 1987) show that the olefin product is favored at high temperatures and low
pressure. But the upper temperature limit is constrained by minimization of thermal cracking.
(Thermal cracking will increase butadiene and coke, and unselective light gas formation).
Pressure is a major variable and thus a trade-off exists between higher compression costs and
increased conversion/pass.
TABLB23
MOGYIELDS
WI" Olefin Feed lDw Severity High Severity
c- O2 3.4
eJ's 6.0 11.9
C4 .. 14.0 23.8
CS~asoline 79.7 60.6
Coke 0.1 0.3
Gasoline Octane
R-IO 92 97
M-IO 79 84
Gasoline Composition
P 9 30
0 89 21
N 0 10
A 2 39
Table 14
Thermodynamics of Is4HlutaDe dehydrO&enatioD
T. F p. pcia i--butme equ.il.. COIIVen;iOll
1100 0 71
1100 30 Sl
1100 100 31
1000 0 53
1000 30 33
1000 100 21
The dehydrogenation process was first commercial ized in the 1940' s (Houdry' s CATADIENE).
The initial catalyst used was chromia on alumina. Most commercial process still use this catalyst
today. However, two recent processes use Pt on alumina catalyst (UOP's OLEFLEX) (Pujado,
1990) or other noble metals (Phillip's STAR) (Brinkmeyer et aI, 1983).
The major factors which control the reactor design are:
1) The large endothermic reaction which requires significant heat input

2) Rapid catalyst deactivation due to high coke formation.
173
3) Low pressure operation
The developers of this process have solved these factors in a variety of ways. (See Table 25
for process descriptions). The CATOFIN process (Lummus) uses adiabatic fixed bed reactors
which swing quite often (approximately 5-30 min cycle time) from reaction to regeneration
(Harnady et al, 1961). The unit is designed to provide fuel to supplement the coke produced
during the reaction cycle to supply the endothermic heat of reaction. UOP's OLEFLEX process
also uses adiabatic beds but their design is based on the CCR moving bed technology. Here, the
catalyst moves through at 3 least adiabatic beds with inter-reactor heat supplied between them.
Coke is burned off in their moving bed regenerator. The cycle time is approximately 3 to 5 days
through the reactors. Coke production is reduced by co-feeding hydrogen. This comes at the
expense of lower conversion (since hydrogen increases the reverse reaction) and higher
compression cost.
Table 25
Highlights of Commerica1 Dehydrogenation Process
hoc... Reactioa TF Pre8S,po;;, CataI)'st Spocial Feacturea

CATOFIN (Air Products) Adiabatic 1000-1250 '5-15 Cr/A1203 Swing Reactor
Fixed Bed '5-30min cycle
UOPOLEFLEX Mulli-SlAje 30-50 PtJA1l03 H2 Co-feed

Moving Bed 3-5 daYice •. time
Phillip's Star FIXed Bed 1000-1100 IS-50 Proprietary Steam Co-Feed

Tubular 3-5 day. cat rcllidance
ti~
S(Ulinpregetti Fluidized Cr/Al203 Fluid Bed

Bed Rxtr-Design
Phillips ' STAR process uses a tubular reactor to supply the heat of the reaction in a fired
furnace. Steam is used to lower the partial pressure of the butanes (and thus increase the
equilibrium conversion) and reduce coking. The STAR process operates on about an 8 hour
cycle before regeneration (Brinkmeyer, et ai, 1983).
Snamprogetti has just recently announced it is licensing fluidized bed dehydrogenation based
on earlier Russian technology using chromia on alumina catalyst. Again, the heat of reaction is
supplied by regeneration of the coked catalyst (Octane Week 1990). Linde has also recently
announced a dehydrogenation process based on isothermal tubular swing reactors using a
proprietary catalyst with no steam or hydrogen dilution.
In order to achieve high conversion to field butanes to MTBE it is important to isomerize the
n- butanes before dehydrogenation. This is usually done by coupling the butane isomerization
reactor (which converts the n-butanes to isobutane) followed by the dehydrogenation reaction.
Since the dehydrogenation catalyst contains virtually no acidity (to prevent excessive coke
laydown) the isobutane will dehydrogenate almost exclusively to isobutene. A de-isobutanizer
(DIB) column upstream of the dehydrogenation reactor, allows the separation of iso-from
n-butanes, thus allowing n-butanes to isomerize to isobutanes which when fed back to the DIB
column will be sent to the dehydrogenation unit (Bakas, et ai, 1991).
In order to be competitive, these plants will have to be highly heat integrated between the
isomerization, dehydrogenation and etherification processes. Minimal recycle is needed with
cost effective use of low level heat.
174
2.9. PROCESSING OPTIONS TO PRODUCE LOW SULFUR/HIGH QUALITY DISTILLATE
2.9.1. MOGD. One way to produce low sulfur high quality distillate is to produce it from light
olefin building blocks. Mobil's Olefin to Gasoline Plus Distillate (MOGD) process will convert
FCC propene and butenes into high octane blending components and to olefinic jet and diesel fuel
components. Upon hydrogenation, the jet and diesel blend fuel components produce jet fuels
with very low freeze points and high smoke points and diesel fuels with very low pour points and
high cetane numbers. The distillate has very low sulfur, nitrogen, and aromatic compounds. The
process uses ZSM-5 in a fixed bed reactor (Yurchak et al, 1990).
The reaction path for converting olefins to gasoline and distillate over ZSM-5 is complex
(Krambeck et al, 1988), as shown in Figure 13. Initially, an olefin, will oligomerize to carbon
number multiples of itself (Le., C3 = reacts to C6 =, C9 =, C12 =, etc.). These oligomers then
crack and re-oligomerize to form a continuous carbon number distribution. The net effect of
these reactions (oligomerization, cracking and re-oligomerization) is that a single olefin can
produce a product whose carbon number distribution is unrelated to the carbon number of the
original monomer (Quann et ai, 1988). The degree of branching of the final product is a
function of thermodynamic constraints, reaction severity, and catalyst selectivity.
Oligomerization CtaCImg Co OligomerizaUon
j Hydrogen Abstraction Reactions

(Conjunct Polymerization)
Cycfoolean.
Aromaltco
Paraffine
Figure 13. MOGD Reaction Path.
The high quality of the MOGD product is due to the shape selectivity of the ZSM-5 catalyst.
The gasoline product consists primarily of straight chain and branched olefins which have a good
octane number; the raw distillate consists of mono-olefins which have methyl groups interspersed
along the linear carbon chain. After hydrogenation, this type of structure leads to an iso-paraffinic
product which has exceptionally good distillate properties, including very low aromatic content,
very low pour point and a high cetane number. Since the product is essentially all mono-olefin,
hydrogen consumption in the hydrogenation step is stoichiometric at 1 mole of hydrogen per mole
of distillate. The properties of the MOGD distillate kerosine and gasoline are compared to
industry standards in Table 26. The high cetane, very low aromatic content plus the low sulfur
and extremely low pour and cloud points make MOGD distillate a superior blend stock. These
exceptional properties give MOGD the potential to play an important role in meeting future
demands for cleaner, low aromatic transportation fuels. Because of its low branching paraffinic
structure after hydrotreating, the MOGD jet fuel meets or exceeds all commercial specifications.
The high thermal stability, low freeze point and low aromatic content make this material a
premium jet fuel or jet fuel blend stock. The gasoline is essentially all mono-olefinic and no
hydrogenation is required. This results in a research octane of 92, but a 79 motor octane.
Density is also low due to its olefinic nature. As a result, this makes a good gasoline blend stock
175
with reasonable octane. Generally, gasoline yield is low in the distillate mode MOGD operation.
To produce higher octane gasoline from light olefins at high yields, Mobil's MOG process was
developed (as discussed previously).
TableU
MOGD Product Properties
MOOD Conventional
Diesel Fuel
90% 331 252 299
Cetane' 52 51 45
CloudPt ·55 ·37 ·17

Sulfur .002 0.07 0.32
Aromatics 2.9 20 32
OJefins 1.3 2 3
Saturates 95.8 78 65
Jet Fuel
Freeze Pt. -60 -47 MAX
Aromatics 4 25 MAX
Smoke Pt. 28 19 MIN
Sulfur 0.002 0.3 MAX
Gasoline
RON 92
MaN 79
Aromatics 2
Olefins 94
2.9.2. Hydroprocessing - For Low Sulfur Fuels. A variety of hydroprocessing applications

ranging from gasoline hydrofinishing to gas oil hydrocracking to resid hydrotreating are used in
the industry today. The primary reactor systems are trickle bed reactors with gas-liquid cocurrent
flow. Operating conditions include temperatures of 500-800°F Pressures of 700-2300 psig,
WHSV of about 1, and Hz circulation of about 1000-2500SCF/Bbl. A variety of catalysts are
used such as sulfided Co-Mo-AI203' and NiMo-AI 2 0 3 for sulfur and nitrogen removal and mild
hydrogenation, to high activity noble metal containing zeolitic catalysts for deep hydrogenation
and hydrocracking. Also, for demetallation applications a range of catalysts are available.
Figure 4 shows a schematic process flow diagram showing FCC feed hydrotreating and also
hydrotreating of cycle oils which are recycled back to the FCC unit. FCC feed hydrotreating has
a beneficial effect on FCC product yields and properties. It saturates polynuclear aromatics and
reduces sulfur, nitrogen, CCR and metals. This results in higher FCC conversion and gasoline
at constant coke. Table 27 summarizes typical results (Derr et ai, 1990). Equally important is
the beneficial effect of hydrotreating on reduced SOx emissions from the FCC, as is reduction in
sulfur and nitrogen in the resulting FCC gasoline and distillate. The catalytic feed hydrotreators
range from low-to-medium pressure units intended for sulfur and nitrogen removal, to high
pressure units where motor diesel is the primary product and FCC feed is what's left over. From
Table 27, we see that the benefits of hydrotreating increase with increasing severity. High
pressure hydrotreating increases FCC conversion due to increased feed aromatic saturation A
choice of the type of catalytic feed hydrotreating is a complex economic decision and depends
on the refinery configuration and feed.
FCC cycle oils are typically high in aromatic content and have low cetane number (10-20) .
Hydrotreating or hydrocracking of these products and recycling them back to FCC to increase
176
gasoline production has been practiced commercially. Properties of hydrotreated LCO and
resulting yields and gasoline properties are summarized in Table 28 (Merlin et al, 1989). As
shown in the table, increasing LCO hydrotreating severity improves gasoline yields, but at the
expense of octane numbers. Coke-conversion selectivity improves significantly, and C4- products
increase. However, the aromatic content of the gasoline does not change dramatically. Here
again the gasoline pool overall balance is critical. Although the process reduces low cetane FCC
distillate, the resulting gasoline is marginal in quality.
Table 21
Tabld7 Hydro...... ted LCO to Catalytic Cracki...
Impact of Hylirotreating on FCC Perf'onnaoce
RAW LOW Higb

HOT HDT
HDT Conditions Hld[2treatmcnl ~~2DI
P,.....,.(ban) 35 60 120
Pressure, psia 1240 1750
LHSV LHSV(Hr·) 0.6
1 1
Temperature 706 753
Temperatwo (C) 350 360 380
H2 Consumption NM31M3 135 200
Peed to FCCU
~
D.....1y 0.893 0.88 0.8<47
Specific Gravity 0.94 0.925 0.918 91 N·D-M/C Arom 36.9 29.1 19.4
Sulfur, wt% 1.28 0.116 0.024 9ICN.ph 23 34.2 36.3
Nitrogen, ppm 5100 2800 1000 ~ C Para 40.1 36.7 44.3
CCR, wt91 0.9 0.2 0.11
CA, 'Ii 27 21 18 FCC Yields Wt"
Converuoo 54.1 63.5 76.3
FCC Yields Gasolino 37 43 54
Coke, wt% 5 Gas (C4-) 16.S 19.2 22
Conversion, vol % 48 64 81 Coke 1.6 I.) 0.6
Gasoline, vol % 34 52 66
GasollDC PropertlCi.
Derrci a1 (1990) RON 92.6 93.7 90.8
MON 82.1 81.6 79.S
Aromatica (wt'li) 49 49.5 41
Merii.a Cla1 (1919)
Hydrotreating of heavy FCC Naphtha is necessary to reduce the sulfur content of the gasoline
pool. Sulfur contents of FCC products are non-uniform with respect to boiling range. For a
nominal Cs to 232°C gasoline containing 0.33 wt% sulfur, approximately 60% of the sulfur is
concentrated in the highest boiling 15 vol%, see Figure 14 (Derr et ai, 1990). Benzothiophene
and substituted benzothiophenes are the primary sulfur species in the heavy boiling range. Figure
14 also summarizes data for olefin, and aromatics composition and octane numbers as a function
of boiling point. It is readily apparent from these figures, that one can achieve substantial sulfur
removal with minimal olefin saturation and octane loss by selectively hydrodesulfurizing only the
higher boiling fraction of the full range FCC gasoline. Such selective hydrotreating processes
will be crucial to minimize capital and operating costs and meet future environmental
regulations.
Hydroprocessing is a critical technology to meet sulfur requirements of distillate fuels.
Recently, the Clean Air Act Amendments mandated new rules limiting sulfur to 0.05 wt% in
highway diesel fuels, and their regulations will become more stringent in the future.
A great deal is known about the current generation of hydroprocessing catalysts. Using in-situ
Mossbauer emission spectroscopy and extended x-ray absorption fine structure (EXAFS), the
Haldor-Topsoe group has conclusively shown that the active sites on the sulfided Co-Mo-AI 20)
catalyst are vacancies associated with the edge sites in the Co-Mo-S phase. In fact, the thiophene
desulfurization rate is linearly proportional to the concentration of the Co-Mo-S phase. A
177
consensus is being reached in the scientific community on the nature of active sites in the
hydrotreating catalysts. Although significant progress has been made in the field of catalysis and
surface science, industrial catalyst development to date has been a trial and error exercise.
However, significant strides have been made in this area of research. The challenge remains to
develop a next generation step-out, breakthrough hydrotreating catalyst using our fundamental
and empirical knowledge. This need is amplified by tightening environmental regulations. For
example, the recent EPA regulations could be more effectively achieved with improVed catalysts.
]~====,=-==-=-='=-=-=-=-= -=: ;:-= .:~

Sulfur
(Wt.%)
Composition
(Vol. '10)
::L?< :; ;:-1
Octane
:~~: : ~_Research I
80 • Motor
75L--=~==~~~ ____L-______-L__~____~
40 90 150 200
Fraction Mid Boiling POint. °C
• Heavy End Will Require HOF to Reduce Sulfur Content
iJerr et aZ, 1990
Figure 14. Sulfur Distribution in FCC Gasoline.
In Figure 15 we compare the empirically observed severity required to achieve 0.05 % S as a

function of total sulfur content of feeds for a variety of distillate boiling range materials which
contribute to the diesel pool (Shih et ai, 1990). Figure 15 clearly shows that reactor temperature
required to achieve 0.05 wt% S in product is not correlated with the total sulfur in feed.
Additional insight in the desulfurization chemistry is gained by exploring the detailed sulfur
distribution in the feed and product.
800
alCO
750
• 6OO"f .. Gas Oil
..
~ 700
..,;
Mixed HOS reed •
~ G50 • Coker CdS Oil
8 Full·Range G.ls 011 •
No.2 Fuel Oil •
'"
~ 600
• Heavy KerOSIne
sso
• GOO·f· Ws 0;1
soo
0.1 I 10
rOb! Sultur In feed, Vv"l %
Figure 15. Severity to Produce 0.05% Sulfur.

178
Figure 16 summarizes the sulfur distributions obtained with high performance chromatographic
separations for a feed containing 1.9 wt% S, and desulfurized products at several extents of
reaction. Below about 0.24 wt % S, the remaining species are predominantly substituted
dibenzothiophenes. Thus, it is not the concentration of the total sulfur that is important, but the
concentration of substituted methyl dibenzothiophenes. These data corroborate earlier work
reported by researchers at the University of Delaware. Table 29 summarizes relative reaction
rates of several model sulfur-containing (S) compounds (Sapre, 1980). At fixed operating
conditions, it is seen that relative to dibenzothiophene, both the lighter S compounds such as
thiophene and benzothiophene, and heavier species such as benzonaphthothiophene react faster.
On the other hand, sterically hindered 4,6-dimethyldibenzothiophene reacts an order of magnitude
slower than dibenzothiophene. Thus, we know precisely, at the molecular level, the kind of S
species we need to convert to meet future environmental regulations. Modern spectroscopic
techniques have significantly imprOVed our understanding of the current generation desulfurization
Icatalyst. The challenge clearly is to develop the "Designer Catalyst", that is a heterogeneous
solid catalytic material with an enzyme like specific selectivity, i.e. to use these "steric
hindrances" to our benefit.
~
c
o
a.
U>
~ Tolal Sulfur - 0.24 WI.%
'"
Z
iii
£ Tolal Sulfur - 0.11 WI.O/O
Total Sulfur - 0.018 WI.%
Tolal Sulfur - 0.008 WI.O/O
nme~
Figure 16. Sulfur in HDS Feed and Products.
3. Process Integration
Saleable products leaving the refinery are blends of intermediate streams produced by the
processes summarized above. The optimal process integration and also the fuel blending are
typically performed by linear programming (LP) techniques. Today this blending is done to gross
product properties (e.g. gasoline octane, gravity). In the future, however, gasoline and distillate
will be blended based on composition (aromatics, oxygenate content) driven by the reformulated
fuel regulations. In order to effectively utilize a refineries' resources, there must be an increased
emphasis on improving the accuracy of our process models to predict the impact of variables on
product composition, and also to produce models that will simultaneously optimize, blend and
schedule the refinery operations to minimize compositional giveaway. Two research areas which
will aid in this effort are the efforts to develop the kinetics of complex mixtures using new
179
analytical developments and the increase in computer power allowing much more complicated
problems to be solved essentially in real time.
TABLE 29
Relative Desulfurization Rates
Thiophene 0 23.0
Benzothiophene ~ 13.0
Dibenzothiophene C§:Jr;J@ 1.0

CK3 CH3
2-8 Dimethyldibenzothiophene ~ 1.0
4-6 Dlmethyldibenzothlophene ~ 0.1
Benzonaphthothiophene CH3 CH3 3.0

©o§@
Sapr •• 198Q
More fundamentals of reaction chemistry are now being integrated with kinetics using the
modern analytical techniques such as high performance liquid chromatography (HPLC) and field
ionization mass spectrometry (FIMS). These techniques provide the ability to characterize the
complex feedstocks and products essentially at the molecular level of detail. Such a detailed
feedstock description allows a deeper understanding of the chemical reactions and accurate
description of the reaction pathways. With this knowledge, group contribution methods are being
developed to describe kinetics of complex mixtures (Sapre and Krambeck 1991). The resulting
product distribution from such kinetics methods has the molecular level of detail. This capability
will allow not only more accurate assessment of product composition and qualities but also more
accurate LP predictions for the refinery of the future qualities. Advances in analytical
instrumentation technology and computer technology will allow us to efficiently develop fuel
products with the compositional constraints needed for the market place of the future.
4. Challenges For The Future
In this paper, we have attempted to summarize key technologies that are currently available which
can increase the production of clean fuels. Some of these technologies involve coupling of
various processes; for example, dehydrogenation (fairly mature technology) is coupled with
etherification (relatively new technology) to produce ethers from light paraffins. Other
technologies which were developed for lead phase down can be used or refined to produce
additional clean fuels. For example, because of lead phase-down, USY low unit cell size FCC
catalysts and ZSM additives have been used to increase octane of the FCC gasoline. These
catalysts at the same time have decreased gasoline aromatic content and increased light olefins
and in the case of ZSM-5, the iso-olefins. These light olefins can than be used to increase
alkyl ate and oxygenate production, further diluting the gasoline aromatic content. Some of the
180
technologies have become more cost effective due to emerging engineering technology. These
include use of molecular sieves to separate iso-paraffins from n-paraffins and catalytic distillation
which increases the yield in reversible reaction sequences (such as TAME/MTBE).
There are still many challenges facing the refining industry in the production of clean fuels.
These include technological challenges such as developing new catalysts or hardware in existing
processes, integration of the new technologies with existing technologies to minimize energy use
and improve efficiency, and developing more efficient separation process schemes. Also, there
are business challenges as well; how to find the capital and manpower necessary to build the new
processes discussed in this report.
There are other challenges as well, which face the industry: Which alternative technology to
use - new technology which has greater potential to reduce costs/increase yields or commercially
proven technology that could be quite inefficient. There are many combinations of process
technology which can produce the reformulated fuels required for the future. This will lead to
different processing routes and alternative paths to be chosen by individual companies. This is
similar to today's refining industry where there are a number of different processing schemes to
produce refined product. However, the companies which aggressively face both the technological
and economic challenges of today, will be leaders in this industry well into the 21st century.
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EVALUATION OF DIRECT METHANE CONVERSION PROCESSES
JAMES C. W. KUO
Mobil Research and Development Corporation
Post Office 480
Paulsboro, NJ 08066-0480, USA
ABSTRACT. This paper describes evaluation studies on direct CR. conversion processes. The processes
are first classified according to their chemistry and then subjected to preliminary evaluations, including
thermochemical calculations and some scoping process calculations. An analysis on selectivity, conversion,
and yield shows the importance of achieving high selectivities in all processes. Furthermore, two
processes, i.e., a "Direct Partial Oxidation to Methanol" process and an "Oxidative Coupling to Ethylene"
process, are selected for engineering evaluations for making liquid fuels. Both are compared against a
conventional Natural Gas-to-Methanol via Steam Reforming process. The DPOM process scheme is simple
because of simple products and easy product separation and could become competitive if> 90 % selectivity
at 7.5 % single-pass conversion or> 80 % selectivity at 15 % conversion is achieved. The OCE process
scheme is relatively complicated and could become competitive if> 88 % selectivity at 35 % single-pass
conversion is accomplished.
1. Introduction
Since CH. at low temperatures is the stablest hydrocarbon, the commercially-established

technologies of converting CH. to CH30H and higher hydrocarbons require an initial formation of
synthesis gases (H 2+CO+C0 2) at 800-1,400· C. The most widely used process for such a
conversion is the Steam Reforming process:
CH. + H20 ~ 3 H2 + CO fill,(870· C)=54 kcal AG,=-15 kcal (1)

CO + H20 ~H2 + CO 2 AH,(870· C)= -8 kcal AG,= Okcal. (2)
Reaction (1) is the main reaction which is highly endothermic and energy intensive. The further
conversion of synthesis gas is illustra~ed by the formation of CH30H:
2 H2 + CO ~ CH 30H fill/27o" C)=-24 kcal AG,= 8 kcal (3)

3 H2 + CO 2 ~ CH3 0H + H20 AH,(270· C)=-14 kcal AG,=12 kcal. (4)
The conversion of CH. to CH 3 0H described above is just one of many possible routes of
converting CH. via synthesis gases. We call these processes "Indirect Methane Conversion."
183
H.l. de Lasa et al. (eds.), Chemical Reactor Technology for Environmentally Safe Reactors and Products. 183-226.
184
Recently, substantial research activity has been conducted in the area of CH4 conversion
without the use of synthesis gas. We classify such processes as "Direct Methane Conversion."
They have the potential of being more energy-efficient since they bypass the energy-intensive
step of synthesis gas formation.
Irrespective of CH4 conversion technologies, there are ultimate constraints resulting from the
large differences of the H/C atomic ratios between CH4 and the final products. While CH4 has a
H/C ratio of 4, all desirable products such as CH 3 0H, olefins, gasoline, or diesel fuel have
substantially lower HlC ratios (1.9 to 2). Such a large reduction in the H/C ratios of the feed to
those of the final products indicates the importance of preserving as much C-atom of the feed in
the products as possible. This is why it is essential for CH4 conversion processes to have high
carbon (C-) efficiencies. To use C-efficiency as a tool for process comparison, one must use the
"net" efficiency which is defined as the percentage of the C-atoms in the total natural gas feed
(including the portion of natural gas used as utility fuel) ending up in the useful products. We
should also use the "net" thermal efficiency which is similarly defined by replacing the C-atom's
with the LHV's (Low Heating Values) of the total feed and products. Note that the thermal
efficiencies are in direct proportion to the C-efficiencies when a single product is produced.
Consequently, it is often sufficient to consider only one efficiency.
It is important to understand the ultimate thermal and C-efficiencies of CH 4 conversion
reactions. These limits are defined with respect to specific feeds and the final product or
products. Table 1 summarizes those limits, as well as the minimum heat-transfer duties, of
making CH 3 0H, CZH 4 , and I-CIOHzo. In making CH30H, CH4 and air at room temperature and I
atm react in a magic black-box to produce CH 30H at the same conditions. The ultimate C-
efficiency is 100% while the ultimate thermal efficiency, given in LHVs, is 80%. A minimum
amount of heat, equivalent to 26% of the CH3 0H LHV, must be transferred out of the box. When
there is CO 2 available, the C-efficiency is improved to 123% by maintaining an exact energy
(HHV) balance on both sides of the second reaction in Table 1. The ultimate thermal efficiency is
improved to 98% and the minimum heat-transfer duty becomes zero. These improvements
clearly demonstrate the importance of COz availability on CH4 conversions. This benefit of COz
availability can be claimed by indirect conversion processes via COz addition during synthesis gas
formation. Based on thermodynamics, the two direct conversion processes cannot claim this
benefit.
The other four reactions in Table I represent the production of hydrocarbons instead of
CH30H. Except for the case of producing liquid hydrocarbons, exemplified by C,JIzo, production
of C ZH 4 and liquid hydrocarbons slightly increases the ultimate efficiencies. Note that the last
reaction consumes no Oz.
The number of direct conversion processes is very large. A logical classification of those
processes will help us to appreciate the scope of these processes and provide a logical framework
for technology reviews and evaluations. Kuo (1987) proposed the following classification based
on the chemistries of the processes:
I. Direct Partial Oxidation (to CH3 0H, methyl halides, or others)

1. Using Oz
2. Using Nitrous Oxide
3. Using Halogens
4. Using Super-Acids as Catalysts
II. Oxidative Coupling (to CZH 4 )
III. Direct Conversion to CzH z and Other Higher Hydrocarbons
185
Table 1. Ultimate Limits of CH. Conversion Reactions
Max. Max. Min. Heat-

Carbon Thermal Transfer
Eff. (% Eff. (% Duty (%
Reactions Feed) FeedLHV) Prod. LHV)
Formation of CH3 0H
CH. + 1/2 02(Air) ~ CH3OH(l) 100 80 26
CH. + .225 COz + .451 HzO(l) +
.162 Oz(Air) ~ 1.225 CH30H(l) 123 98 0
Formation of CzH.
CH. + 1/2 Oz(Air) ~ 1/2 CzH. + HzO(l) 100 82 28
CH. + .262 COz + .107 0iAir) =
.631 CzH. + .738 HzO(l) 126 104 0
Formation of CJ()!10
CH. + 1/2 Oz{Air) ~ .1 C1JI20(l) + HzO(l) 100 77 37
CH. + 1/3 COz ~ 4/30 C1JI20(l) + 2/3 H2O(l) 133 103
1. To CzH z via Thermal Pyrolysis

2. To C2H z Using Electric Arc or Plasma
3. To CzH z via Partial Oxidation
4. To Other Higher Hydrocarbons
IV. Other Direct Conversion Processes
1. Alkylation with Hydrocarbons
2. Activation Using Metals, Metal Oxides, or Metal Complexes
3. Conversion Using Coal or Shale.
Many reviews on various direct conversion processes are available, including those on many
or all classes by Pitchai and Klier (1986), Catalytica Associates (1986), Scurrell (1987), Kuo
(1987), and Baerns et al. (1989); one on DPOM by Gesser et al. (1985); and one on OCE by
Amenomiya et al (1990). Furthermore, abundant relevant papers were published in monographs
as in Catalysis Today (vol. 1 (1987), vol. 3 (1988), vol. 4 (1989), and vol. 6 (1990», in the
Proceedings of the 9th International Congress on Catalysis (vol. 2), in the preprints of the 1989
International Chemical Congress of Pacific Basin Societies (3B Symposium on Methane
Activation, Conversion and Utilization, December 17-20, Honolulu, HI), in the preprints of the
194 th National ACS Meeting (vol. 32, Symposium on Hydrocarbon Oxidation, August 31-
September4, 1987, New Orleans, LA.), and in the preprints of the AIChE 1989 Spring National
Meeting (Session 53 on Natural Gas Conversion, April 2-6, Houston, TX). Consequently, only
pertinent references would be mentioned here.
2. ThermochemIcal and Process Calculations
Thermochemical calculations were based on the latest data from the TRC Thermodynamic Tables
(1991).
186
2.1. DIRECT PARTIAL OXIDATION (to CHPH, methyl halides, or others)
2.1.1. Using 02' CH. can be oxidized to CH3 0H in conditions of deficient O2, 350-500· C and
high pressures. The chemical reactions are
CH. + 1/2 O2 ~ CH3 0H fili,( 400 • C)=-30 kcal ~G,=-22 kcal (5)
CH 30H + 1/2 O2~ HCHO + H20 fili,(4oo· C)=-35 kcal ~G,=-46 kcal. (6)
Both reactions are moderately exothermic. Unfortunately both CH 3 0H and HCHO can be
oxidized further to form CO2 , H20, and CO. This oxidation is called the "deep oxidation" and can
be minimized using low reaction temperatures. The heats of the reaction resulting from the
oxidation of HCHO to CO and CO 2 are 56 and 124 kcal, respectively. The heats of reaction for
converting CH. to CH 3 0H, HCHO, CO, and CO 2 are 60, 67,82, and 95 kcal/0 2 , respectively.
Generally, no elementary H2 or carbon are formed and the product gas mayor may not contain
any unconverted O2,
The work on direct CH. oxidation began in early 1900 and the first and only commercial plant
for converting natural gas to HCHO via DPO was constructed at Copsa Mica, Rumania in 1940
(Holm and Reichl (1947». Among many activities, particularly in making CH 3 0H, carried out
since early 1900, the only major systematic work were carried out by Professors Gesser and
Hunter and their colleagues at the University of Manitoba, Winnipeg, Manitoba (Hunter et al.
(1985), Gesser et al. (1986), Yarlagadda et al. (1988), and Hunter et al. (1990». They used small
reactors and found that the optimal operating pressure was -65 atm. They also found that the
presence of C; paraffins in natural gas allowed oxidation to proceed at -100· C less than that
required for CH. alone. The best CH30H selectivity reported was -81 % for CH. and -90% for a
natural gas. The conversions were determined by the level of O2 used; feed O2 concentrations
ranged from 2-10 mol % with little or no O2 breakthrough. Many catalysts were also evaluated.
Outside of the above work, there were a couple of recent publications showing high
selectivities and conversions. Zhu et al. (1989) reported CH 30H+HCHO selectivities of 86-93%
at 4.1-5.5% conversions using a Mo0 3 • Cr20JSi0 2 catalyst at 475-500· C and 49 atm at high
space velocities. Durante et al. (1989) showed 72% CH3 0H selectivity at 6.5 % conversion using
a silica-bound iron sodalite catalyst at 426· C and 55 atm.
Chemical equilibria of the main CH. oxidation reaction (Eq. (5» were calculated using
400· C(300-600· C), 65 atm(5-100 atm), and 100/50 molar(100/1-100/50 molar) CHJ02 feed.
Major conclusions were:
Essentially complete conversions of either CH. or O2

Higher conversions at lower temperatures and higher pressures.
Consequently, there is no thermodynamic limitation in achieving a very high conversion.

However, CH 30H selectivity decreases with increasing conversion due to further oxidation of
CH30H to HCHO, represented by Reaction (6), and to CO2 , H20, and CO. Inclusion of HCHO in
the chemical eqUilibrium calculations gave
• Essentially little or no CH3 0H formation resulting in 50% CH. conversion

187
• Higher CH30H selectivities at higher temperatures and pressures, and lower O2fed.
From these calculations it seems there is no thermodynamic limitation in the HCHO formation at
low temperatures and at high pressure. Gesser et al. (1986), however, claimed a process of
producing products of CH 30H/HCHO ratios larger than 10,000 at 350-450· C, 10-60 atm, 2-10
mol% O2, and 5-15 s normal contact time while using no catalyst, reactors with inert surfaces, and
intimate O2 and natural gas mixing.
Further inclusion of CO. in the chemical eqUilibrium calculations resulted in 100% selectivity
to COx' This was expected because COx were thermodynamically very stable in this range of
temperatures. Lower COx selectivities could be expected with higher pressures, and lower
temperatures and feed O2,
Low temperatures and feed O2 were required to kinetically avoid deep oxidation of CH4 to
COx' A separate set of chemical equilibrium calculations was then conducted using a lOOn molar
CHJ02 feed instead of the preceding 100/50 feed. However, the conclusions remained the same.
Based on the literature review and the results of thermochemical calculations, this process has
the advantages of having potentially high CH 3 0H/HCHO selectivities, easy product separation,
moderate reaction temperatures and pressures and a potentially low pressure drop operation, and
limited commercial experience in making HCHO. It also has the disadvantages oflow single-
pass conversions, needing an O2plant, large reaction heat removal, and low technology status.
2.1.2. Using Nitrous Oxide. CH4 can be oxidized to CH 3 0HIHCHO using nitrous oxide at 500-
600· C and low to moderate pressures. The main chemical reactions are
CH4 + N 20 ~ CH30H + N2 AH.(500· C)=-50 kcal AG,=-54 kcal (7)

CH3 0H + N20 ~ CH20 + H20 + N2 AH.(500· C)=-55 kcal AG,=-81 kcal. (8)
Both CH 3 0H and HCHO can be further oxidized to H 20, CO, and CO 2 represented by the
following reactions:
CH20 + N 20 ~ CO + H20 + N2 AH.(500· C)= -77 kcal AG,=-l04 kcal (9)

CH20 + 2N20 ~ CO 2+ H20 + 2N2 AH.(500· C)=-165 kcal AG,=-189 kcal. (10)
The heats of reaction of oxidizing CH4 to CH3 0H, HCHO, CO, and CO 2 are 50, 53,61, and 67
kCal/N20, respectively, which are 41-67% higher than the O2case (per O-atom basis).
N20 used in the above reactions must be obtained from an economical source. Commercially
N20 is produced from NH4N0 3 according to the following reaction:
AJI,(25 • C)=-9 kcal AG,=-41 kcal. (11)
This reaction takes place at 200-260· C. However, since one mole of NH4 N0 3 costs more than
one mole of CH3 0H, this process does not make much economic sense.
Chemical equilibria of Reaction (7) were calculated using 500· C(400-700· C), 35 atm(20-50
atm), and 100/100 molar(100/2-100/l00 molar) CHJN20 feed. Since the reaction has no molar
change, there is no pressure effect on the eqUilibrium. Other conclusions were found to be similar
to those of Reaction (5) by replacing O 2 with N 20. Inclusion of HCHO in the equilibrium
calculations gave results resembling those of the O2 case. Inclusion of CO. in the chemical
eqUilibrium calculations again resulted in a 100% selectivity to CO•. These results, once again,
188
resembled those of the O2 case. No equilibrium calculations were carried out for Reaction (11)
because its .6.0;s at reaction temperatures were not available. However, the large negative value
of .6.0, at 25' C indicates a very favorable chemical equilibrium to N 20 formation.
2.1.3. Using Halogens. CH. can be oxidized to methyl halides using halogens. A typical reaction
with C1 2 is
.6.H,( 250' C)=-24 kcal .6.0,=-25 kcal (12)

.6.H,(1,600' C)=-25 kcal .6.0,=-30 kcal.
However over-halogenation represented by the following reactions always occurred:
CH3Cl + Cl2 ~ CH2Cl2 + HCI .6.H,(250' C)=-25 kcal .6.0,=-25 kcal (13)
CH 2Cl2+ Cl2 ~ CHCl3 + HCl .6.H,(250' C)=-23 kcal .6.0,=-23 kcal (14)
CHCl3 + Cl2 ~ CCl. + HCl .6.H,(250' C)=-20 kcal .6.0,=-18 kcal. (15)
To complete the Cl 2 cycle, Cl 2is regenerated from HCl according to
2 HCl + 1/2 O2 ~ H20 + C1 2 .6.H,(250' C)=-14 kcal .6.0,=-6 kcal. (16)
Benson (1980) discovered that, at >700' C and low pressure, Reaction (12) can proceed
further according to the following condensation reaction:
2 CH. + C1 2 ~ 2 HCl + (l-X)C2H6 + X C2H. + x H2. (17)
C2H6 formation, i.e., x=O, is favorable at -700' C, while the C2H. and H2 formation is favored at
1,500-1,700' C. The heat of the reaction is -28 kcal with C2H6 formation (at 700' C) and 6 kcal
with C 2H. formation (at 1,600' C). No selectivity and conversion data were given. In later
related publications by Liebert-Simon Int'! (1984), however, co-production of C 2 H 2 was
mentioned without any operating data.
Combination of Reactions (12) and (16) results in an "oxychlorination" reaction:
CH. + HCl + 1/202 ~ CH3Cl + H20 .6.H,(250' C)=-38 kcal .6.0,=-31 kcal. (18)
Again, over-halogenation, represented by reactions obtained by combining Reactions (13) to (15)

and Reaction (16), is a great concern. Currently, the only major activity in this area seems to be
carried out by Taylor and Noceti (1988) using a CuCl/KCl/LaCl3 catalyst on Silica support. Low
temperatures «350' C) were essential in obtaining good CH 3 Cl selectivities. The best
selectivities were CH3Cl: CH 2CJ 2:CHCJ3 :HCOOH:C02= 74:21:2:2:1 at 28% conversion.
Similar bromination reactions are represented by
CH. + Br2 ~ CH3Br + HBr .6.H,(250' C)= -7 kcal .6.0,=-8 kcal (19)
CH3Br + Br2 ~ CH2 Br2 + HBr .6.H,(250' C)=-1 0 kcal .6.0,=-9 kcal (20)
CH2 Br2+ Br2 ~ CHBr3 + HBr .6.H,(250' C)= -8 kcal .6.0,=-6 kcal (21)
CHBr3 + Br2 ~ CBr. + HBr .6.H,(250' C)= -1 kcal .6.0,= 2 kcal. (22)
189
Note that the above reactions have small heats of reaction, in contrast to the chlorination reactions
(Reactions (12 to 15». To complete the Br2 cycle, we have
lili,(250· C)=-33 kcal aG,=-25 kcal. (23)
The heat of this reaction is substantially larger than that of Reaction (16).
Publications on bromination are very limited. Olah (1985) used antimony and tantalum
oxyfluorides on alumina as catalysts and reported a 77% conversion at 260· C. Although no
"oxybromination" was mentioned in the literature, its reactions can be defined, as similar to the
oxychlorination reactions, by combining Reactions (19) to (22) with Reaction (23).
Chemical equilibria of Reaction (12) were calculated using 250· C(200-1900· C) and 100/1 00
molar(lOO/1O-100/200 molar) CHJCl 2 feed. Major conclusions were:
No pressure effect
Essentially complete conversions of either CH4 or Cl 2 at low temperatures but conversions
declining to -98% at 1,700· C.
For making liquid fuels, over-halogenation is highly undesirable. Since CI in CH 3 CI, CH 2CI 2 ,
CHCI 3 , and CCl 4 must be removed as HCI in later processing, it is convenient to define the
following "Effective H/C Ratio" for them:
Effective H/C Ratio = 2, 0, -2, -4 for CH 3Cl, CH 2Cl 2 , CHCI3 , and CCI4 , (24)
respectively. It is very important to achieve high methyl halides selectivity resulting in an Eff.
H/C ratio of 2. In contrast, methylene halides give an Eff. H/C ratio of O. Since ole fins have an
H/C ratio of 2 and gasolines generally have H/C ratios of -l.9, over-halogenation of CH 4 must be
minimized. Small amounts of methylene halides or higher halides may be tolerable because the
desired liquid hydrocarbons may have an H/C ratio slightly <2. A low Eff. H/C ratio is also
undesirable in later catalytic conversions since carbon-rich feedstocks promote faster catalyst
aging. Unfortunately, no quantification of this aging effect is known. The only standard
available now is Mobil's MTG (Methanol-To-Gasoline) process which has an Eff. H/C ratio of 2.
Table 2 summarizes the results of chemical eqUilibrium calculations with CH 3Cl and CH2 Cl 2
as products. Major conclusions were:
No pressure effect
Essentially complete Cl 2 conversions
Substantial CH 2 Cl 2 formations resulting in incomplete CH4 conversions and low Eff. HlC
ratios
Slightly higher conversions, lower CH 2 CI 2 , and higher Eff. H/C ratios at higher
temperatures.
Note that inclusion of CH2 Cl 2 in equilibria reduced the Eff. H/C ratios from 2 to <1.2. Further
inclusion of CHCl 3 and CCl4 in equilibria made the Eff. H/C ratios slightly worse, as shown in
Table 3. Additional conclusions were:
Small CHCl 3 and CCl4 selectivities

Significantly higher Eff. H/C ratios but lower CH4 conversions at lower feed C1 2•
190
Table 2. Calculated Equilibrium Products of CH. + Cl 2 ~ HCI, CH 3 CI, CH 2Cl 2 (Feed

CHJC12=lOO/lOO)
Temp., ·C 200.00 250.00 300.00 400.00 500.00 700.00

Product in moles:
CH. 34.04 33.32 32.74 31.85 31.22 30.39
O2 0.00 0.00 0.00 0.00 0.00 0.00
HCI 100.0 100.0 100.0 100.0 100.0 100.0
CH 3CI 31.92 33.35 34.52 36.30 37.56 39.23
CH 20 2 34.04 33.32 32.74 31.85 31.22 30.39
Total 200.0 200.0 200.0 200.0 200.0 200.0
Eff. H/C 0.968 1.00 1.03 1.07 1.09 1.13
Temp., ·C 900.00 1100.0 1300.0 1500.0 1700.0 1900.0

Product in moles:
CH. 29.87 29.53 29.32 29.22 29.26 29.44
O2 0.00 0.00 0.02 0.04 0.07 0.13
HCI 100.0 100.0 99.98 99.96 99.93 99.87
CH 30 40.26 40.94 41.38 41.60 41.56 41.24
CH 20 2 29.87 29.53 29.30 29.18 29.18 29.32
Total 200.0 200.0 200.0 200.0 200.0 200.0
Eff. HlC 1.15 1.16 1.17 1.18 1.18 1.17
Chemical equilibria were calculated for the Benson process (Reaction (17)) using
700/1,200/1 ,700· C, 2/20/50 atm, and 100/50 molar CHJCl 2 feed. The results are tabulated in
Table 4 and major conclusions were:
Complete Cl2 conversion

Limited CH. conversions but becoming higher at higher temperatures and lower pressures
Small C2H6 formation at 700· C becoming negligible at 1,700· C
Higher C2H6 formations at higher pressures
Large H2 formation at higher temperatures and lower pressures.
Chemical eqUilibrium calculations were repeated with inclusion of C 2H2 formation in the
above process, and the results are tabulated in Table 5. Additional observations were:
Slightl y lower CH. conversions at 700 • C, becoming higher at 1,700· C

• Drastically higher C2H2 selectivities at higher temperatures and lower pressures, similar to
the conventional CH.-to-C2H2 processes.
It was clear from these calculations that C 2H2 was a major product of this process at high
temperatures and low pressures, similar to the commercial CH.-to-C2H2processes.
Chemical equilibria of Cl 2 regeneration from HCI (Reaction (16» were calculated using
250· C(1 00-400· C), 10 atm(1-50 atm), and 100/25 molar(1 00/20-1 00/50 molar) HClI0 2 feed.
Figure 1 shows results of temperature and pressure variations and Table 6 shows the results of
feed O 2variation. Major conclusions were:
191
Table 3. Calculated Equilibrium Products of CH. + O 2 ~ HCI, CH30, CH2CI2, CH03, ca. (10 atm)
Temperature Variation (feed CH.,ICI:z=I00/100 mol):
Temp., ·C 100.00 150.00 200.00 250.00 300.00 350.00 400.00 450.00 500.00
Product in moles:
CH. 37.13 36.14 35.36 34.74 34.25 33.86 33.53 33.27 33.05
O2 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
HCI 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0
CH 3CI 27.42 29.56 31.25 32.61 33.71 34.61 35.35 35.98 36.51
CH 2Cl2 33.77 32.47 31.42 30.55 29.83 29.22 28.70 28.25 27.86
CH0 3 1.68 1.83 1.97 2.09 2.21 2.31 2.41 2.50 2.58
CCI. 0.00 0.00 0.00 0.00 0.00 0.00 0.00 -.Jill -.Jill
Total 200.0 200.0 200.0 200.0 200.0 200.0 200.0 200.0 200.0
Eff. HlC 0.819 0.868 0.906 0.935 0.958 0.976 0.991 1.00 1.01
Feed Cl2 Variation (250'C):

Feed Cl2 10.00 20.00 30.00 40.00 50.00 60.00 80.00 100.0 120.0
Product in moles:
CH. 90.79 82.67 75.27 68.40 61.96 55.89 44.73 34.74 25.87
O2 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
HCI 10.00 20.00 30.00 40.00 50.00 60.00 80.00 100.0 120.0
CH 3CI 8.42 14.69 19.56 23.41 26.43 28.77 31.69 32.61 31.75
CH 2Cl2 0.78 2.61 5.08 8.00 11.26 14.78 22.41 30.55 38.90
CH03 0.01 0.03 0.10 0.20 0.35 0.56 1.16 2.09 3.48
ca. 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Total 110.0 120.0 130.0 140.0 150.0 160.0 180.0 200.0 220.0
Eff. H/C 1.83 1.69 1.57 1.47 1.37 1.28 1.10 0.935 0.762
Feed Cl2 140.0 160.0 180.0 200.0

Product in moles:
CH. 18.15 11.68 6.64 3.16
O2 0.00 0.00 0.00 0.00
HCI 140.0 160.0 180.0 200.0
CH 3CI 29.25 25.25 19.99 14.07
CH 2Cl2 47.06 54.47 60.13 62.45
CH0 3 5.53 8.59 13.21 20.26
ca. -.Jill -.Jill 0.03 0.07
Total 240.0 260.0 280.0 300.0
Eff.H/C 0.579 0.377 0.144 -0.131
High HCI conversions but far from completion, improved slightly by higher pressures but
moderately by lower temperatures
Impossible to have complete HO conversions even using a large excess of 02.
Separation and recycle of unconverted Hel could be an expensive processing step.

192
Table 4. Calculated Equilibrium Products of Benson Process: CH4 + 1/2 Cl z ~ HCI, Hz, CZH6 ,
CZH4 (Feed CHJClz=lOO/SO mol)
Temp., ·C 700 700 700 1200 1200 1200 1700 1700 1700
Pres., atm 2 20 50 2 20 50 2 20 50
Product in moles:
CH 4 48.81 47.82 46.81 26.54 38.14 41.27 5.89 14.44 19.23
Clz 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
HCI 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0
Hz 0.53 0.17 0.10 23.36 11.44 8.03 44.09 35.47 30.58
CZH6 0.66 2.01 3.09 0.10 0.42 0.70 0.01 0.09 0.19
CZH4 24.93 24.08 23.51 36.63 30.51 28.67 47.04 42.69 40.20
Total 174.9 174.1 173.5 186.6 180.5 178.7 197.0 192.7 190.2
CzHJCzl4 0.026 0.084 0.131 0.003 0.014 0.024 0.000 0.002 0.005
Table 5. Calculated Equilibrium Products of Benson Process: CH 4 + 1/2 Clz ~ HCl, Hz, C ZH 6 ,
CZH4, CzH z (Feed CHJClz=lOO/SO mol)
Temp., ·C 700 700 700 1200 1200 1200 1700 1700 1700
Pres., atm 2 20 50 2 20 50 2 20 50
Product in moles:
CH 4 51.74 48.97 47.57 24.58 43.78 47.32 0.95 7.63 14.53
Cl z 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
HCI 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0
Hz 0.62 0.18 0.11 56.83 21.08 13.12 98.26 86.01 73.27
CZH6 0.63 1.99 3.06 0.04 0.30 0.56 0.00 0.01 0.04
CZH4 20.51 22.40 22.42 6.23 12.65 14.77 0.31 2.52 4.85
C2H2 2.99 -1.n 0.74 31.44 15.16 11.01 49.21 43.65 37.85
Total 176.5 174.7 173.9 219.1 193.0 186.8 248.7 239.8 230.5
C2HJC2H4 0.031 0.089 0.136 0.006 0.024 0.038 0.000 0.004 0.009
CzHjC2H4 0.146 0.051 0.033 5.05 1.20 0.745 157 17.3 7.81
Chemical equilibria of the oxychlorination reaction were calculated using 250· C(150-400· C),
10 atm(2-50 atm), and 100/100/50 molar CHjHCl/O z feed. Essentially complete conversions of
both HCI and O2 were found and the CH4 conversions and the distributions of various chlorides
were the same as those of the chlorination cases (Tables 2 and 3).
Chlorination processes have the potential of achieving high conversion and selectivity.
Among them, the "Oxychlorination" process seems to be the best because of its simplicity and its
moderate conditions. A major deficiency in this process is that special materials are required to
handle the highly corrosive compounds (i.e., HCI and Cl 2 with or without HP, and others). It is
recommended that the additional cost of using these exotic materials must be estimated before
other process evaluations. Furthermore, performance of the second-stage reactor in converting
CH3 CI and higher chlorides to liquid hydrocarbons needs to be better defined. Other major
disadvantages are:
193
t
Temperature, °C
100 150 200 250 300 350 400
~
E 16
14
12
(,)
J: 10 ..
"C 8
(1)
1:: 6
(1)
>
s:::: 4
oo
s::::
::J
Pressure, atm
Figure 1. Calculated equilibrium unconverted HCl of 2 HCI + 1/2 O2 ~ H 20 + Cl2 (Feed HCI/02 =
lOO/2S molar, 2S0·C, 10 attn)
Table 6. Calculated Equilibrium Products of 2 HCl + 1/2 O2 ~ H 20 +C12 (Feed O2 variation, 100
mol HCI feed, 250· C, 10 attn)
Feed O2 20.00 22.50 25.00 30.00 35.00 40.00 45.00 50.00

Product in moles:
HCI 20.01 10.31 5.37 3.81 3.33 3.07 2.90 2.78
O2 0.00 0.08 1.34 5.95 10.83 15.77 20.73 25.70
HP 39.99 44.84 47.31 48.10 48.34 48.46 48.55 48.61
Cl2 39.99 44.84 47.31 48.10 48.34 48.46 48.55 48.61
Total 100.0 100.1 101.3 106.0 110.8 115.8 120.7 125.7
HClConv. 80.0 89.7 94.6 96.2 96.7 96.9 97.1 97.2
O2 Conv. 100 99.7 94.6 80.2 69.1 60.6 53.9 48.6
Regeneration of Cl2 from HCI could be expensive and an O2 plant may be needed
Chlorinated compounds in gasoline are undesirable.
It is interesting to compare bromination against chlorination. Identical base case conditions as

those of chlorination (except that temperature variations are limited to 500· C) were used for the
chemical equilibrium calculations of Reaction (19). Major conclusions were:
• No pressure effect
194
Better than 99.8% conversion and becoming higher at higher temperatures.
Results of the chemical equilibrium calculations including over-bromination reactions (Reactions

(20 to 22» are summarized in Table 7. Major conclusions were:
Table 7. Calculated Equilibrium Products of CH4 + Br2 ~ HBr, CH3Br, CH2Br2, CHBr3,
CBr4 (10 atm)
Temperature Variation (feed CH,JBr:F 100/1 (0):

Temp., 'C 100.00 150.00 200.00 250.00 300.00 350.00 400.00 450.00 500.00
Product in moles:
CH4 68.20 45.66 44.58 43.60 42.73 41.95 41.27 40.68 40.16
Br2 0.00 0.00 0.01 0.03 0.05 0.10 0.16 0.25 0.36
HBr 100.0 100.0 99.99 99.97 99.95 99.90 99.84 99.75 99.64
CH3Br 9.57 12.03 14.30 16.36 18.21 19.86 21.34 22.66 23.84
CH 2Br2 40.39 38.96 37.66 36.49 35.45 34.51 33.67 32.91 32.21
CHBr3 3.22 3.35 3.45 3.54 3.61 3.67 3.72 3.76 3.79
CBr4 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Total 200.0 200.0 200.0 200.0 200.0 200.0 200.0 200.0 200.0
Eff. HlC 0.239 0.319 0.391 0.455 0.510 0.558 0.600 0.637 0.670
Feed Br2 Variation (2S0'C):

Feed Br2 5.00 10.00 20.00 30.00 40.00 50.00 60.00 80.00 100.0
Product in moles:
CH 4 95.76 92.17 85.67 79.67 73.97 68.50 63.22 53.13 43.60
Br2 0.00 0.00 0.00 0.00 0.00 0.01 0.01 0.02 0.03
HBr 5.00 10.00 20.00 30.00 40.00 49.99 59.99 79.98 99.97
CH3Br 3.48 5.70 8.81 10.99 12.63 13.89 14.83 16.00 16.36
CH 2Br2 0.75 2.10 5.38 9.02 12.83 16.74 20.69 28.65 36.49
CHBr3 0.01 0.03 0.14 0.32 0.57 0.88 1.26 2.23 3.54
CBr4 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Total 105.0 110.0 120.0 130.0 140.0 150.0 160.0 180.0 200.0
Eff. HlC 1.64 1.45 1.21 1.05 0.927 0.826 0.738 0.587 0.455
Feed Br2 120.0 140.0 160.0

Product in moles:
CH4 34.64 26.29 18.66
Br2 0.04 0.05 0.08
HBr 120.0 139.9 159.9
CH3Br 16.02 15.03 13.41
CH2Br2 44.06 51.11 57.28
CHBr3 5.27 7.56 10.65
CBr4 0.00 0.00 0.00
Total 220.0 240.0 260.0
Eff. HlC 0.329 0.203 0.068
195
No pressure effect
Essentially complete Brz conversion
Very large CHzBrz, moderate CHBr3 , and negligible CBr4 formation resulting in very low
Eff. H/C ratios
Higher conversions and Eff. HlC ratios at higher temperatures
Significantly higher Eff. HlC ratios at lower feed Brz•
Chemical eqUilibrium calculations of Brz regeneration (Reaction (23» at the conditions of Cl z

regeneration showed that that reaction could achieve higher conversions than those of the
equivalent Oz reaction:
Better than 99.8% conversions up to 500' C, improved slightly by higher pressures but
moderately by lower temperatures
Essentially complete conversion of either HBr or Oz.
Bromination is similar but probably worse than chlorination because it gives much lower Eff. H/C
ratio products, and HBr is more acidic than HO.
Equilibrium calculations were also repeated for the oxybromination reactions using the same
conditions as those for the bromination reactions. As similar to the oxychlorination reactions,
essentially complete conversions of either HBr or 0z were found and CH4 conversions and
bromides distributions were the same as those of the bromination cases (Table 7).
2.1.4. Using Super-Acids as Catalysts. Super-acid catalysts can directly condcnse CH4 into C;
hydrocarbons at relatively mild temperatures. The work in this area were mainly carried out by
Olah and his co-workers (see review by Kuo (1987». The super-acids are generally higher
valency Lewis acid fluorides of metals of Groups IV, V and VI of the periodic table which were
used at 50-200' C and 1 to > 150 atm. Research in this area is exploratory. Also, handling of
strong acids can be quite expensive. No thermochemical calculations were carried out because its
reaction products were not sufficiently defined.
2.2. OXIDATIVE COUPLING (to Czl{.)
The reactions of this class take place using various reducible metal oxides as both O2 carriers and
catalysts at 500-900' C and 1-30 atm. The metal oxides include most of the metal elements in the
periodic table. A typical reaction can be represented by
(25)
Substantial amounts of CzH 6 are usually formed simultaneously, represented by the following
reaction:
(26)
as well as CO. and Hp. The reducible oxides are re-oxidized with 02:
(27)
196
Combination of Reactions (25) and (26) with Reaction (27) gives the following:
CH4 + 1/2 O2 ... 1(2 C2H4 + H20 lili,(800·C)=-33 kcal b.G,=-37 kcal (28)
CH4+1/402 ... l(2C2H6+ l(2HP lili,(800·C)=-21 kcal b.G,=-14 kcal (29)
which also represent the performance of a reactor into which O 2 is co-fed with CH4 • Both
reactions are moderately exothermic.
Among the abundant publications on this topic, the more than forty patents and publications
from the Atlantic Richfield Co. (ARCO Chemical) constitute the major and most important
contributions. Altogether more than ten metal oxides (those of Bi, Ce, Ge, In, Mn, Pb, Pr, Ru, Sb,
and Sn) were used. Among these, the most effective ones were Mn and Pro The promoting
components used included Ba, Ca, CI, K, Li, Mg, Na, P, S, and Te. Among these, the most
important ones were Na, P, and Cl. Six catalyst supports were used, i.e., Si02, a-Al 20 3, 'Y-AI203'
MgO, zr0 2, and Y203' The related references are too numerous to be mentioned here except for
recent references including Gaffney et al. (1988), Leyshon and Bader (1989), Sofranko and Jubin
(1989), and Sofranko et al. (1988a,b).
The best performance data were reported by Sofranko and Jones (1985) using a catalyst of 15
wt% Mn promoted with 5 wt% Na4P20 7 on Si02. 93% Ci selectivity at 26% conversion was
obtained after co-feeding of 5 mol% CH 3CI over two to three cycles. The reaction conditions
were 750· C, 1 atm, and 900 1/h GHSV. A total of 53 cycles was accumulated. All experiments
were carried out using micro-reactors and majority of the experiments were run with cyclic
(reduction-oxidation) fixed-bed operation and at 1 atm. Limited amounts of aging data were also
collected.
As to the pressure effect, Jones et al. (1985a) reported that operation at 7.8 atm resulting in
substantial increases in both conversion and C; selectivity. According to a mechanistic study of a
mixed Mn-Mg oxide at 750-850·C reported by Labinger and Ott (1987), C 2H6 selectivity
increased with increasing pressure. The Ci selectivities increased with higher pressure at about
<8% conversion, whereas the trend reversed at higher conversions.
Jones et al. (1984) also reported co-feeding of C2 H6 with CH 4 over a Mn 30JSi0 2 catalyst.
C2H6 conversion was 12% comparing with 0.7% for CH4 •
Many reactor designs and operations other than the cyclic mode were mentioned:
Fluidized-bed operation using two beds; one for OCE and the other for re-oxidation using
air (Jones et al. (1985b»
• Air co-feeding to fixed-beds (Jones et al. (l985c»
• Moving-bed operation using two beds (Jones et al' (1987c»
• Molten-salt reactor operation (Mazurek (1987» using 50%NaMnOJ16%Li2COJ
l7%N a2COJ17%K2C0 3•
• C2H4 oligomerization after the OCE unit (Jones et al. (l986a».
However, little process data were given which greatly hindered process evaluation.
Jones et al. (1986b and 1987a) summarized ARCO's work up to that time, including both the
catalysts and process options. Among many metal oxides investigated, only manganese and tin
were nonvolatile at reaction conditions; and the manganese also had the highest activity. Further
optimization of this catalyst resulted in large improvement on Ci selectivity by supporting it on
silica and by doping it with sodium pyro-phosphate. About 80% selectivity at 20% conversion
197
was reported. They also reported that co-feeding air with CH. resulted in a small penalty (-5%)
on the selectivity.
Publications other than ARCO's were numerous. The major researchers in this topic include
Baems and his colleagues, and Wohlfahrt and his colleagues in Europe
Otsuka, Morikawa, and their colleagues in Japan
• Ito and Lunsford, and Kimble and Kolts in USA
Edward and Tyler in Australia.
Recently, fluid-bed OCE data began to appear (Edward and Tyler (1989), Edward et al. (1990),
and Andorf and Baems (1990». They were obtained in small. single fluid-bed reactors using 02
co-feeding. None of them reported selectivity-conversion combinations better than the best
ARCO data from cyclic fixed-bed runs. Other data showed very good selectivities including
Bartek et al. (1988). Bi et al. (1988). and Pereira et al. (1990),
Chemical equilibria of C 2H. formation were calculated using 800· C(600-1 ,000· C), 10 atm(l-
50 atm). and 100/7.5 molar(l00/1-100/50 molar) CHJ02 feed. Major conclusions were:
• No pressure effect
Complete conversion of either CH. or 02.
Calculations were repeated including C2H 6 formation, and results are summarized in Table 8.
• Some C2H6 formation

Lower C2H6 selectivities at lower pressures and feed 02' and higher temperatures.
Equilibrium C2 H 6 sclectivities were generally less than those reported in the literature. This
indicates that C 2 H 6 was an intermediate which was later converted to C 2 H. via an oxy-
dehydrogenation reaction. This description was consistent with mechanisms proposed by Kimble
and Kolts (1986) and by Sofranko et al. (1987). Theoretically. high C2H. selectivities could be
obtained by increasing reaction severity. In reality. however, increasing severity almost always
resulted in increasing deep oxidation. Table 8 also includes the temperature and pressure effects
which were calculated using a more realistic CHJ02 feed molar ratio of 100/7.5. Inclusion of
CO. in the chemical eqUilibrium calculations again resulted in the complete formation of CO•.
Lower CO. selectivities could be expected with higher temperatures and pressures, and lower feed
02·
Thermochemical calculations of reactions involving metal oxides (Reactions (25) to (27»
were not carried out because of unknown oxidation states and thermodynamic properties of many
metal oxides. However, according to Jones (1987), the heats of reaction of Reactions (25) and
(26) are small.
This process has favorable chemical eqUilibrium but the following potential disadvantages:
Low single-pass conversion

Large reaction heat removal
Majority of data were obtained at 1 atm under cyclic operation in micro-reactors
Significant light paraffins formation
Further conversion of low olefin concentration product streams
198
Table 8. Calculated Equilibrium Products of C~ + O2= H20, C2H., C2H,; (Feed: 100 mol CH.,)
Feed O2 Variation (SOO'C, 10 aim):

O2, mol 1.00 2.00 3.00 5.00 7.50 10.00 15.00 20.00 25.00 30.00
Product in moles:
C~ 97.54 95.34 93.20 89.01 83.86 78.76 68.70 58.73 48.84 39.00
O2 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
H2O 2.00 4.00 6.00 10.00 15.00 20.00 30.00 40.00 50.00 60.00
C2H. 0.77 1.67 2.60 4.50 6.93 9.38 14.35 19.37 24.42 29.50
C2H,; 0.46 0.66 0.80 0.99 1.14 1.24 1.30 1.27 1.16 1.00
Total 100.8 101.7 102.6 104.5 106.9 109.4 114.3 119.4 124.4 129.5
C2HJC2~ 0.597 0.395 0.307 0.220 0.165 0.132 0.091 0.066 0.048 0.034
O2, mol 35.00 40.00 45.00 50.00

Product in moles:
C~ 29.21 19.44 9.71 0.00
O2 0.00 0.00 0.00 0.00
H2O 70.00 80.00 90.00 100.0
C2~ 34.60 39.72 44.86 50.00
C2H6 0.79 0.56 0.29 0.00
Total 134.6 139.7 144.9 150.0
C2HJC2H. 0.023 0.014 0.006 0.000
Temperature Variation (feed CHJ02=100(7.5 molar, 10 aim):

Temp., 'C 600 700 800 900 1000
Product in moles:
CH. 82.38 83.33 83.86 84.17 84.36
O2 0.00 0.00 0.00 0.00 0.00
H2O 15.00 15.00 15.00 15.00 15.00
C2~ 6.19 6.67 6.93 7.08 7.18
C2H,; 2.62 1.67 1.14 0.83 0.64
Total 106.2 106.7 106.9 107.1 107.2
C2HJC2~ 0.423 0.250 0.165 0.118 0.089
Pressure Variation (feed CHJ02=lOO(7.5 molar, SOO'C):

Pres.,atm 1.00 2.00 3.00 5.00 10.00 15.00 20.00 30.00 40.00 50.00
Product in moles:
C~ 84.63 84.47 84.36 84.18 83.86 83.61 83.41 83.09 82.82 82.59
O2 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
HP 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00
C2H. 7.31 7.24 7.18 7.09 6.93 6.81 6.71 6.54 6.41 6.30
C2H,; 0.37 0.53 0.64 0.82 1.14 1.39 1.59 1.91 2.18 2.41
Total 107.3 107.2 107.2 107.1 106.9 106.8 106.7 106.5 106.4 106.3
C2HJC2~ 0.051 0.073 0.089 0.116 0.165 0.204 0.236 0.292 0.340 0.383
Difficult separation of useful products.
It appears that among all CH. direct conversion processes this process attracts the most
researchers and generated the most publications. This author feels that after the significant
199
exploratory work developed it is time for chemical engineers to give more definite consideration
to this process.
2.3. DIRECT CONVERSION TO C2H2 AND OTHER HIGHER HYDROCARBONS
Direct conversion to C 2H 2 is a commercial process. CH 4 is dehydrogenated and coupled to

become C2H2 at 1,500-2,000· C and near 1 atm according to
lili,(1,700· C)=48 kcal ~G,=-16 kcal. (30)
This reaction is highly endothermic. To supply the large amounts of heat of reaction at very high
temperatures was the major challenge encountered during commercial developments. Pyrolysis
uses the high temperature sensible heat storaged in a fixed bed as the heat source for this reaction.
The bed is re-heated by burning a fuel after each cycle. Electricity, as electric arc or plasma, is
another high potential energy that is used (for example, the Huels Arc Process (Duncan (1978».
Another way of supplying this heat of reaction is by "partial oxidation" using O2, Ideally only the
surplus H2 is oxidized resulting in thc following reaction:
~H,(1,700·C)=-42 kcal ~G,=-65 kcal. (31)
This reaction is highly exothermic. In reality, however, part of the carbon in the feed is also
burned resulting in lower selectivity.
The major penalty of making C2H2is the need of very large amounts of high potential energy.
To pay this penalty may be alright for making high valued chemicals but probably not for making
liquid fuels. Another penalty is the low operating pressure which demands substantial
compression work for further processing of C2H2. Furthermore, additional processing steps are
needed to convert C2H 2 into liquid fuels. A logical step of improving the economics of this type
of process is to lower the reaction temperature to 900-1,200· C resulting in making C2H. and
aromatics which can be an interesting route for making chemicals. The reactions will shift to the
Oxidative Coupling class if the temperature is reduced further to <900· C.
There is little difference between electric arcs and plasmas, which exist only at >2,000· C,
since in practice, the latters are usually generated using the formers. However, local temperature
of electric arcs can also be very high. In both cases, electric energy is used to supply the heat for
Reaction (30). Low cost electricity is essential for the economic success of these processes.
The partial oxidation of CH. was first developed by BASF before the 60's (Friz (1968». It
involved the reaction of pre-mixed and pre-heated (600· C) gases in a stable flame.
Unfortunately, performance information of this process is scarce.
2.3.1. To CZH2 • The main reaction is represented by Reaction (30). Some C 2H. is also co-
produced as given by the following reaction:
~H,(1,700·C)=26 kcal ~G,=-6 kcal. (32)
This reaction is also highly endothermic. A substantial amount of carbon and some heavy
hydrocarbon oil are also produced. When partial oxidation is used to supply the heat of reaction,
oxidation of excess H2 results in Reaction (31) and the following C2H4 formation:
200
bH,(l,700·C)=-34 kcal bG,=-39 kcal. (33)
Both reactions are highly exothennic.

Chemical equilibria of Reactions (30) and (32) have been calculated using 1.700· C(1 0400-
2,000·C) and 1 atm(0.5-20 atm). Results of the calculations are summarized in Table 9 and
major conclusions were:
Limited conversions but becoming higher at higher temperatures and lower pressures
Small CzH. selectivities but becoming higher at lower temperatures and higher pressures
Possible carbon fonnation
• Negligible CZH 6 fonnation.
Table 9. Calculated Equilibrium Products of CH. ~ Hz. CzH., CzH z (Feed: 100 mol CH4)
Temperature Variation (I atm):

Temp., ·C 1400 1500 1600 1700 1800 1900 2000
Product in moles:
CH. 8.56 4.14 2.08 1.10 0.62 0.37 0.23
Hz 135.2 142.8 146.4 148.0 148.9 149.3 149.6
CzH. 1.92 1.00 0.53 0.30 0.17 0.11 0.07
CzH z 43.79 46.94 48.43 49.15 49.51 49.71 49.82
Total 189.5 194.9 197.4 198.6 199.2 199.5 199.7
CzHjCzH z 0.044 0.021 0.011 0.006 0.003 0.002 0.001
100PCHJPH2z 887 395 192 100 55.7 32.7 20.2
100~,l/atm 65.7 51.1 41.2 34.3 29.4 25.7 22.9
Pressure Variation (1700' C):

Pres., atm 0.50 1.00 2.00 5.00 10.00 15.00 20.00
Product in moles:
CH. 0.56 1.10 2.16 5.10 9.32 12.90 15.99
H2 149.0 148.0 146.2 141.0 133.6 127.3 121.9
C2H. 0.15 0.30 0.58 1.35 2.45 3.36 4.13
C2H2 49.57 49.15 48.34 46.10 42.89 40.18 37.87
Total 199.3 198.6 197.3 193.5 188.2 183.7 179.9
C2HjC 2H2 0.003 0.006 0.012 0.029 0.057 0.084 0.109
IO'PCHJPH22 50.1 100 200 496 984 1460 1940
100~.l/atm 34.3 34.3 34.3 34.3 34.3 34.3 34.3
The carbon fonnation reaction can be represented by
CH. ~2H2 + C bH,(1,700" C)=21 kcal bG,=-30 kcal (34)
which becomes thennodynamically possible when
P CHJPH22> Kp of Reaction (34) at 1700" C (= 34). (35)

201
As shown in Table 9, this inequality held at all conditions except the one at 2,000 C. An obvious
0
but important aspect of optimization of these processes was to minimize carbon formation. This
could be achieved by controlling the temperature, the pressure, and the residence time and by
diluting CH4 with H2. Table 10 summarizes the results of the chemical eqUilibrium calculations
with H2 in the feed. The feed CHJH2 varied from 100/0 to 100/500 molar. Major conclusions
were:
Carbon formation was still possible but became less favorable

Small increase in C,H4 selectivities
Slight decrease in conversions.
Table 10. Calculated Equilibrium Products of CH4, H2 ~ H2, C2H4, C2H 2 (Feed H2 variation, feed
CH4 100 mol, 1700·C, 1 atm)
Feed H2 0 50 100 150 200 250 300 400 500

Product in moles:
CH 4 1.10 1.36 1.58 1.78 1.97 2.l3 2.29 2.58 2.84
H2 148.0 197.6 247.3 297.0 346.7 396.4 446.2 545.8 645.4
C2H4 0.30 0.31 0.33 0.34 0.34 0.35 0.35 0.36 0.36
C2H2 49.15 49.01 48.88 48.77 48.67 48.59 48.50 48.35 48.22
Total 198.6 248.3 298.1 347.9 397.7 447.5 497.4 597.1 696.8
C2HJC2H2 0.006 0.006 0.007 0.007 0.007 0.007 0.007 0.007 0.007
1Q4PCHJP~ 100 86.5 77.2 70.4 65.1 60.8 57.2 57.7 47.5
lQ4~,l/atm 34.3 34.3 34.3 34.3 34.3 34.3 34.3 34.3 34.3
Chemical equilibrium calculations were repeated for the partial oxidation process (Reactions
(31) and (33)) using 100/75 molar(1 00/10-1 00/75 molar) CHJ02 feed. Major conclusions were:
Essentially complete O2 conversion, preferably at low temperatures and pressures

Very small C2H4 selectivities, preferably at higher temperatures and pressures
Drastically higher C 2HiC 2H 2 ratios at lower O 2 feed (from 0 to .26 when feed CHi02
varied from 100/75 to 100/10 molar)
Possible carbon formation.
The carbon formation is represented by the following reaction:
lili,(1 ,700 C)=-99 kcal

0 aa,=-95 kcal. (36)
In the following, the thermal and C-efficiencies of CH4 conversion via two commercial C2H 2
processes, i.e., the Huels Arc Process and the BASF Process, are examined. Material and energy
requirements and product selectivities for the Huels Arc Process were given by Duncan (1978).
In this analysis, all major energies were accounted for except those required for C2H 2 separation.
In the present analysis, it was assumed that the C2H2 was selectively hydrogenated to C2H4 as a
final product without any loss of efficiencies -- an optimistic assumption. Various forms of
energy were converted to feed LHV equivalence according to guidelines based on thermal
202
efficiencies of conventional knowledge. The estimated thermal and C-efficiencies are

summarized in Table 11. The actual efficiencies were expected to be somewhat lower than those
values because the following efficiency losses were not taken into account:
Compression of CzH z for later selective hydrogenation

Conversion of CzHz to CZH4•
Table 11. Thermal and Carbon Efficiencies of Natural Gas to C ZH4 and/or CH30H via CzH z by
Huels Arc and BASF Partial Oxidation Process
Via C,H, by Huels Arc Process:

Bases:
-- Material and Energy Requirements and Selectivities were from Duncan (1978).
-- Not Account for Efficiency Losses due to Product Separation.
-- Assumed 100% Efficiency of Converting CzHz to CZH4•
Scoping Thermal and C-Efficiencies: LHV C-Atom
Feeds: CH4 (process) 48 48
CH4 (Energy) ..2l. ..2l.
Total 100 100
Products: CZH4 35 43
Carbon Black 5 9
Resid. Oil 3 4
Hz ~ ~
Total <53 <56
Via C,H, by BASF Partial Oxidation Process:

• Bases:
-- Material and Energy Requirements and Selectivities were from Friz (1968).
-- Not Account for Efficiency Losses due to Product Separation.
-- Assumed 100% Efficiency of Converting CzHz to C ZH4 •
-- Assumed 90% Hz+CO Conversion to CHpH.
Scoping Thermal and C-Efficiencies: LHV C-Atom
Feeds: CH4 100 100
Products: CZH4 25 31
C3H 6 2 2
CH30H 28 35
Carbon 1 -1
Total <56 <70
lliOH via Steam Reforming:

Thermal and C-Efficiencies 65-68 81-85
Both the thermal and the C-efficiencies were lower than those of conversion of natural gas to
CH30H via steam reforming given later. Note that the material balance data were imperfect since
203
the C-efficiency was larger than the C-atoms in the process feed which is impossible. This
imbalance was partially due to the fact that the process feed used had a H/C ratio lower than that
ofCH4 •
Material and energy requirements and product selectivities for the BASF's Partial Oxidation
Process were given by Friz (1968). Again, all energies were accounted for in this efficiency
calculation except for those required for C2H2 separation. It was again assumed that C2H2 was
selectively hydrogenated to C2H4 without any loss of efficiencies. The large amounts of H2+CO
produced by the partial oxidation process were converted to CH30H assuming a 90% conversion.
The estimated thermal and C-efficiencies are also summarized in Table 11. Again, the actual
efficiencies were expected to be somewhat lower because of the same reasons mentioned earlier
for the Huels Arc Process. Both the thermal and the C-efficiencies were also less than those
estimated for the CH 30H synthesis from natural gas via steam reforming.
In conclusion, these two commercial natural gas to C2H2processes are economically valid for
making high valued C2H2 but not for making liquid fuels.
2.3.2. To Other Higher Hydrocarbons. While making C2H 2 from CH 4 requires very high
temperature, making C2H4 and aromatics, such as benzene, may require substantially lower
temperature according to thermodynamics. In 1928, Fischer et al. first reported thermal pyrolysis
ofCH4 at 900-1,IIO°C. At 1,110 C, 9.4 wt% light oil, 1.8% tar, and 6.2% higher ole fins were
0
obtained from 1 m 3 of gas containing 83 mol% of CH4 • Since then, scattered studies were
reported using various catalysts (see review by Kuo (1987)). Substantial tar/coke formation is the
major obstacle to the development of these processes.
Reactions for making C2H4 together with C2H2 and C2H6 are
CH4 *> 1!2 C2H4 + H2 lili,(1, 100 0 C)=26 kcal ~G,=3 kcal (37)
CH4 *> 1!2 C2H 2+ 3/2 H2 ~H,(1,I00°C)=48 kcal ~G,=4 kcal (38)
CH4 *> 1!2 C2H6 + 1/2 H2 ~H/ 1,100 C)=9 kcal
0 ~G,=8 kcal. (39)
Chemical equilibrium calculations were carried out at 1,100 C(700-1 ,400 C) and 2 atm(0.5-15
0
0
atm) and results are summarized in Table 12. Major conclusions were:
Limited conversions but becoming higher at higher temperatures and lower pressures
Higher C2H4 selectivities at lower temperatures and higher pressures
Higher C2H2 selectivities at higher temperatures and lower pressures.
Direct conversion of CH4 to liquid hydrocarbons is an interesting concept. All publications in

this area included the formation of aromatics which are thermodynamically stable. These
reactions can be illustrated with a benzene formation in addition to Reactions (37) to (39):
lili,(1,IOO° C)=24 kcal ~G,=-1 kcal. (40)
Chemical eqUilibrium calculations have been repeated and the results are tabulated in Table 13.
Significant increase in conversions

• High C6H6 selectivities but becoming lower at higher temperatures
• Higher C2H 2selectivities at higher temperatures.
204
Table 12. Calculated Equilibrium Products of CH. ~ H2, C2H., C2H 2, C2H 6 (Feed: 100 mol Cf4)
Temperature Variation (2 attn):

Temp., ·C 700 800 900 1000 1100 1200 1300 1400
Product in moles:
CH. 96.30 92.38 85.78 75.77 61.76 44.41 27.38 14.90
H2 3.31 7.43 14.96 27.88 48.22 75.43 103.4 124.3
C2H2 0.02 0.20 1.08 3.91 10.29 19.93 30.77 39.23
C2H. 1.42 3.22 5.69 7.94 8.81 7.78 5.51 3.31
C2H 6 0.41 0.39 0.34 0.26 0.17 0.09 0.04 0.01
Total 101.5 103.6 107.8 115.8 129.1 147.6 167.0 181.8
Selectivities, C-Atom%:
C2H2 1.20 5.18 15.14 32.28 53.05 71.70 84.72 92.19
C2H. 76.75 84.57 80.08 65.57 46.08 27.99 15.18 7.78
C2H6 22.05 10.25 4.78 2.14 0.87 0.31 0.10 0.03
Pressure Variation (1,100·C):

Pres., atm 0.50 1.00 2.00 3.00 5.00 7.50 10.00 15.00
Product in moles:
CH. 41.86 52.60 61.76 66.27 71.15 74.45 76.52 79.09
H2 80.27 62.79 48.22 41.22 33.86 29.05 26.09 22.51
C2H2 22.18 15.48 10.14 7.71 5.33 3.89 3.08 2.19
C2H. 6.84 8.13 8.81 8.92 8.78 8.48 8.18 7.68
C2H6 0.05 0.09 0.17 0.23 0.32 0.40 0.47 0.59
Total 151.2 139.1 129.1 124.4 119.4 116.3 114.4 112.1
C2H 2 76.29 65.32 53.05 45.76 36.94 30.47 26.27 20.96
C2H. 23.55 34.29 46.08 52.90 60.87 66.37 69.69 73.42
C2H 6 0.16 0.39 0.87 1.34 2.19 3.16 4.04 5.62
Although we have not found any publications that suggested the use of O 2 to remove the
excess H2 when aromatics were formed, the following reaction is interesting from the
thermodynamic point of view:
CH. + 3/4 O2 ~ HP,C2H2,C2H"C3H6,C6H6,C6HsCH3 (41)
which is highly exothermic. Chemical equilibrium calculations were carried out at 500· C(5OO-
1,600· C), 10 atm, 100n5 molar(100/1O-100/80 molar) CHJ02 feed and results are tabulated in
Table 14. Major conclusions were:
Complete conversion of either CH. or O2

Dominant products being C6H6 and C2H2 with the latter at high temperatures
Feed O2variation at 500· C also showing aromatics as dominant products.
205
Table 13. Calculated Equilibrium Products of CH4 ~ Hz, CZH4 , CzH z, C ZH6, C6H6 (Feed: 100 mol
C~)
TemQerature Variation (2 aun):

Temp., 'C 700 800 900 1000 1100 1200 1300 1400
Product in moles:
CH 4 90.77 82.34 70.55 56.58 42.50 30.20 20.40 12.90
Hz 13.58 26.09 43.51 64.08 84.71 102.7 117.1 128.4
CzH z 0.00 0.00 0.04 0.22 1.02 3.68 10.70 24.35
CZH4 0.08 0.22 0.50 0.93 1.45 1.95 2.28 2.22
CZH6 0.09 0.09 0.08 0.06 0.05 0.03 0.02 0.01
C6H6 1.48 2.84 4.70 6.83 8.74 9.75 8.94 5.65
Total 106.0 111.6 119.4 128.7 138.5 148.3 159.4 173.5
CzH z 0.01 0.05 0.25 1.02 3.55 10.56 26.88 55.92
CZH4 1.70 2.53 3.42 4.29 5.05 5.59 5.72 5.10
CZH6 1.92 1.00 0.54 0.29 0.16 0.08 0.04 0.02
C6H 6 96.38 96.42 95.79 94.40 91.25 83.77 67.36 38.95
Pressure Variation (l,lOO'C):

Pres., atm 0.50 1.00 2.00 3.00 5.00 7.50 10.00 15.00
Product in moles:
CH 4 24.91 33.34 42.50 47.93 54.57 59.57 62.91 67.30
Hz 111.4 98.56 84.71 76.52 66.49 58.96 53.91 47.28
CzH z 2.96 1.75 1.02 0.74 0.49 0.35 0.28 0.20
CZH4 1.26 1.38 1.45 1.47 1.46 1.43 1.41 1.36
C2H 6 0.01 0.02 0.05 0.06 0.09 0.13 0.16 0.20
C6H6 ILl 1 10.06 8.74 7.92 6.89 6.10 5.57 4.86
Total 151.6 145.1 138.5 134.6 130.0 126.5 124.2 121.2
CzH z 7.87 5.25 3.55 2.84 2.16 1.75 1.51 1.22
C ZH4 3.36 4.15 5.05 5.63 6.42 7.09 7.59 8.33
CZH6 0.03 0.07 0.16 0.24 0.42 0.63 0.83 1.24
C6H6 88.73 90.53 91.25 91.29 91.01 90.53 90.06 89.20
Further evaluation of CH4 pyrolysis to benzene and/or Cz~ was not warranted because of the
lack of process data. However, continued research in this area is recommended since this group
of processes is the only one that can convert CH4 to liquid hydrocarbons in one step.
A novel concept of using microwave radiation with a metal catalyst to convert CH4 into CZH4
and Hz at 50' C and 1 atm was patented by Wan (1986). The reaction is the same as Reaction
(37), and the ~H, and the ~G, (at 50' C) are 24 and 20 kcal, respectively. The chemical
equilibrium calculation showed that there was essentially no conversion at these conditions. To
achieve the 71 % conversion claimed in the patent, temperatures as high as 1,077' C would be
required. It was obvious that the catalytic active sites were highly excited during the radiation
which probably requires a large amount of high potential energy. No further evaluation of this
process was warranted because of poor chemical equilibrium and lack of process details.
206
Table 14. Calculated Equilibrium Products of CH. + O2 ~ H 20, C 2H 2 , C2H., C3H6 , C6H 6 , C~sCHJ
(Feed CH. 100 mol, 10 atm)
Temperature Variation (75 mol O2 in feed):

Temp., ·C 800 900 1000 1100 1200 1300 1400 1500 1600
Product in moles:
CH. 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01
O2 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.01 om
H 2O 150.0 150.0 150.0 150.0 150.0 150.0 150.0 150.0 150.0
C2H2 0.00 0.02 0.12 0.49 1.62 4.55 11.01 22.66 37.34
C2H. 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.01 0.02
C3H6 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
C6 H6 16.66 16.65 16.62 16.49 16.11 15.13 12.98 9.09 4.21
C6 HSCH3 0.00 0.00 0.01 0.01 om 0.02 0.02 om 0.01
Total 166.7 166.7 166.7 167.0 167.7 169.7 174.0 181.8 191.6
Feed O2 Variation (500·C):

O2 Fed ,mol 10.00 20.00 30.00 40.00 50.00 60.00 70.00 75.00 80.00
Product in moles:
CH. 86.55 73.10 59.67 46.26 32.87 19.52 6.27 0.00 0.00
O2 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 5.00
H2O 20.00 40.00 60.00 80.00 100.0 120.0 140.0 150.0 160.0
C2H2 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
C2H. 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
C3H6 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
C6H6 1.84 3.68 5.58 7.53 9.57 11.75 14.25 16.67 16.67
C6H SCH3 0.35 0.68 0.98 1.22 1.38 1.42 ~ 0.00 0.00
Total 108.7 117.5 126.2 135.0 143.8 152.7 161.7 166.7 171.7
2.4. OTHER DIRECT CONVERSION PROCESSES
2.4.1. Alkylation with Unsaturated Hydrocarbons. CH. is thermodynamically favorable to react

with lower olefins to form higher paraffins using super-acids (Sommer et al. (1982), and Olah et
al. (1983)) according to the following reaction with C2H.:
CH. + C2H. ~ C3HS MI,(50· C)=-20 kcal llG,=-9 kcal. (42)
Chemical equilibrium calculations were carried out at 50· C(30-100· C), 10 atm(1-15 atm), and
100/100 molar(100/1O-100/100 molar) CHJC 2H. feed. Major conclusions were:
Better than 99.7% conversion using stoichiometrical C2H.

Complete conversion of CzH. with deficient CzH.
Low temperatures and high pressures were preferable.
207
In reality, "undesirable" olefin oligomerization reactions also take place, resulting in undesirable
C2H. consumption. To illustrate this point, additional C3H6 and C.Hs formations were included in
the chemical equilibrium calculations. The reactions are
C2H. ¢> 2/3 C3H. MIl 50· C)= -9 kcal llG,=-6 kcal. (43)
C2H. ¢> 1/2 C.Hs (equil. mixtures) llH,(50· C)=-14 kcal llG,,,,-9 kcal. (44)
The results of the chemical equilibrium calculations are summarized in Table 15. Major
conclusions were:
Substantial C.Hs formation resulting in lower CH. conversion

Small C3H6 formation
Decreasing oligomerization at lower temperatures, higher pressures, and lower feed C2H•.
Table 15. Calculated Equilibrium Products of CH., C2H. ¢> C3Hs, C3H 6, C.Hs (Feed: 100 mol CH.)
Temperature Variation (feed CH./C2H.=I00/100, 10 atm):

Temp., ·C 30 40 50 60 80 100
Product in moles:
CH. 26.30 30.67 35.24 39.90 49.20 57.95
C2H. 0.00 0.00 0.00 0.00 0.00 0.00
C3HS 73.70 69.33 64.76 60.10 50.80 42.05
C3H6 0.01 0.01 0.02 0.03 0.06 0.13
C.Hs(at equil.) 13.14 15.33 17.61 19.93 24.55 28.88
Total 113.2 115.3 117.6 120.0 124.6 129.0
Pressure Variation (feed CHJC 2H.=100/100, 50· C):

Pres., atm 1.00 2.00 5.00 10.00 15.00
Product in moles:
CH. 58.36 51.08 41.75 35.24 31.73
C2H. 0.00 0.00 0.00 0.00 0.00
C3HS 41.64 48.92 58.25 64.76 68.27
C3H6 0.05 0.04 0.03 0.02 0.02
C.Hs 29.14 25.51 20.86 17.61 15.85
Total 129.2 125.5 120.9 117.6 115.9
Feed C?H. Variation (50·C, 10 atm):

Feed C2H., mol 10.00 20.00 30.00 40.00 50.00 60.00 80.00 100.0
Product in moles:
CH. 90.11 80.52 71.43 63.09 55.75 49.60 40.73 35.24
C2H. 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
C3HS 9.89 19.48 28.57 36.91 44.25 50.40 59.27 64.76
C3H6 0.00 0.00 0.00 0.00 0.00 0.01 0.01 0.02
C.Hs 0.05 0.26 0.71 1.54 2.87 4.80 10.36 17.61
Total 100.1 100.3 100.7 101.5 102.9 104.8 110.4 117.6
208
Similar reaction can also takes place in the presence of O2 to make higher olefins (Khcheyan et
al. (1983)):
6.Hl750· C)=-47 kcal 6.0,=-35 kcal. (45)
With O 2 , the reaction becomes highly exothermic. Chemical equilibrium calculations were
carried out at 750· C(500-900· C), 20 atm(5-100 atm), and 100/100/50 molar CHJC2HJ02 feed
and major conclusions were:
Complete CH. and O2 conversion

High pressures and low temperatures were preferable.
However, since olefins are considerably more reactive than CH., one would expect that
substantial amounts of olefins would be oxidized into COx'
Very limited amounts of work were carried out on the area of reacting CH. with C2 H2 to fonn
higher olefins. Origoryan et al. (1981) reported making C3H6 using a ferric
ariacetylacetonate/triethylaluminum catalyst at 20· C and .84 atm according to
6.H,(20· C)=-32 kcal 6.0,=-24 kcal. (46)
Allenger et al. (1991) also reported achieving high selectivities of i-butene at 10-29% CH.
conversions using solid acid catalysts containing fluoride at room or lower temperatures and 1
atm. The net reaction was unclear and may be represented by
6.H,(25 • C)=-40 kcal 6.0,=-28 kcal. (47)
In both cases, the competitive C2H2 polimerization reaction was expected. Chemical equilibrium
calculations of both reactions at 25-100· C and 100/100 molar CHJC 2H2feed showed essentially
complete conversions which decreased with increasing temperatures.
CH. can also be alkylated with aromatics to form higher aromatics (Loeffler et al. (1984))
represented by the following reaction with benzene:
6.H,(350· C)= 11 kcal 6.0,=10 kcal. (48)
Chemical equilibrium calculations were carried out using 300· C(2oo-500· C), and 100/100 molar
CHJC 6 H6 feed. The major conclusion was that conversions were <4% but increasing with
increasing temperatures. Thermodynamically, this reaction becomes more favorable in the
presence of O2 as shown by
6.H,(750· C)=-47 kcal 6.0,=-36 kcal. (49)
Again, actual product distribution is very complex. With O2, this reaction also becomes highly
exothermic. Chemical eqUilibrium calculations at 750· C(500-900· C), 20 atm(5-100 atm), and
100/100/50 molar CHJC~J02 feed, showed
Better than 99% conversion

Low temperatures and high pressures to be preferable.
209
Khchcian et al. (1974) reported CH 4 alkylation with toluene in the presence of O2 to make
styrene according to the following reaction:
Although the actual reaction products were very complex, chemical equilibrium calculations were
carried out for Reaction (50) at 750· C(500-900· C), and 100/100/100 molar CHJC 6 H sCH,J02
feed and major conclusions were:
No pressure effect
Essentially complete conversion, favorable at lower temperatures.
Under influence of a super-acid, alkylation of CH4 with itself to form higher hydrocarbons can
also take place (Olah et al. (1969)) as illustrated by
lili,(140· C)=8 kcal llG,=8 kcal. (51)
This reaction is also called "self-condensation" reaction and is slightly endothermic. Chemical
eqUilibrium calculations using 100-300· C showed
No pressure effect
Less than 0.2% conversion.
The higher conversion observed by Olah et al. (1969) was probably due to the consumption of H2
in reducing super-acids.
The alkylation processes are inefficient in carbon usage since at least two C-atoms were
needed for converting one mole of CH 4 • Few alkylation reactions show favorable chemical
equilibrium. Furthermore, the undesirable olefin or C2 H2 oligomerization reaction can also be
significant and, in most cases, the alkylation agents (Le., olefins, C2H z, and benzene) are more
valuable than the products. The Khchcian et al. (1974) work of converting toluene with CH4 to
styrene might deserve special consideration for making a high-valued chemical. Also, all
research in this area was basic in nature and offered little in process details. Consequently, no
further evaluation of this process was attempted.
2.4.2. Activation Using Metals, Metal Oxides, or Metal Complexes. The C-H bond in CH4 is one
of the most stable bonds. To break this bond in a controlled manner is one of important goals of
many research efforts. This type of reaction is generally called "Methane Activation." In last few
years, much basic research was carried out in this direction resulting in many interesting scientific
discoveries. However, most results are restricted to the area of basic research. Practically all
attention was concentrated on breaking CH4 into CH3 radical while little or no work was carried
out in trying to convert this radical into usable compounds. Furthermore, no data were obtained
either in practical operating conditions or in such details to warrant a process evaluation.
Nevertheless, this basic research may have long-range potential. Publications in this area are too
numerous to be listed here. For readers who are interested in them, many reviews (by Catalytic a
Associates (1986) and Kuo (1987)) are available.
210
2.4.3. Conversion Using Coal or Shale. To make liquid fuels, CH. is Hz-rich while solid fuels,
such as coal or shale, are Hz-poor. An ideal combination will be that CH. reacts with solid fuels
to make liquid fuels. This situation can be typified by a reaction of CH. with carbon to make
CzH.:
lili,(850· C)=30 kcal L1G,=23 kcal. (52)
This reaction is moderately endothermic.

Research in this area was conducted mainly by researchers at the Brookhaven National
Laboratory. The nominal reaction conditions were 900-1,000· C and 1.4-3.4 atm. Using a 13C
tracer technique (Sundaram and Steinberg (1986», it was concluded that 1.9% of the carbon in
CH. was converted to CzH. comparing with 1.6% from the coal.
Chemical eqUilibrium calculations of Reaction (52) using 800-1,000· C showed that
Conversions were less than 0.2% at 800-1,000·C but were increasing with increasing
temperatures
• No pressure effect.
No further evaluation was attempted due to its poor chemical equilibrium.
3. Selectivity, Conversion, and Yield
Selectivities and conversions mentioned in current CH. direct conversion publications were
essentially all based on single-pass operations. The selectivities were usually defined based on
the C-atoms in the converted CH. while the conversions were defined based on the C-atoms in the
feed CH.. The yields which usually implied single-pass yields of useful C-atoms were defined as
follows:
Yield (of useful C-atoms) = Selectivity (of useful C-atoms) x CH. Conversion. (53)
One, however, must establish an understanding between the overall and the single-pass
selectivities and between the total and the single-pass conversions since the single-pass
conversions were always too low to be practical. High total conversions could be achieved using
recycle. Recycle operation, however, always results in lower overall selectivity due to a loss of
useful C-atom in product separation.
Unfortunately, the single-pass yield defined by Eq. (53) was often inappropriately used as
criteria for catalyst and/or process selections. This important point is best illustrated by
examining the Oz requirements and the minimum heat rejected for making either CzH. or CH 30H,
COz, and HzO at a constant single-pass yield, e.g. 10% C-atom. Results are given in Figure 2.
Both the Oz requirement and the minimum heat rejection increase drastically with decreasing
selectivities. For example, at 50% selectivity the excess heat to be rejected is -1.65 times of the
product LHV, which is more than six times higher than a value of .26 at 100% selectivity. Note
that the differences on the minimum heat rejections between CzH. and CH 30H formations are
rather small. The O2 consumptions for making either CzH. or CH3 0H are identical at the same
selectivity. At 50% selectivity, the oxygen consumption is exactly five times that at 100%
211
-
"0
II)
~>
'-:1:
II)...J
0:_
16 ()
II) :::s
:1:'8 10..
r:::c"
:E'#.
Selectivity, C-atom%
Figure 2. O2 requirement and minimum heat rejected for CH4 , O2 .... C2H4 or CH3 0H, CO 2 , H2 0
(10% C-atom yield)
selectivity. Although some of CH4 would convert to CO instead of CO 2 , most of the CO would
further convert to CO 2 during recycle operation anyway.
Furthermore, lower selectivity also implies larger heat of reaction and so more difficult reactor
temperature control problem. Since both heat removal and supply of O2 can be very capital
intensive, high selectivities are much more beneficial than low selectivities. Of course, some of
the rejected heat may be recovered as surplus energy, as in steam or electricity, for export.
However, the plant would then become a costly combustor. In the case of plants utilizing remote
natural gas, export of surplus energy would be impractical.
Penalties in achieving high total conversions depend strongly on the degree of difficulty in
separating the useful products from the reactor effluents. CH 30H from a DPOM reactor can be
easily separated from the reactor effluent by cooling and condensation while separation of C2H4
and C~ from an OCE reactor can only be separated from the reactor effluent by further conversion
and/or cryogenic fractionation. Consequently, the single-pass conversion of a DPOM process
could be lower than that of an OCE process to be competitive.
4. Engineering Evaluation of Two Direct Conversion Processes
Since 1980s, extensive research activities were dedicated to the direct conversion processes
involving hundreds of professionals throughout the world. Among more than a thousand
publications, only very few dealt with some engineering aspects of the processes (Edward and
Foster (1986), Dautzenberg et al. (1986), Fox et al. (1990), and Geerts et al. (1990». This author
feels that after devoting so much research activities to the process chemistries it is now time to
study engineering aspects of some processes. Results of such a study would provide practical
goals for achicving commcrcial applications and idcntify potential high cost areas of the
processes. This author also feels that it may be premature to conduct detailed process and
212
economic studies at the present time since detailed reactor and process designs can not yet be
properly defined.
Based on results of above thermochemical and preliminary process calculations, the following
two were selected for engineering evaluation:
Direct Partial Oxidation to Methanol (DPOM); and

Oxidative Coupling to C2H4 (OCE)
with an emphasis in making liquid transportation fuels. Details of the study were given by Kuo
(1992) and only highlights of the study are given here.
The following engineering factors were examined:
Reactor conditions including selectivities and conversions, reactor type, and feed
conditions
Recycle of unconverted CH 4 to achieve acceptable total conversion and/or reactor
temperature control
Separation of products.
The two direct conversion processes were compared against a conventional indirect conversion
process. In performing process comparisons, emphases were:
Net Thermal and C-efficiencies

Heat-Transfer Duty (per product LHV)
Gas Compression Duty (per product LHV)
Gas Expansion Duty (per product LHV).
Although the net thermal efficiency is a useful criterion for process comparison, the three process
duties are also needed. The major cost of an industrial plant is usually associated with the
facilities for moving heat and mass. In this sense, the use of the heat-transfer duties is
straightforward. The major cost of mass transfer is the moving of the gaseous streams, i.e., gas
compression and expansion. The moving of the liquid streams consumes little energy, and there
is negligible movement of solids in the current studies.
In computing thermal efficiencies, one must deal with various energy forms. Since all energy
forms are certainly not equal, their equivalencies must be established. In dealing with
technologies of energy conversion, it is natural to select the chemical energies in LHV as the
standard. The equivalencies of other energy forms, including energy for making O2 , thermal
energy, steam, compression and expansion works, and electricity, were then constructed
according to understandings based on conventional energy conversion technologies and common
sense (Kuo (1992».
To put all case studies on a consistent basis, a natural gas containing 97.2 mol% CH 4 , 1.6%
C2H6 , 0.7% CO 2, and 0.5% N2 was used throughout this evaluation. This composition was similar
to the one used by Hunter et al. (1985) after removing H20 and C;. Whenever needed, O2 of 98%
purity at 1 atm was produced in a typical O 2 plant and then was compressed to any required
pressure. The high purity in O2 was needed to avoid very high system pressure.
213
4.1. ENGINEERING EVALUATION OF DIRECT PARTIAL OXIDATION TO METHANOL
4.1.1. Process Design Basis and Process Scoping Studies. Among the numerous DPOM data, the
work done by Gesser et al. was most extensive, gave the most optimistic results, and therefore
was adopted for this study. Highlights of their work are:
Non-catalytic system (cold-flame combustion) or catalytic system (SnO)
300-SOO • C and SO-6S atm
IO.S mm inside diameter glass-lined reactor
100· C lower reaction temperatures and higher CH 3 0H selectivities with C; paraffins in
feed
CH 30H selectivities up to 90% and CH. conversion up to 15%
Increasing selectivity with decreasing conversion
Negligible HCHO formation under non-catalytic system.
The status of their work is exploratory and the only published duplicated work by Burch et al.
(1989) showed substantially lower selectivities. More work will be needed to confirm their best
data.
A DPOM process scheme was constructed for evaluation. the scheme was very simple
because of the simple products and easy CH 3 0H separation. The major bases and assumptions
for the process design are:
6S atm CH.+0 2 partial pressure

90% single-pass CO 2 removal in the recycle loop
SO/SO CO/C0 2 split in CH. and C2H6 oxidation
Reaction rates for CO and C2H6 oxidation were five times of that for CH. oxidation
3S0· C temperature for an isothermal and 300-4S0· C for an adiabatic reactor
No HCHO formation
Recycle loop pressure drops equivalent to 4.4-S.9% of the reactor inlet pressure.
The relatively low DPOM reactor temperature was based on natural gases containing some C2H6
(Gesser et al. (1986)) and resulted in a higher CH 3 0H selectivity. However, using a somewhat
higher reactor temperature, such as 4S0· C, was not expected to significantly alter the results of
this study as long as the product selectivity remained unchanged. Several sets of CH 3 0H
selectivity were used in this study. It was found that, at high total CH. conversions, essentially
complete CO and C2H6 conversions were obtained as long as their oxidation rate are reasonably
higher than that of CH. conversion.
Several process scoping studies were conducted to better understand the effect of process
parameter variations on process performance. Major conclusions were:
Larger than 20% CO 2 removal in the recycle loop was essential for maintaining reasonable
recycle ratios and system pressures. However, the cost difference between 20 and 90%
removal was judged to be small
High total CH. conversions could be achieved at reasonable single-pass conversions and
recycle ratios
Higher recycle ratios could greatly reduce the reactor adiabatic aT but also increase the
reactor pressure due to greater accumulation of inert compounds
Recycle ratios larger than 20 were needed to maintain an adiabatic ll.T below 200· C.
214
Both non-catalytic and catalytic reactors were mentioned for DPOM. Adiabatic reactors are
judged to be quite inadequate because of large adiabatic temperature rises.
A Base Case (DPOM-I) was defined as follows
7.5% single-pass conversion and 90% CH30H selectivity

Isothermal DPOM reactor,
as well as three Sensitivity Cases:
DPOM-2: 15% single-pass conversion

DPOM-3: 15% single-pass conversion and 80% CH30H selectivity
• DPOM-4: Adiabatic DPOM reactor and no CO 2 removal.
The selectivity and conversion adopted in the Base Case were within the upper range of data
reported by Hunter et al. (1985). Conditions of the three Sensitivity Cases were chosen to show
effects of process variations. Note that Case DPOM-4 was the same as the Base Case except for
using an adiabatic reactor and no CO 2 removal. It was found that, since CO 2 has a high molar
heat capacity, no CO 2 removal in the recycle loop resulted in a lowering of the recycle ratio for
the same adiabatic tH. A water scrubbing column, however, was added after the separator to
minimize the amount of CH30H being recycled back to the DPOM reactor.
4.1.2. Process Calculations and Results. An audit of major energy inputs and outputs, including
the equivalent energies (in feed LHV) required for O 2 production and gas compressions, of all
cases was carried out. Thermal energy losses were estimated based on a difference between the
feed LHV and the sum of all other energy items. An audit of major heat-transfer duties, including
those from the O2 plant, the steam-turbine condensate coolers, and the compressor pre-coolers,
was also carried out. Similarly, an audit of the major gas compression duties, including those in
the O2 plant, was also done.
Results of process calculations of all cases are summarized in Table 16. The major variations
on the thermal and C-efficiencies were lower values in Case DPOM-3 resulting mainly from a
lower CH3 0H selectivity. There was a small reduction in the heat-transfer duty in Case DPOM-2
due to lower recycle flow. In Case DPOM-3, higher CO, selectivity resulted in a 23% increase in
O2 consumption, a 35% increase in steam generation, and a large increase in energy required for
gas (mainly OJ compression. All of them contributed to substantial increases in both the heat-
transfer and the gas compression duties.
In Case DPOM-4, a 29.5 recycle ratio was needed to maintain an adiabatic temperature rise
from 300· C to 450· C. Such a large recycle flow resulted in higher reactor pressure, lesser steam
generation, and moderate to large increases in gas compression and heat-transfer duties. The
large heat degradation due to the large recycle flow made this case the only case that required
diversion of a portion of natural gas feed for steam generation.
4.2. ENGINEERING EVALUATION OF MAKING LIQUID FUEL VIA OXIDATIVE COUPLING TO

ETHYLENE
4.2.1. Process Design Basis and Process Scoping Studies. Among the abundant OCE data, the
work by ARCO was most extensive, gave one of the most optimistic results, and therefore was
adopted for this study. Highlights of the work are:
215
Table 16. Natural Gas-to-Methanol via Direct Partial Oxidation: Process Efficiencies and Duties
(Kuo (1992»
Cases
DPOM-l DPOM-2 DPOM-3 DPOM-4
Partial Oxidation Reactor
Reactor Type Isothermal Isothermal Isothermal Adiabatic
Inlet Temp., • C 52.4 52.4 52.4 300.0
Outlet Temp., • C 350.0 350.0 350.0 450.0
Pressure, atm 96.7 99.4 108.0 150.0
Single-Pass CH. Conv.,% 7.5 15.0 15.0 7.5
CHPH Select.,C-Atom% 90.0 90.0 80.0 90.0
Molar Recycle Ratio 18.0 9.0 10.0 29.5
Total C-Conversion,% 96.7 97.3 97.5 98.8
Thermal Products (%Feed LHV)

CrudeCHpH 69( 73) 70( 73) 63( 68) 70( 70)
Steam 19( ---) l8( ---) 24( ---) 15( ---)
O2Production -6( ---) -6( ---) -8( ---) -6( ---)
Compression Work -8( ---) -8( ---) -9( ---) -1O( ---)
Loss 26{ 272 26{ 272 30{ 322 31{ 302
Total 100(100) 100(100) 100(100) 100(100)
C-Efficiencies 87( 91) 88( 91) 78( 85) 88( 87)
Major Process Duties (%CHPH LHV)

Heat-transfer 83( 76) 72( 66) l00( 87) 124(125)
Compression 21( ---) 20( ---) 26( ---) 23( ---)
Numbers in ( ) are those after credit of surplus steam
More than 40 patents and publications

• Reducible metal oxides as catalysts and O2carriers: 15Mn/5N~PPiSi02 best
750-900' C and 1-30 atm claimed although majority of experiments at 1 atm
14 mm inside diameter fixed-bed quartz reactors used
Less olefins produced as a result of higher pressure operation
C;, especially olefins. in the feed converted at substantially higher rate than CH. and
yielded more coke and CO.
Five operation modes claimed:
Fixed-bed cyclic operation
Fixed-bed O2co-feeding operation
Two-fluid-beds with one for re-oxidation
Moving-bed operation
Molten-salt reactor operation
Few experiments of air co-feeding operation conducted and demonstrated -5% less in C;
selectivities than those of cyclic operation
216
• Little catalyst aging data.
Since there were considerable uncertainties in experimental details, independent experiments to

confirm the best data of this work are essential.
Process schemes of aCE were not as simple as DPOM's because of difficulties in separating
useful products from aCE reactor effluents containing a low concentration of C2H.. A "light
olefin condensation" reactor must be used for making liquid fuels. Scoping studies were done on
two process schemes; one with a C; fractionation before the condensation reaction and the other
with a C; fractionation after the condensation reaction. The latter scheme was judged to be better
than the former one because of easier separation. A schematic flow diagram of the latter scheme
would consist of the following processing steps in series: aCE, cooling and separation, CO 2
removal, olefin conversion, cooling and separation, gas compression, hydrocarbon fractionation
with Ci recycle, and ClC. alkylation. Major bases and assumptions for a Base Case (aCE-I)
were:
Two-fluid-beds with one for re-oxidation at same pressure

aCE reactor at 850' C with the following selectivities in C-Atom%:
from CH.: CO 10.5%, CO 2 10.5%, C 2 H. 48%, C2H6 14.2%, C3H6 6%, C; 9.8%, and
carbon 1% (Jones et al. (1987b))
from C2H6: CO 1.5%, CO 2 1.5%, CH. 3%, C2H. 90%, and carbon 4% (assumed)
from C2H.: CO 2 25%, C3H6 65%, and carbon 10% (assumed)
from C3HS: CO 1.5%, CO 2 1.5%, C3H6 89%, and carbon 8% (assumed)
from C3H6: CO 2 30%, C.Hs 55%, and carbon 15% (assumed)
20% single-pass CH. conversion in aCE reactor and 8/1 recycle ratio
C2H6oxidation rate was ten-times of that of CH. (assumed)
Complete conversion of C2H. and C; in aCE reactor
CO oxidation rate was five times of that for CH. (assumed)
Complete combustion in aCE catalyst re-oxidation reactors using 15% excess air
• 0.02 N2 for each O2 carried by the catalyst from the re-oxidation reactor
No heat of reaction for the aCE reaction (assumed)
90% single-pass CO 2 removal
"Olefin Conversion" unit:
An adiabatic reactor at 400' C exit temperature
No minimum olefin partial pressure requirement
Adopted the best MTG yield, i.e., that of fluid-bed MTG process (Avidan et al. (1986)),
as the product yield (C-efficiency, in C3H6plus C;, >95%)
"Hydrocarbon Fractionation" unit:
34 atm pressure
-- Separation factors: 100% of C2-, 25% of C3H6, and 15% of C3HS in the gaseous phase
(estimated from similar streams from Schreiner (1978))
Alkylation unit:
-- Used ideal yields of i-C7/i-C s formation from C3HJC.Hs with i-butane
-- Imported a small amount of i-butane to achieve perfect olefin/i-butane balance
10 atm total pressure drop across the recycle loop.
Whenever possible, optimistic assumptions were made to show the best side of the process.
First, the assumed high c; aCE reaction rates were highly optimistic. However they had little
217
impact on the overall results of all cases since the total C; conversions were essentially complete
anyway. Lastly, low C2lI.; selectivities are essential for achieving a good process economics. The
14.2% C2H 6 selectivity used in the Base Case was one of the lowest ever reported. Also, in all
cases, the C,+C2 partial pressures at the OCE reactor inlet were much higher than the 1 atm used
in majority of ARCO's experiments. According to our earlier thermodynamic calculations and
Labinger and Ott (1987), higher C2H6 and lower C2H. selectivities were expected with increasing
pressure. OCE selectivities for other converted hydrocarbons were highly speculative but
optimistic.
Among the five modes of OCE reactor operation quoted by ARCO, the one with two-fluid-
beds was chosen for all studies except one because its operation, which is similar to a FCC (Fluid
Catalytic Cracking) operation, was judged to be most practical. Unfortunately, no process data of
this mode are available in the public domain. For this study, the conversion and selectivity of a
cyclic fixed-bed mode were adopted for this mode.
Five Sensitivity Cases were designed to have improvements over the Base Case:
OCE-2: 10% CH. single-pass conversion (from 20%) and 88.3% C; selectivity (from
78.0%) (Jones et al. (1987a,b»
OCE-3: Same as Case OCE-2 except minimizing the cooling of the OCE reactor effluent
and the re-heating of the feed gas to the olefin conversion reactor and moving the
gas compression and the CO 2 removal unit to a location after the "cooling and
separation" of the olefin conversion reactor effluent
• OCE-4: Same as Case OCE-2 except reducing the recycle ratio to 10 and the OCE reactor
pressure to 13 atm while adding a compressor before the "hydrocarbon
fractionation" and an expander in the recycle loop
• OCE-5: Same as Case OCE-4 except reducing the OCE reactor pressure further to 4.1
atm, raising the single-pass CH. conversion to 35%, setting the pressure after the
OCE unit by a 1.7 atm olefin partial pressure (on C 2 H. basis) at the olefin
conversion reactor inlet, and removing the minimum pressure requirement in the
hydrocarbon fractionation unit
• OCE-6: Same as Case OCE-5 except for replacing the fluid-bed OCE and re-oxidation
reactors with an O2 co-feeding fluid-bed reactor and 5% lower overall C;
selectivities (Jones et al. (1987a».
The recycle ratio in Case OCE-2 was increased from 8 to 15 to maintain about the same total
conversion. The higher recycle flow resulted in a slight increase in the CH,+C2 partial pressure at
the OCE reactor inlet (from 17 to 19 atm) and a significant reduction in the light olefin
concentration (from 4.2 to 2.5 mol%) and partial pressure (from 1.7 to 1.0 atm on C2H. basis) in
the olefin conversion reactor feed.
In Case OCE-3, the olefin conversion reactor exposing to a large amount of steam might cause
permanent catalyst aging there. There was a slight reduction of the olefin concentration (to 2.3
mol%) but a large reduction in light olefin partial pressure (to 0.73 atm) in the feed to the olefin
conversion reactor. The total pressure drop across the recycle loop was estimated to be 9.2 atm.
In Case OCE-4, the reduced OCE reactor pressure gave an 11 atm CH,+C2 partial pressure at
the reactor inlet. The total conversion was reduced from 97 to 91 %. The estimated light olefin
concentration at the olefin conversion reactor inlet was 3.5 mol% while the corresponding partial
pressure was 1.4 atm (on C2H4 basis).
218
The objective of Case OCE-5 was to show the targeted process conditions under which the
OCE process could become efficient with the above process variations. The recycle ratio was
drastically reduced to 3.5 at a 97.6% total C-conversion. The low OCE reactor pressure resulted
in a low CH4+C2 partial pressure (2.6 atm) at the OCE reactor inlet. With lower recycle ratio, the
olefin concentration at the olefin conversion reactor inlet increased drastically to 10.0 mol%. The
total pressure drop across the recycle loop was estimated to be 4.7 atm.
In Case OCE-6, no coke formation was assumed. Among many ARCO's patents on co-
feeding, none used high purity O2 , However, to minimize N2 accumulation in the recycle and to
achieve easier product fractionation, use of high purity O2 was essential. Same recycle ratio as
that of Case OCE-5 was adopted. The total pressure drop across the recycle loop remained the
same as well as the olefin concentration at the olefin conversion reactor inlet.
4.2.2. Results of Process Calculations. To simplify process calculations of all OCE cases,
energy consumption and process duties required for the hydrocarbon fractionation unit were not
accounted for, although, in reality, they could be quite substantial. In the Base Case, separation
factors based on a similar hydrocarbon fractionation unit of a reference Fischer-Tropsch case
(Schreiner (1978)) of using a refrigeration unit (to _43 C) achieving a 74% C3 recovery was used.
0
Similar separations in all OCE cases were judged to be more difficult than that of this reference
case based on the fact that the C; concentrations and partial pressures of all cases were much
lower than those of the reference case. Furthermore, a fractionation unit is a must since the
gaseous streams before the fractionation contained substantial amount of C;.
An audit of other major energy inputs and outputs, including the equivalent energies (in feed
LHV) rcquired for gas compression and O 2 production, and energies recovered from gas
expansion, was carried out. Thermal energy losses were estimated based on a difference between
the feed LHV and the sum of all other energy items. An audit of major heat-transfer duties,
including those from the steam-turbine condensate coolers, the compressor pre-coolers, and the
O2 plant, was also carried out. An audit of the major gas compression duties, including those in
the O2 plant, was also done. Lastly, an audit of the major gas expansion duties, including the flue
gas from the re-oxidation reactor, was also performed.
Results of process calculations of all OCE cases are summarized in Table 17. Major
conclusions from the OCE case studies were:
Better than 35% single-pass C-conversion and 88% C; selectivity were essential in making
the OCE processes competitive with the DPOM processes of lower conversion and about
the same selectivity
• Moderate OCE reactor pressures were essential in minimizing the compression duties
required for recycle and hydrocarbon separation
• All OCE cases studied exported undesirably a large quantity of surplus energy
• Low OCE reactor pressures combined with high single-pass conversions could
significantly reduce the compression and expansion duties
An increase of the C; selectivity from 78% to 88% and a corresponding reduction of the
single-pass conversion from 20% to 10% showed no clear trade-off
Limited process improvements were obtained by minimizing the cooling, separation, and
re-heating steps between the OCE reactor and the olefm conversion reactor
• O2 co-feeding did not show significant impact on the thermal efficiency and process duties.
219
4.3. COMPARISON OF DIRECT AND INDIRECT CONVERSION PROCESSES
Table 17. Natural Gas-to-Gasoline via Oxidative Coupling: Process Efficiencies and Duties (Kuo
(1992»
Cases
OCE-1 OCE-2
Oxidative Coupling Reactor (850·C)
Pressure, atm 31.6 31.6 31.0 13.3 4.1 4.1
Single-Pass C-Conv., % 20.0 10.0 10.0 10.0 35.0 35.0
Molar Recycle Ratio 8.0 15.0 15.0 10.0 3.5 3.5
Total C-Conv.,C-Atom% 97.7 97.2 97.2 91.2 97.6 97.4
Product Selectivities, C-Atom%:
C; 78.0 88.3 88.3 88.3 88.3 85.0
C2H6inHydrocarbons 18.1 18.1 18.1 18.1 18.1 18.3
Carbon in Hydrocarb. 1.3 1.3 1.3 1.3 1.3 0.0
Olefin Conversion Rx.: Cascaded
Thermal Products (%Feed LHV)

C~ Gasoline 53( 63) 59( 63) 59( 65) 56( 63) 59( 73) 58( 67)
C3 LPG 3( 4) 3( 4) 3( 4) 3( 3) 3( 4) 3( 4)
Fuel Gas 2( ---) 3( ---) 3( ---) 9( ---) 3( ---) 3( ---)
Steam 31( ---) 21( ---) 24( ---) 19( ---) 26( ---) 25( ---)
Expansion Work 11 ( ---) 1O( ---) 9( ---) 14( ---) 7( ---) 4( ---)
Compression Work -28( ---) -27( ---) -27( ---) -31( ---) -17( ---) -1O( ---)
O2Production O( ---) O( ---) O( ---) O( ---) O( ---) -8( ---)
Loss 28e 33) 31( 33) w....m 30e 34) .!2Lru 25( 29)
Total 100(100) 100(100) 100(100) 100(100) 100(100) 100(100)
~ C-Efficiencies 74( 88) 83( 88) 83( 91) 78( 88) 83(102) 81( 94)
Major Process Duties (%C~ LHV)

Heat-transfer 2 13( 186) 253(248) 215(205) 232(227) 124( 97) 1I9( 99)
Compression 51( ---) 43( ---) 43( ---) 53( ---) 28( ---) 30( ---)
Expansion 20( ---) 15( ---) 15( ---) 25( ---) 1I( ---) 8( ---)
Numbers in ( ) after credit of surplus steam and fuel gas.

Energies for product fractionation were not accounted for.
Using Fluid-bed MTG yields (97.9 C-atom% C;) for olefin conversion.
4.3.1. Introduction. Indirect natural gas conversion consists of two major steps in series, i.e.,
natural gas conversion to synthesis gas and synthesis gas conversion to liquid fuels. The
dominant commercial practices of the two steps are Steam Reforming and methanol synthesis,
respectively. Consequently, the Natural Gas to Methanol via Steam Reforming (SRM) is adopted
as the standard indirect conversion technology for comparison.
A typical process scheme for this indirect conversion technology consists of the following
steps in series: steam reformer, cooling and separation, CH 3 0H synthesis, and cooling and
220
separation and gas recycle. The purge gas plus a portion of the feed natural gas are burnt in the
refonner furnace to provide the heat for the refonning reaction (Reaction (1)). A large portion of
the gas from the last "cooling and separation" unit is recycled to the CH 3 0H reactor to obtain
higher synthesis gas conversion and to achieve proper reactor temperature control.
The commercial CH 3 0H synthesis processes are identified mostly by their reactor designs
which are tailored for removing the large amount of heat of reaction. Proper reactor temperature
control is essential in maintaining catalyst stability and high synthesis gas conversion which is
favorable at low temperatures according thennodynamics. Today, the dominant processes are
those of ICI and Lurgi. The ICI process uses an adiabatic, multi-zoned, inter-zone quenching
reactor (peltman and Humphreys (1975)), while the Lurgi process uses a tubular reactor design
(Supp (1973)). Although both processes are suitable for the current studies, the ICI process was
chosen because of its wide uses and abundant process data.
There are a number of current R&D activities in indirect conversion. However, none of their
potential benefits are included in this studies. Of course, a large number of indirect conversion
tcchnologies is possible simply by combining the various natural gas to synthesis technologies
and synthesis gas conversion technologies. Readers are referred to a brief review by Kuo (1992)
in reaching the above choice.
4.3.2. Natural Gas to Methanol via Steam Reforming. According to Reactions (3) and (4), H2,
CO, and CO 2 must have the following stoichiometry for fonning CH 3 0H:
(H2 - COz)/(CO + COz) = 2 (54)
while synthesis gases produced by Steam Refonning almost always contain too much H2• This
imbalance, however, can be remedied when there is CO 2 available. This CO 2 usage, which is
unique for making CH 3 0H via synthesis gas, results in higher CH 3 0H yield. Consequently, a
proper comparison against the indirect route must include the following two cases:
Case SRM-I - No CO 2 addition to the refonner feed

Case SRM-2 - Maximum CO 2 addition to the refonner feed.
The major bases and assumptions for the process design are:
Steam Refonner:
Hp/(C-atom in hydrocarbons) = 3 using a saturator and additional steam
454· C and 871· C refonner inlet and exit temperatures, respectively
20 atm refonner exit pressure
An 11· C approach to the chemical eqUilibrium of Reactions (1) and (2) for estimating
the refonner exit gas composition
A 20· C ~T driving force at the refonner exit and 15% excess air, pre-heated to 454· C,
for estimating the refonner furnace heat duty
(H2 - COz)/(CO + COz) = 2.03 for feed CO 2 (at 25· C and 1 atm) in Case SRM-2
CH3 0H Synthesis:
CH 3 0H reactor exit temperature and pressure were 270· C and 96 atm, respectively.
A 12.5· C approach to the chemical eqUilibrium of Reactions (3) and (4) for estimating
the exit gas composition
Recycle ratio =5
221
-- 6.8 a1m pressure drop across the recycle loop.
An audit of other major energy inputs and outputs, including the equivalent energies (in feed
LHV) required for gas compression and energies recovered from gas expansion. Thermal energy
losses were estimated based on a difference between the feed LHV and the sum of all other
energy items. An audit of major heat-transfer duties, including those from the steam-turbine
condensate coolers and the compressor pre-coolers, was also carried out. An audit of the major
gas compression duties, including air to the steam reformer furnace and CO 2 (Case SRM-2 only),
was also done. Lastly, an audit of the major gas expansion duties, including the CH 3 0H unit
purge gas and natural gas to steam reformer furnace (Case SRM-2 only), was also performed.
Table 18 summarizes the results of process calculations for both Cases SRM-l and -2. 0.267
moles of CO 2 per hydrocarbon C-atom was added to the reformer feed in Case SRM-2. CO 2
addition to the reformer feed resulted in a -5% increase in CHPH yield, a 22% reduction of the
feed to the reformer tubes, a 19% reduction of the synthesis gas fed to the CH 30H synthesis unit,
and a 13% reduction in the heat-transfer duty.
4.3.3. Comparison oj Direct and Indirect Conversion Processes. To make direct comparison
between the OCE cases and the SRMlDPOM cases, a fluid-bed MTG process must be attached to
the end of the latter cases to convert CHPH into C~ hydrocarbons. Following approximate rules
of this process, derived based on commercial plant design data (Avidan et al. (1986», were used:
A net thermal efficiency of95.8%

A heat-transfer duty of 9.6% CH30H LHV
• A small compression duty.
The thermal efficiencies of the SRM and DPOM cases, adjusted for producing C~ instead of
CH 3 0H, would decrease by less than 5% (in a relative term). The corresponding heat-transfer
duties would increase by less than 14%. These small increases did not have any significant
impact on results of our comparison.
After these minor adjustments, major conclusions from the process comparison were:
A DPOM process could have lower heat-transfer duty and moderately higher thermal
efficiency than those of the SRM processes if it could achieve higher than 90% selectivity
at 7.5% single-pass conversion or 80% selectivity at 15% single-pass conversion
An OCE process could be a potential contender if it could achieve larger than 88% C;
selectivity and 35% single-pass conversion concurrently.
5. Acknowledgement
Acknowledgement is made to the US Department of Energy. The major portion of the work
reported here was carried out under the DOE Contract No. DE-AC22-86PC90009.
6. Nomenclature
DOE Department of Energy

222
Table 18. Natural Gas-to-Methanol via Synthesis Gas: Process Efficiencies and Duties (Kuo
(1992»
Cases
Steam Refonning
COJC-Atom in Feed .007 .274
NG to Reactor,% 96.8 78.3
Useful C-Atom, % 86.5 87.3
(H 2-COz)/(CO+COz) 2.95 2.03
Q!,OH Synthesis
CO+C0 2 Conv., % 96.9 96.4
Thennal Products (%NG LHV)

Crude CH 30H 65( 66) 68( 68)
Steam 12( ---) 12( ---)
Expansion Work 4( ---) 2( ---)
Compression Work -14( ---) -13( ---)
Loss 33( 34) 31( 32)
Total 100(100) 100(100)
C-Efficiencies 81( 83) 84( 85)
Major Process Duties (%CH 30H LHV)

Heat-transfer 171(168) 149(147)
Compression 21( ---) 19( ---)
Expansion 5( ---) 2( ---)
Numbers in ( ) are those after credit of surplus stearn
DPO(M) Direct Partial Oxidation to (Methanol)

FCC Fluid Catalytic Cracking
flG, Gibbs enthalpy of reaction, (kcal)
flH, Enthalpy of reaction. (kcal)
HHV High Heating Value. (kcal)
ICI Imperial Chemical Industries
LHV Low Heating Value, (kcal)
LPG Liquefied Petroleum Gas
MTG Methanol-To-Gasoline process
NG Natural Gas
OCE Oxidative Coupling to Ethylene
SRM Steam Refonning to make Methanol.
223
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ENGINEERING ASPECTS OF THE CONVERSION OF NATURAL GAS INTO
MIDDLE DISTILLATES
M.M.G. SENDEN*, S.T. SIE*, M.EM. POST**, J. ANSORGE**

*Koninklijke/Shell-Laboratorium, Amsterdam
(Shell Research B. v.)
P.o. Box 3003
1003 AA Amsterdam
The Netherlands
** Shell Internationale Petroleum Maatschappij

P.O. Box 162
2501 AN The Hague
The Netherlands
ABSTRACT. Shell's research has been involved in syngas chemistry for a very long time. Special at-
tention has been focussed on routes to convert natural gas into the more easily transportable liquid
hydrocarbons. The first commercial Shell Middle Distillate Synthesis (SMDS) plant being erected in
Sarawak, Malaysia, is the result of this work. An enhanced Fischer-Tropsch Synthesis forms the heart
ofSMDS.
Engineering aspects of the SMDS process are reviewed here. They include the manufacture of
synthesis gas, the production of paraffinic Fischer-Tropsch waxes and the control of the chain length
distribution by a selective hydrocracking step. The close interaction between the properties of the
individual catalyst particles, the choice of the reactor technology and the overall process performance
is discussed in detail.
1. Introduction
Today, the energy requirements of the transport sectors are met primarily by liquid fuels
derived from crude oil and this situation will most probably continue to exi:;t for quite some
time. Gaseous fuels, such as liquefied petroleum gas and compressed natural gas, have had
only limited success even in countries where considerable fiscal incentives have been given
to their use. Forecasts indicate a further growth of the consumption of transportation fuel
till the year 2000 and thereafter, while the oil reserves are diminishing and are very much
concentrated in small parts of the world, e.g. the Middle East. Interest has therefore grown
in manufacturing liquid fuels suitable for use in existing engines, starting from alternative
resources particularly from the world's abundant gas and coal reserves.
Various conversion processes have been proposed. Generally, they are classified into
two groups: direct and indirect processes. The indirect processes all consist of a high-
temperature stage to break up the raw material into synthesis gas, i.e. a mixture of carbon
monoxide and hydrogen, followed by a synthesis stage to selectively yield the desired
products. The direct processes have no other common denominator than the avoidance
of an intermediate product and they may differ widely as to the chemical principles and
technology involved. Examples are the high-pressure hydrogenation of coal (Baerns et aI.,
227
H.I. de Lasa et af. (eds.), Chemical Reactor Technology for Environmentally Safe Reactors and Products. 227-247.
© 1992 All Rights Reserved.
228
1976) and the oxidative coupling of methane as in the ARea process (Jones et aI., 1987).
The term "direct" may suggest simplicity, but generally speaking, the direct processes are
far from being simple. They tend to be less selective towards the desired products than the
indirect processes, thereby requiring complex product work-up sections and providing less
control over product quality. Hence both in coal and in gas upgrading Shell has primarily
focussed its efforts on the indirect routes.
The composition of the hydrocarbon feedstock sets the preferred conversion routes
for the production of liquid transportation fuels, e.g. gasoline or middle distillate fuels
(kerosine and gas oil). When the carbon/hydrogen ratios of feedstock and product are
well matched as is the case with, e.g. coal and aromatic gasoline and with natural gas and
paraffinic middle distillates, a relatively high theoretical conversion efficiency is possible.
If the carbon/hydrogen ratios of feedstock and product differ substantially, rejection of
carbon or hydrogen, as the case may be, is inevitable and lower conversion efficiencies
are the result. Figure 1 shows, schematically, the resource selection routes for the various
conversion processes.
Because of the vast coal reserves, much attention was initially paid to developing the
indirect liquefaction of coal (coal gasification followed by synthesis). The high level of
investment remains, however, a major constraint on its commercial application. The con-
version of natural gas into liquid hydrocarbons, on the other hand, is seen as an attractive
alternative since the specific capital expenditure is significantly lower.
The main reasons why Shell had decided to focus its efforts primarily on developing an
indirect process for the production of liquid transportation fuels from natural gas can be
summarized as follows (Van der Burgt et aI., 1985):
- Remote and relatively small gas fields often cannot support the high investments
needed to develop a gas pipeline system or liquified natural gas production facilities,
and may well remain unutilized otherwise.
- Locally produced synfuels derived from an indigenous resource may carry a premium
owing to the high cost of importing and manufacturing transportation fuels.
- Energy policy in terms of balance of payments as well as strategic considerations can
playa decisive role in a national economy.
- Synfuels derived from natural gas (and coal) via syngas in the Fischer-Tropsch
process have an inherent high quality (being, for example, sulphur- and aromatics-
COKE/COAL NATURAL GAS

·CH· CH.
·C
k
GASOLINE GASOll
Figure 1. Resource selection routes for the manufacture of transportation fuels from coal and natural
gas.
229
free) and, hence, could be used as quality improvers with conventional components.
Moreover, the capital expenditure required for a natural-gas-based plant is about
half that of a coal-based synthesis plant.
The Shell Middle Distillate Synthesis (SMDS) process has been developed with these
considerations in mind. It produces high-quality middle distillates from natural gas via
synthesis gas and a hydrocarbon synthesis/cracking step. In August 1989, it was announced
that the world's first commercial SMDS plant will be built in Bintulu in Sarawak, Malaysia,
and that it will come on stream in the last quarter of 1992.
2. The concept of the Shell Middle Distillate Synthesis Process
The SMDS process consists of three stages (Fig. 2):

(1) Syngas manufacturing
(2) Heavy Paraffin Synthesis (HPS)
(3) Heavy Paraffin Conversion (HPC).
In the second stage, which constitutes the heart of SMDS, carbon monoxide and hy-
drogen are converted into paraffins via the Fischer-Tropsch eFT) reaction. The synthesis
catalyst and the associated reactor design represent the essential technology of the SMDS
process. Another and equally important feature in terms of the selective production of
middle distillate fuels is, however, the two-stage, HPS-HPC concept as shown in Fig. 3.
The paraffinic hydrocarbons produced via the FT reaction are highly linear. This implies
that the synthesis reaction can be regarded as a stepwise addition of a C 1 segment to the
end of an existing chain. Since atoms of the alkyl chain remote from the end will hardly
be capable of influencing this reaction, it is plausible that the relative probabilities of
chain growth and chain termination (0' and 1 - 0', respectively) will be independent of the
SYNGAS
MANUFACTURE HPS HPC
SHELL GASIFICATION
r-
-t -...
PROCESS
NATURAL ~ --. HEAVY

-+ O 2 PLANT
~ f-+ PARAFFIN ~ DISTILLATES
GAS
---- 6 I+-
CONVERSION
HYDROGEN MANU·
....... ./
1"
FACTURING UNIT
CH. + 112 02 ---. CO+ 2H2 ---. (-CH2 -)+ H20
HEAVY
PARAFFINS
Figure 2. The three stages of the SMDS process.

230
FUEL GAS
INCLUDING LPG
SYNGAS HPS FLASH
TOPS/NAPHTA
HPC DIST. KEROSINE
GASOIL
HPS: HEAVY PARAFFIN SYNTHESIS

HPC: HEAVY PARAFFIN CONVERSION
Figure 3. Shell Middle Distillate Synthesis - simplified flow scheme.
length of the alkyl chain. The carbon number distributions of the Ff product can therefore
be described fairly accurately by a simple statistical model with a as a single parameter
(the Anderson-Flory-Schulz (AFS) distribution (Anderson, 1961)), the value of a being
dependent upon the catalyst and reaction conditions. In a few hundred formulations under
different operating conditions it was confirmed that the carbon number distributions were in
close agreement with the AFS chain growth kinetics discussed above, with a-values varying
between 0.70 and 0.95 (Fig. 4).
The above feature implies, however, that the Ff process will yield either large amounts
of gaseous hydrocarbons such as methane, or products which have a very wide carbon
number distribution. Theoretically, only methane can be produced with 100% selectively.
All other products including fractions boiling in specific ranges, such as gasoline, kerosine
and gas oil, can be produced only with relatively low selectivities (Fig. 5). The only product
fraction, besides light gases, which can be produced with high selectivity is heavy paraffin
wax. It is for this reason that the synthesis part of the SMDS process has been designed to
produce a long-chain hydrocarbon wax.
The Heavy Paraffin Conversion process has now been developed to convert the heavy
paraffins selectively into the desired middle distillates, kerosine and gas oil. It is a mild
hydrocracking process using a dual functional (Shell proprietary) catalyst.
231
MOLES IN PRODUCT, ARBITRARY UNITS

100
80
60
40
20
10
8
1 ~ __ ~ ____ J-2L~L- __ ~ ____J -____L -_ _ ~ ____ ~
o 5 10 15 20 25 30 35 40
CARBON NUMBER
Figure 4. Carbon number distribution for a variety of Ff catalysts.
3. Process Description and Engineering Aspects

3.1. SYNGAS MANUFACTURE
Syngas manufacture, the first stage of the SMDS process, is very important for the total
process not only from a technical point of view but also from a economical standpoint, since
some 50-60% of the process capital cost relates to the syngas manufacturing units.
Steam reforming of methane (SMR) is a well-known option. SMR uses a nickel catalyst
and is operated at about 850°C. It produces, however, a synthesis gas with an H 2 /CO ratio
of at least 3, unless an expensive CO 2 recycle is incorporated or the natural gas used
as a feed already contains carbon dioxide. As the H 2 /CO usage ratio of the FT reaction
amounts to about 2.1 mol/mol, it is clear that the combination will always result in surplus
hydrogen production, to be burned in the SMR furnace. Theoretically, such a system is still
water-balanced, but in practice schemes based solely on SMR as a syngas manufacturing
process will require substantial amounts of make-up water. Another disadvantage is that the
maximum SMR pressure is about 30 bar, while the Ff reaction is preferably carried out at
somewhat higher pressures.
232
%w
100
80
60
40
o~ii1ltR
0.75 0.80 0.85 0.90
ex = PROBABILITY OF CHAIN GROWTH
0.95
.... CLASSICAL CATALYST
NEW CATALYST SHELL
DEVELOPMENT CATALYST
Figure 5. Product distribution in Fischer-Tropsch Synthesis.
A gas with an H 2/CO ratio of about two can be produced by non-catalytic autothermal
partial oxidation, for example, via the Shell Gasification Process (SGP). SGP was developed
in the 1950s, primarily with the objective to convert heavy residues; commercial plants have
been in operation since 1956. The process is operated at 1300 to 1500°C and pressures up
to 70 bar; the carbon efficiency is in excess of 95% with a methane slip of about 1%. For the
natural-gas-to-middle-distillate route the SGP gas requires little adjustments of the H 2/CO
ratio, giving a high overall process efficiency and producing water as the only by-product. A
small SMR unit is installed to provide the hydrogen to compensate for the slight shortage
on the hydrogen balance in the HPS stage and to serve as the feed gas for the HPC stage.
Methane is partially combusted with oxygen according to the following reaction:
CH4 + ~ O2 -> 2 H2 + CO
The feedstock is gasified in an empty, refractory-lined vessel. All gases are fed through
a burner. The oxidant is preheated in an exchanger prior to being fed to the burner.
The burner and reactor are designed such that this oxygen is intimately mixed with the
feedstock.
The primary product of the partial oxidation reaction is a raw synthesis gas at a temper-
ature of about 1300°C and higher; it consists mainly of CO and H2 (up to 95% vol), the
233
remainder being CO 2 , N 2, H 2 0 and traces of CH4 and solids. Some solids are entrained by
the gas originating from soot produced in the reactor.
The recovery of the sensible heat in this gas is an integral feature of the SGP process.
Primary heat recovery takes place in a waste heat exchanger generating high pressure-
saturated steam in which the raw syngas is cooled to some 340°C. The waste heat exchanger
is of a special design developed spccifically for these operating conditions. Part of the steam
thus generated is used for feedstock and oxidant preheating; the remainder is fed to a
superheater before being used in the utility area for power generation or in the oxygen
plant to drive the air/oxygen compressors. Secondary heat recovery takes place in a boiler
feed water economizer immediately downstream of the waste heat exchanger. The cooled
syngas is freed from trace components in a two-stage water-wash.
3.2. HEAVY PARAFFIN SYNTHESIS
The Fischer-Tropsch reaction is highly exothermic and operates in a relatively narrow

temperature range, placing high demands on heat removal and temperature control. This
characteristic of the reaction and the variability in product carbon number impose limits on
eligible reactor technology and give rise to a close interrelation between type of product, re-
actor type, and catalyst shape and size. Taking into account the requirement for substantial
removal of reaction heat, the following types of reactor technology can be considered:
- fluid bed
- fixed bed, e.g. multitubular fixed bed, and ebulliating- (three-phase fluidized) bed
- slurry, e.g. bubble column
The basic limitations of these reactor catalyst systems will now be analysed in more
detail. In particular, the limitation on product carbon number imposed by fluid-bed tech-
nology and the pore diffusion limitation of the larger particles applicable in fixed-bed and
ebulliating-bed technology will be discussed.
3.2.1. Fluid-Bed Processes. For the very exothermic and pore diffusion-limited synthesis re-
action, a fluid-bed mode of operation would seem ideal on account of the feasibility of high
heat transfer coefficients and small catalyst particles. However, the presence of relatively
heavy compounds in the product spectrum may cause deposition of these compounds on
the catalyst, leading to agglomeration of particles and fluidization problems.
As long as product is deposited within the micropores of the catalyst by capillary
condensation only, there should be no problem, as the particle will behave as a dry one.
Incipient wetness corresponds to a situation where hydrocarbon product starts to condense
on the outer surface of the porous catalyst particle. This situation, which is characterized by
the hydrocarbon dew point, marks the onset of particle agglomeration and defluidization.
Sie et al. (1988) have derived a relation that gives the maximum a value permissible, and
the limits of operating pressure, temperature and conversion level, ensuring trouble-free
fluid-bed operation. For the synthesis of a product following AFS kinetics with a probability
of chain growth a, the condition for operation above the hydrocarbon dew point can be
stated as
x/3(1-a)2 pj3n,ef 00 (a)n
a[1 - x/3(1 - a)]· P~ef . ~ 7i < 1, (1)
in which n is the carbon number of a paraffin molecule, X the fraction of synthesis gas
234
converted, P the total pressure, and po the vapour pressure at the operating temperature.
The subscript "ref" denotes a carbon number chosen as reference. The term (3 is a constant
which is the relative volatility of two paraffins differing by one carbon number and which is
related to the incremental energy of vaporization per -CH 2- segment; it is given implicitly
by:
(2)
At 280°C, (3 has the value of 0.7l.
Since n can, in principle, assume very large values and since the factor in front of the
summation sign in eqn. (1) has a positive value, the above condition can only be satisfied if
a is smaller than (3. In this case the summation represents a convergent series, yielding an
additional condition for dry operation:
P~ef > x/ 3(1- a)2 = F (3)

p. (3nref [1 - x13(1 + a)]((3 - a)
It can be deduced from eqn. (3) that this condition is best met at high temperature
(high P~f)' low operating pressure P and low conversion x. On the basis of the above
consideration, it is plausible that the known commercial Ff processes which operate in
a fluidized regime, i.e. the Hydrocol, and Synthol (Dry, 1982a,b,c; Hoogendoorn, 1981,
1982a,b) processes, produce a relatively light product at relatively high temperature and
moderate operating pressure. According to Table 1, which lists a values determined by
fitting published product distributions and other particulars of the processes, the condition
for stable fluidized operation is indeed met.
The condition that a should be smaller than (3, i.e. a < 0.71, rules out the formation
of very heavy products in a stationary, non-regenerative fluidized bed. Accumulation of
condensed products on the catalyst beyond the amount which can be accommodated within
the catalyst pores can in principle be avoided by periodic removal of this product from the
catalyst. However, for product distributions corresponding to very high a, the proportion of
condensable product would be so large that very frequent catalyst regenerations would be
necessary. In addition, removal of very heavy, strongly adsorbed material from the catalyst
by evaporation or stripping will be difficult, whilst burning-off may entail an intolerable loss
of product.
It appears, therefore, that fluid-bed technology is not suitable for the SMDS process,
which is based on the concept of synthesizing a very heavy product in combination with
selective hydrocracking. Figure 6 shows reactor systems which are suitable, in principle,
TABLE 1. Commercial-scale Fischer-Tropsch processes operating in thc fluidizcd mode

(3 = 0.71; reference = n-CIO
Process: Hydrocol Synthol
T,OC 300-350 300-350
P, bar 18- 30 20- 30
Conversion per pass, ~ 0.38 0.28
a 0.68 0.67
(3-a +0.03 +0.04
P~ecl(P . (3"ref) 11- 37 11- 33
F 0.55 0.26
235
FIXED BED REACTOR EBULLIATING SLURRY REACTOR

BEDRACTOR
SYNGAS PROD.1 PROD.1
' - - - - - - 1 - COOLANT
PROD 1
PROD 2 SYNGAS SYNGAS
Figure 6. Reactors suitable for synthesis of heavy paraffins.
for the synthesis of heavy hydrocarbons. Their basic limitations from the point of view of
physical transport phenomena will be discussed below.
3.2.2. Fixed- and Ebulliating-Bed Processes: Intraparticle Diffusion Limitations in FT Catalysts.

In a fixed-bed mode of operation, pressure drop considerations will dictate a minimum
particle size, which in general is of the order of one or a few millimetres. Heat removal
and minimization of temperature gradients in the bed rely on the effective heat conductivity
in the bed, which is favoured by high fluid velocities and large particles. In an ebulliating
bed, too, catalyst particles should not be too small lest they be entrained by the fluid as in a
slurry reactor.
It can be envisaged that, in particles a few millimetres in size, intraparticle diffusion
limitations will prevail, and this constitutes a constraint on the use of large-sized particles,
which are desirable from the viewpoints of pressure drop and heat conductivity in a fixed
bed.
Post et al. (1989) have carried out detailed studies on the occurrence of pore-diffusion
limitation with various FT catalysts. Under the experimental conditions of their study, mass
transfer limitations outside the catalyst particles were negligible, as followed, for instance,
from the observation that changes in bed length at equal values of space time did not give
rise to changes in the degree of synthesis gas conversion. With all catalysts studied, synthesis
gas conversion and catalyst productivity for hydrocarbons (expressed as space-time yield)
were found to increase significantly when the average catalyst particle size decreased from
about 2 mm to less than 1 mm.
It was found that, for these FT catalysts under the reaction conditions studied, the
synthesis of hydrocarbons proceeds almost exclusively via the reaction:
nCO + m H2 -7 Cn H 2(m-n) + n H20,
236
The rates of conversion of carbon monoxide (-reo) and hydrogen (-rHJ have been
expressed in terms of concentrations of hydrogen (CH2 ) and carbon monoxide (Ceo) in the
gas phase via the equation:
(4)
where UR is the Hz/CO usage ratio (min) and kco denotes the rate constant for CO
conversion. On the basis of literature data (Dry et ai., 1972; Feimer et ai., 1981; Huff et
ai., 1984; Karn et ai., 1965; Satterfield et aI., 1980; Vannice, 1976), we checked whether our
experimental results on the Ff catalyst could be described by a rate equation that was first
order in hydrogen gas-phase concentration (i.e. a = 1) and zero order in carbon monoxide
gas-phase concentration (b = 0). In that case, for a plug-flow reactor, the relation between
space time T" the conversion of CO(Xco), the hydrogen pressure in the reactor (PH2)' and
the CO pressure at the reactor inlet (Peo) can be written as (Levenspiel, 1972),
Ts =Peo l o
XCO dxeo
---
k co PH 2
(5)
Taking into account the gas contraction (fg) which occurs during the conversion, eqn. (5)
can be transformed into:
_ [XCO (1 + fgXCO)
(6)
kcoTs - Jo ( U R ) dXco
FR 1- FR Xco
whereFR = P'H)Peo and UR is the H 2 /CO usage ratio (min).
Integration of eqn. (6) gives:
kCOTs = (d~)2 In ( 1 - ~; xeo) - ;~ Xco (7)
3600 273 pO
Ts = GHSV . T . 105
where pO denotes the total pressure of hydrogen and carbon monoxide at the reactor inlet.
The gas contraction fg can be conveniently expressed as a function of the Hz/CO feed and
usage ratios:
UR
fg = - FR +1 (UR:S: FR)
or
(UR?: FR)
when it is assumed that the volume of gaseous hydrocarbons formed can be neglected with
respect to that of unconverted synthesis gas and water vapour formed.
Results obtained with crushed catalyst particles showed that the first-order rate constant
for carbon monoxide conversion (k co ) calculated on the basis of equation (7) is fairly
independent of space velocity and Hz/CO feed ratio. This demonstrates the validity of the
kinetic expression.
The study of the possible effects of particle size and pore diameter on intraparticle
diffusion limitations was invariably carried out with synthesis gas having a Hz/CO feed ratio
of 2 mol/mol. As the Hz/CO usage ratios observed were also very close to 2 mol/mol in this
237
case, the gas contraction tg has a value of -2/3 and eqn. (7) can be simplified to:
kCOTs = -lln(l - Xco) + ~ Xco (8)

In order to allow a proper comparison of chemical conversion rates with transport
(diffusional) rates of the reactants, it is more convenient to express eqn. (8) in terms of
hydrogen conversion and the rate constant for hydrogen conversion, kH2' since rates of
conversion depend on hydrogen pressure rather than on carbon monoxide pressure. The
relation between kH2 and keo follows from stoichiometry considerations:
-reo = keo CH2 = -~rH2 = ~kH2 CH2 (9)

and the integrated rate equation in terms of kH2 can then be expressed as:
kH2 Ts = -~ In(l - XH2) + ~ XH2 (10)

Figure 7A shows the results obtained with a series of "wide-pore" (50-65 nm pore
diameter) catalysts of similar chemical compositions and porous textures. Catalyst activ-
ity, expressed as observed first-order rate constant for hydrogen conversion, decreases
significantly with increasing particle size and this is observed over the entire range of tem-
peratures studied. The apparent activation energy for hydrogen conversion observed with
the catalyst supported on 2.4 mm spheres is of the order of 60-70 kllmol and is about half
of that found for the catalyst sample having a particle size in the sub millimetre range (120
kl/mol). A similar effect of particle size and temperature on rate constant is found for a
0.1
0.03
0.01
PARTICLE
DIAMETER,mm
0.003 A o ~8 A 038
0 1.4 o 0.75
0 24 o 24
0.001 '--_--'-_ _...L-_ _' - - _ - - - '

1.90 1.95 2.00 2.05 2.10 1.95 2.00 2.05 2.10
1000/T, K- 1 1000/T, K- 1
A. WIDE-PORE CATALYSTS B NARROW- PORE CATALYSTS
Figure 7. Arrhenius plots for the conversion of hydrogen over Ff catalysts of various particle diameters.
238
series of "narrow-pore" (10-15 nm pore diameter) catalysts, as is illustrated in Fig. 7B. Both
the substantial loss in activity observed with larger catalyst particles and the much lower
energy of activation indicate that intra particle mass transfer limitations playa significant
role in catalysts with particle sizes in excess of about 1 mm. It has been verified in separate
experiments using, for example, temperature-programmed reduction that variation of the
particle size within a series of FT catalysts of similar chemical compositions and porous
textures has no effect on the response of the catalyst to the reductive pretreatment applied.
This means that the differences in performance observed are entirely due to physical effects
(i.e. diffusion limitations), as possible chemical effects such as differences in degree or state
of reduction can be ruled out.
The effect of particle size on reaction rate can be quantified using the well-known
relation between the effectiveness factor T/ (defined as the ratio between observed rate
constant k and the intrinsic rate constant kO) and the Thiele modulus ,p. For spherical
particles (radius R) and first-order kinetics the relation can be expressed as
(11)
where
Setting the rate constant observed with 0.38 mm particles equal to the intrinsic rate
constant allows the experimental data to be fitted to the Thiele relation using a single value
for the diffusivity D of 1.2 x 10- 9 m2 /s.
The occurrence of diffusion limitation in FT catalyst particles with dimensions in the
millimetre range is supported by the effect of particle size on energy of activation and the
almost perfect fit of the experimental results to the Thiele relation. The question that now
needs to be addressed concerns the physical significance of the apparent effective hydrogen
diffusivity D emerging from the Thiele relation. Though D is based (owing to the kinetics
expression used) on gas-phase concentrations, the possibility that the transport-limiting
step originates from diffusion of hydrogen in gas-filled pores can be ruled out. Gas-phase
diffusion proceeds orders of magnitude faster than a transport process characterized by a
diffusivity of about 10- 9 m2 /s. Moreover, the class of catalysts under discussion shows a
pronounced tendency to form high-molecular-weight hydrocarbons, as is illustrated by the
Anderson-Flory-Schulz plot in Fig. 5, from which a high growth chance can be deduced.
Under the prevailing reaction conditions the major part of the hydrocarbon product will
be in the liquid phase. The liquid will fill the pores of the catalyst carrier material so that
transport of hydrogen and carbon monoxide to the reactive sites occurs by diffusion of these
reactants through this liquid medium inside the pores.
The apparent effective diffusivity D can be related to the molecular diffusivity Dm(H2)
and solubility H(H z) of hydrogen in the paraffinic liquid by the following expression:
E
D = Dm(H2) -RT .H(Hz ) (12)
T
The catalyst particle porosity E (based on total catalyst bed volume) has a value of about
0040 for the catalyst samples investigated. The tortuosity T is expected to have a value in the
range of 1.0-2.0. The solubility of hydrogen in a heavy paraffinic liquid (average molecular
239
weight 300-400; density 650 kg/m3; temperature 500 K) was obtained by interpolation of
data from Kolbel et al. (1955-1956) and Peter and Weinert (1955) and is estimated to be
of the order of 5 x 10- 5 mol/(m 3 .Pa). Using the correlation proposed by Wilke and Chang
(1955) to predict the molecular diffusivity of hydrogen in the liquid phase in the catalyst
pores, we thus arrive at a value for D in the range 0.9 x 10- 9 m2 /s to 1.8 x 10- 9 m 2 /s, which
is in excellent agreement with the experimental value obtained from the Thiele relation.
It appears, therefore, that the diffusion mechanism which limits the reaction rate in
catalyst particles of a diameter greater than 1 mm is in essence the diffusion of dissolved gas
(hydrogen and carbon monoxide) through liquid-filled pores. This makes it understandable
that the pore diameter has little or no effect on pore-diffusion limitation, in contrast
with the situation for a gas-phase reaction under relatively low pressure, where Knudsen
diffusion is rate-determining.
The occurrence of pore-diffusion limitation in catalyst particles of a size that can be
used in fixed-bed (and ebulliating-bed) FT synthesis producing relatively heavy products
has important implications: catalyst size and shape should be carefully tailored such that a
good combination of a reaction kinetics, pressure drop and heat transfer characteristics is
attained.
3.2.3. Slurry Process: Extra Particle Mass-Transfer Limitations. In a slurry process, very fine
catalyst is suspended in a liquid medium, which in the case of an FT process may be the
heavier fraction of the liquid product itself. The slurry mode of operation allows effective
removal of reaction heat and good temperature control. Because of the small catalyst
particles (particle diameter a few hundred micrometers or less), intraparticle diffusion
limitation is not a constraining factor for reaction rate. However, compared with a fixed-bed
mode of operation the advantage of better catalyst utilization may be offset by the reduced
volume of catalyst that can be accommodated in the reactor space.
Although catalyst particle size in a slurry process is of no consequence from the view-
point of intraparticle diffusion limitation, its choice is still important since it determines
the maximum allowable concentration in the liquid: very small catalyst particles can only
be used in relatively low volume concentrations if unduly high slurry viscosities are to
be avoided. Larger particles are acceptable in higher concentrations, but may give rise to
problems due to their higher tendency to settle in regions where upward liquid velocities
are inadequate to keep the particles fully suspended. Separation of catalyst from the liquid
product is also an important factor which determines the choice of particle size.
An important factor in an FT slurry process is the mass transfer outside the catalyst
particles, in particular the transport of synthesis gas components from the gas bubbles
to the liquid. Satterfield and Huff (1980) have analysed previously published studies of
the FT synthesis in slurry reactors and concluded that, in particular at higher reaction
temperatures, significant gas-liquid mass transfer limitations do occur, as evidenced by the
curvature of the Arrhenius plots.
In the classical slurry reactor processes analysed by Satterfield and Huff, mass transfer
limitations were already manifest at relatively low reactor productivities obtained at low
space velocities (typically about 200 N I gas per litre of slurry per hour) and low catalyst
concentrations of typically 50 g catalyst per litre of slurry). In view of the gas-liquid mass
transfer limitations, the occurrence of bubble coalescence is an important phenomenon in
large bubble columns since the formation of big bubbles reduces the gas-liquid interfacial
area and hence the effectiveness of mass transfer from gas to liquid.
240
3.3. THE HEAVY PARAFFIN CONVERSION OR THE FEASIBILITY OF THE SELECTIVE

PRODUCTION OF HYDROCARBONS OF A SPECIFIC CARBON NUMBER RANGE
The Ff growth mechanism implies that only methane (n = 1) and polymethylene (n ->
00) can theoretically be obtained with 100% selectivity. Intermediate products of a specific
carbon number range can only be made at substantially lower selectivities. A way to
circumvent this limitation is to combine the chain-length-independent growth process with
a selective cracking process, which has to meet the following two conditions:
- heavier components than those in the specified range have to be converted selectively
into components within this range;
- the heavier components must be more reactive than those in the contemplated range
to avoid overcracking.
For the selective production of hydrocarbons in the intermediate carbon number range
of, say n = 10-20, hydrocracking over a dual functional catalyst is a suitable process, as will
be demonstrated and discussed below.
To clearly illustrate the features of the hydrocracking process in relation to the two
conditions specified above, three narrow carbon number range fractions (C IO- l1 , C14- 16 ,
FIRST-ORDER RATE CONSTANT FOR

HYDROCRACKING (ARBITRATY UNITS)
10
1.0
0.1
e"
0.01
1.55 1.60 1.65 1.70 1.75
Figure 8. Hydrocracking reactivity of n-paraffins of different chain lengths using a dual-functional cat-
alyst.
241
TABLE 2. Relative reactivities of n-paraffins of different chain length (derived from

Fig. 8)
Reactant First-order rate constant for hydrocracking
(arbitrary units)
n-CIO 1.0
n-Cll 1.8
n- C 12
n-C!3
n- C 14 10
n- C 15 22
n-C 16 37
n-CJ7 87
C16- J7 ) obtained from a total FT product, were separately processed over a hydrocracking
catalyst. The reactivities observed for each of the hydrocarbons in the range from C IO to
C J7 are presented in Fig. 8 in a first-order Arrhenius plot; Table 2 summarizes the relative
reactivities for a typical set of hydrocracking conditions. The reactivity appears to increase
sharply with increasing carbon number, thereby fUlfilling the second condition.
Published work of Weitkamp (1975) on the hydroisomerization and hydrocracking of
n-paraffins in the range from C6 to C n , over a Pt on Ca-Y-zeolite catalyst, indicates sim-
ilarly large differences in reactivity. Weitkamp considered possible interpretations of the
influence of chain length on reactivity; however, these were too speculative, in view of the
complex reaction mechanism: rearrangement of the n-paraffin via a cyclopropane mecha-
nism into branched carbenium ions followed by ,6-scission. Other workers (e.g. Coonradt
and Garwood, 1964; Steyns and Froment, 1981), who presented kinetic models for hydroiso-
merization and hydrocracking of n-paraffins, hardly discussed the causes for the increasing
cracking rate found with increasing carbon number.
An important observation in this report is the carbon number distribution of the total
product obtained after hydrocracking of a Fischer-Tropsch fraction containing primarily
n-hexadecane. Figure 9 shows that very little methane and ethane, if any at all, is formed,
and that propane too is underproduced. The yields of the high-carbon-number products
corresponding with the splitting off of CJ, C2 or C3 fragments obviously show the same
trend. The intermediate cracking products reveal an approximately equal molar production
rate. This symmetrical product distribution, indicative of pure primary cracking, has also
been found by others (e.g. Baltanas et aI., 1983), and can be explained from the energetically
unfavourable intermediates that have to be formed if scission is to occur on an a, ,6 or ,
position. Simplifying the reaction mechanism, we may interpret this selectivity pattern as a
high and about equal reactivity of internal C-C bonds in a paraffin chain, whilst terminal
(a) or near terminal (,6 and ,) C-C bonds show relatively little tendency to break. Along
this line of reasoning, the intrinsic reactivity of n-paraffins becomes chain-length-dependent
and is proportional to the number of C-C bonds minus 6, or the carbon number minus 7.
In addition, process conditions can be chosen such as to allow partial evaporation of
the lighter hydrocarbons so that they can easily escape from the reactor. Since the heavier
paraffins may then preferentially condense or adsorb on the catalyst surface, they will
remain longer in the reactor and thus have a better chance to react. A schematic adsorption
curve as a function of the carbon number has been included in Fig. 10. Initially, one
242
% mol
12 r-
- r-
r-
10 f- r--
- r-
8 '- f--
4 f-
r-- -
2 f-
o I I I I I ~I
o 2 4 6 8 10 12 14 16
CARBON NUMBER
Figure 9. Molar product distribution after hydrocracking a Fischer-Tropsch fraction (88 %wt C16,
12 %wt C17) over a dual-functional catalyst.
may expect the curve to follow an approximately exponential increase with an increase
in carbon number as the adsorption coefficient is an exponential function of the heat of
adsorption, while this heat of adsorption for n-paraffins is known to increase about linearly
with increasing carbon number; the increment per carbon number amounts to some 10-15
kJ/mo!. Above a certain chain length one may expect, however, the effect to level off since
the degree of adsorption approaches 100%. As shown in Fig. 10, the result would be a
chain-length-dependent reactivity, which shows a very steep increase in the lower carbon
number range and an about linear increase at high carbon numbers.
Assuming an equimolar production ratio for all cracked compounds except for those
resulting from breakage of a, f3 or I bonds, it may be calculated that a C 20 + paraffin can be
converted to some 80% by weight of Cto -C20 material, while only some 20% by weight ends
up in the < C to fraction.
The principle of combining the length-independent chain growth process with a selective,
chain-length-dependent conversion process has been applied to the selective production of
mid-distillate paraffins (n = 10-20) from synthesis gas. To take full advantage of this
concept, the Fischer-Tropsch catalyst and the operating conditions were so chosen as to
produce a heavy product with a high a-value, which minimizes the formation of undesired
light products (n < 10). The effectiveness of the two-stage approach is further illustrated
in Fig. 11, which shows experimentally determined distributions of a Fischer-Tropsch liquid
product before and after hydroconversion at two different severities. Under the conditions
applied, too heavy paraffins were preferentially cracked, so that the ultimate product
distribution shows a peak in the desired mid-distillate range with a minimal amount of
additionally formed light products.
243
RELATIVE REACTIVITY
OR DEGREE OF ADSORPTION
ON CATALYST SURFACE AREA
o 5 10 15 20 25 30 35
CARBON NUMBER
Figure 10. Schematic representation of the reactivity of n-paraffins.
PRODUCT COMPOSITION, "low

10
HIGH-SEVERITY HYDROCRACKING
8
6 MEDIUM-SEVERITY
4
FISCHER-TROPSCH
/ PRODUCT
2
o
o 10 20 30 40
CARBON NUMBER
Figure 11. Carbon-distribution of a Fischer-Tropsch product before and after selective hydrocracking.
244
This principle is applied with success in the HPC (Heavy Paraffin Conversion) step of the
SMDS process.
The HPC is a mild trickle flow hydrocracking process using a Shell proprietary catalyst
and operating at typically 30-50 bar total pressure and at a temperature of about 300-
350°C. The plant lay-out is very similar to that of a conventional gas oil hydrotreater. The
HPC stage performs actually four functions:
1. hydrogenation of the olefins present in the Ff product,
2. removal of the small amount of oxygen-containing compounds, i.e. mainly primary
alcohols,
3. hydro-isomerization, and
4. hydrocracking of the n-paraffins to iso-paraffins of the desired length or boiling
rangc.
The HPC product is subsequently fractionated in a conventional distillation scction. The
product fraction which is still boiling above the gas oil range is recycled to the HPC section.
By varying the process severity or the conversion per pass one can influence the selectivity
towards a preferred product. Hence one may opt for a kerosine mode of operation yielding
some 50% kerosine on total liquid product or for a gas oil mode of operation producing
some 60% gas oil.
4. General Concluding Remarks
The theoretical maximum thermal efficiency for the conversion of methane into paraffins is
78% (based on lower heating values). The practically attainable efficiency is of course much
lower.
Owing to proper heat integration, the SMDS plant is heat balanced, i.e. no extra natural
gas has to be burned for utility purposes. The steam produced in both the SGP and the HPS
process is used in, for example, the turbines of the oxygen-manufacturing plant and the
various process off-gases are used to fire the SMR. As a result the overall thermal efficiency
of the Bintulu SMDS plant will amount to 63%, or in other words 80% relative to the
theoretical maximum. It is beyond discussions that major engineering problems have been
resolved to achieve this excellent process result.
The production of middle distillates from natural gas has a low environmental impact.
Off-gases of the various process units are used inside the plant for utility generation e.g. to
fire the SMR. Flue gases leaving the plant are free of sax x
and low in NO and fulfil the
stringent European specifications.
As a general principle, process water and condensate would be re-used to minimise the
discharge of waste water. The process based on partial oxidation of natural gas is, however,
a net producer of water. Waste water leaving the plant would first have to be treated to such
an extent as to allow its discharge into a river. In areas of water scarcity, however, this water
may even be turned to advantage e.g. for irrigation purposes.
The only solid effluent is spent catalyst which will be recycled to recover the metallic
components.
Furthermore, it is important that owing to the exceptional quality of both the kerosine
and gas oil products, the emission of harmful exhaust products is very low when the
products would be used as neat transportation fuels.
245
Capital and operating costs of synfuel complexes are known to be high and strongly de-
pendent on the location. The total investment of the 12,000 bbl/d Bintulu project amounts
to about US $660 million. A large SMDS plant using inexpensive remote natural gas will be
economic at crude oil prices of about 20 US $/bbl.
New process developments are very much focussed on the reduction of the costs per
unit of product. Though the unit as designed now for Bintulu is a full-scale commercial
plant, the matter of scaling-up to still larger units is actively pursued. In scaling-up efforts
many engineering challenges remain present in the areas of synthesis gas manufacture, the
Fr-reactor design and scale, and the plant integration as a whole.
5. Acknowledgement
The authors gratefully acknowledge the contributions of E Schrauwen, D. Agoropoulos,

AC. van 't Hoog, J.K. Minderhoud and J. Eilers. This publication is based to a considerable
extent on the results of their work in Fischer-Tropsch technology.
Nomenclature
C concentration of reactant in gas phase
D apparent effective hydrogen diffusivity based on gas phase
concentrations
Dm(H2) molecular diffusivity of hydrogen based on liquid phase
concentration
GHSV gas hourly space velocity of synthesis gas Nm 3 (CO+H2)/(m 3 cat·hr)
H(H2) solubility (Henry coefficient) of hydrogen in liquid mOI/(m 3 .Pa)
paraffinic Ff product
k first order rate constant
n carbon number
nref carbon number of reference paraffin
p total pressure Pa
pO inlet pressure Pa
P:: vapour pressure at operating temperature of paraffin Pa
with carbon number n
vapour pressure at operating temperature of reference Pa
paraffin
r rate of conversion of reactant per unit catalyst bed volume mOI/(m 3 cat.s)
R (1) in equation(12): gas constant 8.2 (m 3 Pa)/(Kmol)
(2) in general: particle radius m
T temperature OK
UR H2/CO usage ratio mol/mol
a Anderson-flory-Schulz growth chance
(3 relative volatility of two paraffins differing by one carbon
number
fg gas contraction
1) effectiveness factor
T tortuosity
space time
Thiele modulus
X conversion of reactant
246
References
Anderson, RB. (1961) 'Kinetics and reaction mechanism of the Fischer-Tropsch Synthesis', in P.H.
Emmett (ed.), Catalysis, VoL W, 2nd Ed., Reinhold, New York, p. 350.
Baltanas, M.A, Vansina, H. and Froment, G.F. (1983) 'Hydroisomerization and hydrocracking. 5.
Kinetic analysis of rate data for octane', Ind. Eng. Chern. Prod. Res. Develop. 22,531-539.
Baerns, M., KOibel, H., Rottig, w., Schnur, F. and Scholz, H. (1976) 'Stand und Entwicklungsmoglichkeiten
der Fischer-Tropsch-Synthese zur Erzeugung von Chemiegrundstoffen und Chemierohstoffen",
Bundesministerium fUr Forschung und Technologie, Forschungsbericht T 77-43, Thchnologische
Forschung und Entwicklung-Nichtnukleare Energietechnik.
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Des. Develop. 3, 38-45.
Dry, M.E. (1982a) 'Sasol's Fischer-Tropsch experience', Hydrocarbon Processing, August, 12l.
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Dry, M.E., Shingles, T. and Boshoff, LJ. (1972) 'Rate of the Fischer Tropsch reaction over iron
catalyst',l Cata!. 25, 99.
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reaction', Ind. Eng. Chern. Prod. Res. Develop. 20,609.
Hoogendoorn, J.C. (1981) 'Motor fuels and chemicals from coal via the Sasol Synthol route', Phil.
Trans. R. Soc. Lond. A300, 99.
Hoogendoorn, J.C. (1982a) 'Producing automotive fuels from coal in South Africa', Hydrocracking
Processes, March, 34E.
Hoogendoorn, J.c. (1982b) 'Gasoline from coal- the pioneering South African experience', Energy
Processes 2 (1), 32.
Huff, G.A, Jr. and Satterfield, C.N. (1984) 'Intrinsic kinetics of the Fischer Tropsch synthesis on a
reduced fused-magnetite catalyst', Ind. Eng. Chern. Process Des. Develop. 23,696.
Jones, C.A, Leonard, J.J. and Sofranko, J.A. (1987) 'Fuels for the future: remote gas conversion',
Energy and Fuels 1, 12.
Karn, F.S., Schultz, J.F. and Anderson, RB. (1965) 'Hydrogenation of carbon monoxide and carbon
dioxide on supported ruthenium catalysts at moderate pressures', Ind. Eng. Chern. Prod. Res.
Develop. 4, 265.
Kolbel, H., Ackermann, P. and Engelhardt, F. 'Neue Entwicklungen zur Kohlenwasserstoff-Synthese',
Proc. 4th World Petro Congress, Rome, Section IV-6, Paper 9 (1955); Erdal und Kohle 3, 153
(1956).
Levenspiel, 0. (1972) Chernical Reaction Engineering, Wiley, New York.
Peter, S. and Weinert, M. (1955) 'Uber die Uislichkeit von H 2 , CO, CO 2 und Wasserdampf in
fiiissigen Kohlenwasserstoffen', Z. Phys. Chern., Neue Foige (Frankfurt/Main) 5, 114.
Post, M.F.M., Van 't Hoog, A, Minderhoud, J.K. and Sie, S.T. (1989) 'Diffusion limitations in
Fischer-Tropsch catalysts',AIChE.J. 35 (7), 1107-1114.
Satterfield, C.N. and Huff, G.A, Jr. (1980) 'Effects of mass transfer on Fischer-Tropsch synthesis in
slurry reactors', Chern. Eng. Sci. 35, 195.
Sie, S.T., Eilers, J. and Minderhoud, J.K. (1988) in M.J. Phillips and M. Thrnan (Eds.), Proc. 9th
Internat. Congress on Catalysis, Calgary, 1988, Chern. Inst. Canada 2, 743-750.
Steyns, M. and Froment, G.F. (1981) 'Hydroisomerization and hydrocracking: Kinetic analysis of rate
date for N-decane and N-dodecane', Ind. Eng. Chern. Prod. Res. Develop. 20,660-668.
Van der Burgt, M., Van Kiinken, J. and Sie, S.T. (1985) 'The Shell Middle Distillate Synthesis Process',
Paper presented at the 5th Synfuels Worldwide Symposium, Washington, D.C., November 11-13.
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n-alkanes', in J. W. Ward and S.A Qader (eds.), Hydrocracking and Hydrotreating, Am. Chern. Soc.
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1,264.
STEAM REFORMING
OPPORTUNITIES AND LIMITS OF mE TECHNOWGY
JENS ROSTRUP-NIELSEN, IB DYBKJAER and LARS J. CHRISTIANSEN

Haldor Topsoe AIS
Nymoellevej 55
DK-2800 Lyngby
Denmark
ABSTRACT. Steam reforming is a well-known process for converting natural gas and other hydrocarbons
into synthesis gas and important products. The increased interest in CJ-chemistry and advanced energy
systems has lead to a wish to explore the limits of the technology. The paper describes the advances in
mechanical design and modelling of the conventional tubular reformer as well as the heat exchange
reformer. The role of adiabatic pre-reforming, autothermal reforming and CO2-reforming is discussed. The
main requirements of the catalyst are described with emphasis on control of tube wall temperatures and
carbon formation. The application of steam reforming for manufacture of synthesis gas is illustrated by
examples. Also the technology is compared with the direct conversion of methane, concluding that indirect
conversion via steam reforming is still the preferred choice.
1. Introduction
1.1. THE REACTIONS
Steam Reforming is an essential process for the manufacture of synthesis gas and hydrogen from
hydrocarbons (Rostrup-Nielsen, 1984a) and (Ridler et al, 1989) with the corresponding heat of
reactions:
CH4 + H 20 = CO + 3H2 -49 kcal/mol (1)

CO + H 20 = CO2 + H2 + 10 kcallmol (2)
Higher hydrocarbons in natural gas, LPG or liquid hydrocarbons will react in a similar way:
CnHm + nH20 = nCO+(n+~)H2 Endothermic (3)

2
Steam may be replaced by CO2, which gives a much more favorable H 2 /CO ratio for many
syntheses:
CH4 + CO2 = 2CO + 2H2 -59 kcallmol (4)
Reactions (1) - (4) require a catalyst, which typically is supported nickel. Methane may also be
converted by means of oxygen into synthesis gas by partial oxidation:
249
H.l. de Lasa et al. (eds.), Chemical Reactor Technology for Environmentally Safe Reactors and Products, 249-281.
250
+9 kcallmol (5)
This reaction may be non-catalytic or use a catalyst, typically supported nickel.
1.2. THE EQUILIBRIA
The methane reforming reaction (1) and the water gas shift reaction (2) are reversible at
reforming temperatures. Reaction (4) is the difference of reaction (1) and reaction (2). It is
evident, from the principle of Le Chatelier, that at higher temperatures less methane and more
carbon monoxide are present in the equilibrium gas, and that methane content increases with
pressure and decreases with increasing ratio of steam to carbon. This is illustrated in Figure 1.
Composition Dry Mole %

100
80
60
40
20
o
400 600 800 1000
Temperature °C
Figure 1. Equilibrium compositions (dry gas). Steam reforming of methane. P = 30 bar,
H 20/C = 4.0
TABLE 1. Equilibrium Constants (standard conditions

25°C, 1 atm. abs).
Reactions SOO"C 700"C 900"C
CH.+H,o = CO+3H2 9.945-10-3 12.71 1493
CO + H20 = CO2 +H2 4.999 1.576 0.7694
2CO =C+C02 232.1-10" 0.9563 2_668-10-2
CH. = C + 2H2 0.4617-10- 1 7.715 51.76
Equilibrium constants for reactions (1) and (2) at selected temperatures are listed in Table 1.
A complete list may be found in (Rostrup-Nielsen, 1984a). In principle, the equilibrium
composition is determined by the atomic ratios OIC, HIC, inertlC, pressure and temperature.
The product gas composition from a reformer can be estimated from thermodynamic
calculations because it will in most cases be close to that of the equilibrated gas. In industrial
251
practice, the "approach to equilibrium" at reformer outlet for the reforming reaction is expressed
by a temperature difference defined as:
I>. TRee = T(exit catalyst) - T(QR) (6)
in which T(QJ is the equilibrium temperature corresponding to an equilibrium constant equal to

the reaction quotient QR' which is the product of the partial pressures of the individual
components raised to the power of their stoichiometric coefficients. The various gas compositions
which can be obtained by reaction (1) to (3) have resulted in the use of the reforming process as
the essential step in the preparation of synthesis gas for several purposes. In practice, the pressure
is often determined by the overalilay-out of the process. This leaves the steam to carbon ratio
and the catalyst exit temperature as the major parameters determining the gas composition.
Although the irreversible reaction (3) is strongly endothermic, the overall heat of reactions (1)
to (3) may be positive, zero, or negative, depending on the process conditions. At low steam to
carbon ratios and at low catalyst exit temperatures, the overall heat of reaction is positive. This
is reflected by the high contents of methane in the product gas. In such cases, it is possible to
carry out the process without external heating in an "adiabatic reformer". However, for the
production of gases with lower methane contents such as towns gas, synthesis gases, and
hydrogen, a high catalyst outlet temperature is required, and the overall reaction becomes
endothermic. In order to supply the required heat, the catalyst is loaded into a number of tubes
placed inside a furnace. This reactor is called a "tubular reformer" (Figure 2). This version of
the reforming process is the most important for industrial applications.
Figure 2. Tubular Steam Reformer, 1350 tid Ammonia Plant (Thal, India).
The conversion of hydrocarbons with oxygen (reaction (5)) is done in the partial oxidation
processes (Texaco, Shell) and also in a hybrid between thermal and catalytic reaction in an
"autothermal reformer".
1.3. CARBON FORMING REACTIONS
Reactions (1) and (3) may be accompanied by the following reactions forming carbon.
2CO = C + CO2 +41 kcal/mol (7)

252
-18 kcal/mol (8)
CH - nC +
m
_J.J (9)
• m 2"2
Reaction (7) is normally referred to as "the Boudouard reaction". At high temperatures (above
about 650°C), higher hydrocarbons may react in parallel to reaction (3) by thermal cracking
(Albright et ai, 1983) (pyrolysis or "steam cracking") into olefins which may easily form coke
via reaction (9):
CoRm .... olefins .... polymers .... coke (10)
Reactions (7) and (8) are reversible, whereas (9) and (10) are irreversible for n > 1. Equilibrium
constants for reactions (7) and (8) are listed in Table 1.
1.4. APPLICATIONS
The applications of the reforming technology are widespread in the petrochemical industry as well
as in the energy related industries. Most of the world ammonia production is based on steam
reforming of hydrocarbons, with natural gas being the preferred feedstock. Oil refineries use
hydrogen from steam reforming for desulphurization and hydrocracking. In the petrochemical
industry, steam reforming is used for production of synthesis gas for methanol and oxo-alcohols
and for Ccchemistry reactions such as synthesis of acetic acid, etc.
The steam reforming process is an important element in solving the problem of the huge
amounts of associated gas produced jointly with oil production. The gas may be converted either
into methanol or synthetic liquid hydrocarbons. Other applications include gases for direct
reduction of iron ore, conversion of hydrocarbons for fuel cells, and advanced energy transfer
systems, in which nuclear heat or solar energy are absorbed by the endothermic steam reforming
process.
2. The Reforming Technology
2.1. THE TUBULAR REFORMER
2.1.1. Transferred Duty. In order to supply the heat for the overall endothermic steam reforming
reaction, the catalyst is loaded into a number of high alloy tubes placed inside a furnace equipped
with burners. Typical inlet temperatures are 450-650°C, and the product gas leaves the reformer
at 700-950°C depending on the applications.
The required heat input, the reformer duty, Q, is the enthalpy difference between the exit and
the inlet gas, and it can easily be calculated from enthalpy tables. The duty consists of heat of
reaction as well as the heat required to raise the temperature to the level of the reformer exit. In
a typical tubular reformer furnace, about 50% of the heat produced by combustion in the burners
is transferred through the reformer tube walls and absorbed by the process (in an ammonia plant:
60% for reaction, 40% for temperature increase). The other half of the fired duty is available in
the hot flue gas and recovered in the waste heat section of the reformer for preheat duties and
for steam production. In this way, the overall thermal efficiency of the reformer approaches 95 %.
The balance between heat input through the reformer tube walls and the heat consumption in
the endothermic reforming reaction is the central problem in steam reforming. The maximum
allowed stress value in the tubes is strongly influenced by the maximum tube wall temperature
253
and by the maximum heat flux. Even a slight increase in the maximum tube wall temperature may
result in a serious decline of the expected tube life time.
Typical values of the average heat flux, q.., in modern reformers are about 70000 kcal/m2/h.
The average heat flux is, however, not a very good measure of the operating severity. More
important is the maximum heat flux and the temperature at which the peak in the heat flux is
reached.
2.1.2. Mechanical Design. Tubular reformers are designed with a variety of tube and burner
arrangements (Rostrup-Nielsen, 1984a). Basically there are four types of reformers as illustrated
in Figure 3.
Bottom Fired Top Fired Terrace Wall Side Fired
Figure 3. Typical Configurations of Reformer Furnace.
The bottom fired type has an almost constant heat flux profile along the length of the tube. The
furnace approaches a counter-current design resulting in high metal temperatures at the outlet.
The terrace wall fired reformer is a modification of the bottom fired type, having slightly lower
tube wall temperatures. The top fired reformer is characterized by a peak in the tube wall
temperature in the upper part of the reformer, and it has the highest heat flux where the metal
temperature is at its maximum. The side wall fired furnace allows adjustment and control of the
tube wall temperature. The maximum temperature is at the outlet of the tube, whereas the highest
heat flux is at a relatively low temperature. The side wall fired design thus offers more flexibility
in design and operation, and higher average heat flux and more severe operating conditions are
possible. As an added advantage, the short flames in the side wall fired furnace ensure very low
NOx levels in the flue gas, typically below 50 ppm.
The reformer tubes are subject to very large stresses since they operate at high temperatures
with very large temperature gradients. Reformer tubes are normally designed for an average
expected lifetime of 100,000 hours, and great care must be taken when choosing heat flux, tube
dimensions, design temperatures and tube materials.
The tube materials are limited by design temperature and creep rupture strength. Recent
progress in the formulation of construction materials (Jones, 90/91) and (Thuillier et aI., 1978)
has allowed safe designs with exit gas temperatures exceeding 950°C corresponding to tube wall
temperatures up to 1050°C. The new materials which have superior creep rupture characteristics,
allow a design with a considerable reduction in tube wall thickness. The use of a thin tube wall
254
improves the tube lifetime by increasing the tolerance of the tube to thermal cycling and thermal
shock.
Figure 4 shows a Topsoe reformer furnace seen from the end. The tubes are arranged in a
single row, and the burners are placed in the furnace walls at six levels. With this arrangement,
it is possible to adjust and control the heat input along the length of the tube, thus ensuring an
optimum temperature profile at all operating conditions. Hot flue gas leaves the radiant chamber
through a refractory-lined duct, and the heat is utilized in the flue gas waste heat section. Feed
gas passes from a distribution header through the inlet hairpins to the tubes. In this case the inlet
hairpin is connected to the side of the reformer tube, allowing a high preheat temperature. The
inlet hairpin is flexible, allowing expansion of the tube.
The tubes are supported at the bottom and expand upwards through the furnace. In order to
reduce the load on the refractory-lined collector and to eliminate any risk of tube bending, most
of the tube weight is supported by a spring arrangement connected to the top flange of the tube.
Process gas from the outlet of the reformer tubes passes through the transition joint outside the
furnace to the refractory lined outlet collector. This outlet system is used when the outlet
temperature is high (above ca. 900°C). In other applications, an alternative outlet system with
hairpins and hot collector is used (Kawai et aI., 1984) and (Dybkjaer et aI., 1989).
Figure 4. Topsoe Reformer designed for High Outlet Temperature.
2.1.3. Refonner Optimization. The tube geometry has a complex influence on the reformer
design. Increasing the length of the tubes is more economical than increasing the number of
tubes, because more tubes mean enlargement of the complex inlet and outlet systems. However,
the tube length is limited by the risk of tube bending and by restrictions in pressure drop across
the catalyst.
For a given tube length, feed flow, and reformer duty, Q, the number of tubes, n, is
determined by the selected tube diameter, d., the average heat flux, 'laY> and the space velocity,
SV. These parameters are interrelated. It can be shown by a total heat balance and by assuming
255
constant inlet and outlet conditions that, independent of n:
(11)
This means that only two of these three parameters can be selected freely. If <lay is kept constant
and d, increased, the number of tubes decreases, also decreasing the number of inlet and outlet
hairpins. The pressure drop over the reformer also decreases, whereas the dimensions of the
furnace box remain roughly constant. The catalyst volume, however, increases linearly with d,
(reduced SV, eq. (11», and the total weight of the tubes increases more than proportional to ct.
due to the increased tube wall thickness. Thus, the total cost of the reformer tends to increase
with increasing ct. above a minimum diameter below which the tube wall thickness must be kept
constant for other reasons.
2.2. THE HEAT EXCHANGE REFORMER
2.2.1. Principles. The transferred duty to the catalyst bed is typically about 50% of the fired duty
in the tubular reformer. This can be increased to about 80% when using a heat exchange
reformer. The flue gas as well as the hot product gas is cooled by heat exchange with the process
gas flowing through the catalyst bed.
The most efficient heat exchange is achieved by counter-current flows, but at the high
temperatures applied there is a risk for overheating of hot metal parts, and this could have serious
impact on the life of the unit. A viable design is obtained (Stahl et al., 1985) when co-current
flow is applied in the hot part and counter-current flow in the cold part of the reformer as shown
in Figure 5. The co-current flow allows better temperature control at the high temperatures and
the counter-current flow is used at the low temperatures where effective heat transfer is more
critical. Pilot tests (Laursen et ai., 1990) showed that all gas streams leave the reformer at about
500"C so that the amount of waste heat was reduced from 50% of the fired duty in the
conventional design to about 20% in the heat exchange reformer. At the same time, it was
possible to reduce the production of NOx to a level of about 20 ppm in the flue gas, by using a
special burner design.
2.3. MODELLING OF THE REFORMER
2.3.1. Heat Balance. The heat transferred per unit time and unit volume of catalyst, H, is
proportional to the heat transfer coefficient, U, and the difference between the outer tube wall
temperature, Tw , and the catalyst temperature, Te. This term can also be obtained from a one-
dimensional pseudo-homogeneous model as:
4 dT
H = -UCT -T) = (-.1.H)r +u Q C - (12)
d, W C v • g P dz
The two terms on the right-hand side represent the heat absorbed by the reforming reactions
and that used for increasing the gas temperature, respectively.
The heat input through the reformer tube wall results in radial temperature and concentration
gradients in addition to the axial gradients. Therefore, a two-dimensional model is required when
a detailed knowledge of the conversion and temperature profile is necessary as is the case when
the operation of the steam reformer is critical with respect to carbon formation (Rostrup-Nielsen,
1984a).
256
Process Gas ____

Inlet _..--=
First Catalyst
8,"
Figure 5. Heat Exchange Reformer. The Topsoe HER Design.
The heat is transferred from the tube wall in the radial direction of the catalyst bed and then
across the gas film surrounding each catalyst particle. A detailed description would therefore in
principle require a three-dimensional model. However, the gradients in and around the catalyst
pellet are taken into consideration by using an effectiveness factor for each reaction based on the
bulk phase conditions.
On this basis, the two-dimensional model (Froment et aI., 1979) can be derived from the basic
equations of continuity assuming that axial dispersion of heat can be neglected and that the heat
transfer in the radial direction can be described by an effective thermal conductivity independent
of radial distance.
The heat balance equation is then:
or
az
= ~.!.~(r or)
p~ 1 at at
+ f
j-I
lvj<
Gcp
-,m; (13)
where PeH is the Peclet number for heat transfer. The boundary conditions reflect the observation
that the largest resistance to heat transfer is at the tube wall:
(14)
The temperature difference on the right side of the equation is between the temperature of the
outermost layer of the catalyst bed T R and the inner tube wall temperature Tw. Ciw is consequently
a film heat transfer coefficient.
257
In the center, the boundary condition is:
or =0 atr=O allz (15)

at
In the heat exchange reforming case with heat exchange between the catalyst bed and a fluid with
temperature T f either on the outside at r = R., or with an internal tube at r = R" the boundary
condition can be written as:
dT
-A..-dr = U(TR -T) (16)
r
where the overall heat transfer coefficient, U, is calculated as a combination of the individual
resistances in the catalyst bed, the wall and the adjacent channel. Typical values for U are in the
range 200-400 kcal/m21hlK, to a large extent dependent on the type of heat transfer in the
adjacent channel. A similar equation can be written for the outside boundary condition.
The balance equations for the fluid in the adjacent channels must also be taken into
consideration:
(17)
The sign on the right side depends on whether the flows in the inner and outer channels are
counter- or co-current to the flow in the catalyst bed.
The inlet condition at z = 0 is:
T = Tin all r (18)
2.3.2. Mass Balance. The continuity equation for component A is set up with the same
assumptions as those for the heat balance equation.
The equation is normally for a single component in a single reaction. In the general steam
reforming case, the equations are set up for K reactions and C components. It is therefore
convenient to define a conversion Fj in reaction j as the amount in kmollh formed via reaction
j only per unit feed mixture and for a component with stoichiometric coefficient + 1. The
reaction rate Rj is then the rate in kmollh/m 3 bed for a component with stoichiometric coefficient
+ 1 and also appearing in reaction j only.
With the fractional conversions known, the mole fraction of component i is calculated as:
(19)
From the real gas law, the relationship between mole fraction and concentration can be inserted
in (19) and the mass balance equation can then be written for a component with stoichiometric
coefficient + 1 appearing in reaction j only:
aFj = ~ !~(raFj) + M r (20)

az PeM r at at Po vj
It has consequently been assumed that the radial diffusion of the individual components can be
258
lumped into a single effective diffusion coefficient, as characterized by the Peclet number for
mass transfer, PeM and that the axial dispersion term is neglected here, too, as in equation (13).
The latter simplification is permissible due to the large value of the Reynolds number, which is
more than 1000.
The boundary conditions are:
dF
_J ~O atr~Ri,r~Ro (21)
dr
The inlet condition is:
Fj =0 all j, r (22)
A similar equation can be set up for the pressure drop. The combined model now contains K + 1
coupled parabolic partial differential equations and one ordinary first order differential equation.
They are solved by discretization in the radial direction by use of the orthogonal collocation
method, and integration of the resulting set of coupled first order differential equations by use
of a semi-implicit Runge-Kutta method. With this model and the used solution method, one can
now concentrate on the effective transport properties given in Pt\J, PeM and the wall heat transfer
coefficient, with the latter being the most important parameter for design.
An application of the model is shown in Figure 6, which shows a comparison between
calculated and measured axial and radial catalyst bed temperatures at measured outer tube wall
temperatures. The data are from an experiment carried out on a monotube pilot under conditions
at a low steam-to-carbon ratio (1.18) but also with a low average heat flux of 50500 kcal/m 2/h
on the inner tube surface. Together with the radial gradients is also shown the temperature
approach to equilibrium for the methane reforming and the methane decomposition reactions. It
is seen that there is a good agreement with the measured temperature data, and the mathematical
model has therefore been used to design the heat exchange type reformer shown in Figure 5,
without further adjustments of the parameters.
2.4. THE CATALYST
2.4.1. Intrinsic Activity. The steam reforming catalyst is normally based on nickel (Rostrup-
Nielsen, 1984a). Cobalt and the noble metals are also active, but more expensive. Attempts to
use non-metallic catalysts (Rostrup-Nielsen, 1984a) have not had commercial success, because
of low activity and thereby the impact of pyrolysis (reaction (9».
The catalyst properties are dictated by the severe operating conditions, Le. temperatures of 450-
950·C and steam partial pressures up to 30 bar. The activity depends on the nickel surface area
(Rostrup-Nielsen, 1984a). The nickel crystals will sinter quickly above the Tammann temperature
(Le. Ih'T,j being 590·C for nickel. This may be partly prevented by a stable micropore system
because the nickel particles may hardly grow larger than the pore diameter of the support
(Rostrup-Nielsen, 1984a).
The chemisorption of methane on nickel involves the breakage of a C-H bond (Ceyer et aI.,
1987) and this requires that the molecule has sufficient energy to overcome a barrier of about 52
kJ/mol (Beebe et al., 1987 and Chorkendorff et al., 1990) and that it hits a free nickel site with
free neighbor sites (Alstrup et al., 1990). The rate of adsorption is an order of magnitude higher
on the open (110) nickel surface plane than on the dense (111) surface plane. The activated
chemisorption of methane is the rate determining step in steam reforming (Rostrup-Nielsen,
259
1984a). There is general agreement on first order kinetics with respect to methane, but the impact
of steam and hydrogen on the rate is complex (Khomenko et al., 1971 and Xu et al., 1989). The
kinetics depend on the temperature range and the catalyst composition. The rate of the shift
reaction (2) is much faster and it can be assumed to be at equilibrium in all positions of the
reformer.
Temp",atu'e
'~Tc __________________--,
800
75U
700+---+----cI----+---+~"'i
A.. ald,Slance
,ml
Figure 6. Measured and Calculated Axial and Radial Temperature Profiles. Topsoe Monotube
Steam Reformer Pilot Data. Temperature approaches are shown for CH 4-reforming (reaction (I»
and CH 4-deposition (reaction (8». If t. T (1) > t. T (8), there is not potential for carbon
formation. This should be fulfilled at any position in the tube.
2.4.2. Transport Restrictions. For normal steam reforming catalysts, the utilization of the activity,
the effectiveness factor, is far less than 10% because of transport restrictions. The mass transport
restrictions are related mainly to pore diffusion, whereas heat transfer restrictions are located in
the gas film. The strong endothermic reaction results in a temperature drop of ca. 5-HfC over
the gas film (Rostrup-Nielsen et aI., 1988a). This means that the activity is roughly proportional
to the external surface area. The low effectiveness factor means (when assuming first order
kinetics) that the effective reaction rate for the methane reforming reaction can be written as
(Rostrup-Nielsen, 1984a):
6
r =- (23)
v dp,s
Similar rate expressions can be written for the other reactions taking place, but since the steam
reforming reaction is rate-limiting, it is permissible to use the simple correction for the
260
effectiveness factor as used in equation (23). The surplus of activity can be used in more
advanced reformer designs with only thin layers of active catalyst material e.g. for honey-comb
catalysts having low pressure drop (Stahl et aI., 1985) or even in metal supported catalysts on the
heat transferring surfaces. A special development has been "catalyzed hardware" (Laursen et aI.,
1990) for internal reforming in high temperature fuel cells.
2.4.3. Physical Propenies. The catalyst support material must be stable under process conditions
and under the conditions used during start-up and shut-down of the plant. In particular, resistance
to conditions during upsets may become critical. Degradation of catalyst may cause partial or total
blockage of some tubes, resulting in the development of "hot spots", "hot bands" or totally hot
tubes. Coking may cause similar problems.
The catalyst particle size and shape should be optimized to achieve maximum activity and
maximum heat transfer while minimizing the pressure drop. The high mass velocities in steam
reforming plants (G M = 40.000 - 70.000 kg m·~·l) necessitate a relatively large catalyst particle
size to obtain a low pressure drop across the catalyst bed; but the particle size is limited by the
requirement for effective packing. The pressure drop depends strongly on the void fraction of the
packed bed and decreases with particle size (Figure 7).
Also, the particle size has a minor impact on the heat transfer coefficient (CXw - lIdpo.2.l). The
optimum choice is a catalyst pellet with high voidage and high external surface area. Figure 7
shows an optimized catalyst shape, the 7-hole catalyst.
'\lIhil\
d,.
p t
t1 II tI,
Figure 7. Steam Reforming Catalyst. Topsoe R-67-7HR.
To summarize, effective catalyst activity is a complicated function of the particle size and shape
and the operating conditions . This, however, does not diminish the requirement for a high
intrinsic catalyst activity, in particular in those parts of the reformer having a high heat flux.
2.4.4. Heat Flux and Activity. The Approach to Equilibrium . The acceptable maximum heat flux
in reformer tubes is dictated by mechanical and metallurgical constraints rather than by the
catalyst activity. Present catalysts could work at average heat fluxes twice the present design
practice if the heat flux profile can be controlled (Rostrup-Nielsen, 1984a). However, deactivation
of the catalyst or unsuitable flux profile may result in overheating of tubes .
The approach to equilibrium for the reforming reaction can be expressed by (Rostrup-Nielsen,
1984a):
261
-AT _ C -C = u. des•."" dT (24)

It m. m.,oq ky dT dz
The equation illustrates that the approach to equilibrium depends not only on catalyst activity (k.),
but also on load (u.) and the slope of the temperature profile.
Most commercial catalysts have a surplus of catalyst activity. This means that apart from the
inlet of the reformer tube, the gas composition is at all positions in the tube not far from
equilibrium at the average catalyst temperature. In other words, dT/dz is the "driving force" for
the reaction, and the reaction proceeds as fast as the required heat can be supplied through the
tube wall.
If dT/dz becomes very high as in the upper part of top fired reformers or in the bottom of
bottom fired or terrace wall fired reformers, or if the catalyst looses activity, e.g. by poisoning
or ageing, then the reaction rate may not be able to follow the rate of heat input, and the
temperatures of the gas and the tube wall and also the approach to equilibrium will increase.
It is evident from the above and also from eq. (12) that lack of catalyst activity will cause high
temperature both in the gas and in the tube. The advantage of high catalyst activity (and the
disadvantage of an unsuitable flux profile) is illustrated in Figure 8 which shows calculated tube
wall temperatures in a top fired reformer for various relative catalyst activities in the upper half
of the reformer tube. It is seen that loss of activity in the upper part of the tube may lead to
significant overheating of the tube.
Tube Wall
Temperature °c
950 TF ~ 0.20
900
TF ~ 1.0
850 Catalyst Activity in Bottom Part

of the Tube is Constant
800
750
700
0 25 50 75 100
Tube Length %
Figure 8. Tube Wall Temperatures in Top Fired Reformer at various Catalyst Activity Levels
(TF) in the upper 50% of the Tube (Storgaard, 1991).
2.4.5. Laboratory Experiments. The scale-down to laboratory reactors involves a substantial

change of the reaction conditions. Neither heat fluxes nor mass flows can be reproduced in bench-
scale units (Rostrup-Nielsen et al., 1988a).
The most serious problem in scaling down is associated with transport restrictions over the gas
film. Whereas industrial reformers operate at high Reynolds numbers (Re = 1000 - 10.000),
laboratory reactors are typically in the laminar flow range, and therefore the impact of film
restrictions can be significant. In particular, low pressure tests on large catalyst particles may be
misleading.
262
As a consequence, one should rather, on the one hand, perform experiments which have been
planned to achieve a full understanding of the catalyst system by means of gradientless
measurements, and on the other hand perform experiments in a full-size monotube pilot plant,
specially planned to provide the best possible design data.
A compromise may be to study industrial-size pellets in internal recycle reactors (Rostrup-
Nielsen et al., 1988a), which at a high recycle rate approach a continuously stirred tank reactor
(CSTR). The mass velocity in such Berty-type reactors is still one order of magnitude lower than
in industrial reformers, and the temperature gradients over the gas film on the catalyst surface
are still significant. Hence, it is necessary to measure the catalyst pellet temperature directly by
fitting a thin thermocouple well into a drilled hole in one of the pellets.
2.4.6. Sulphur Poisoning. Sulphur is the most severe poison for steam reforming catalysts
(Rostrup-Nielsen, 1984a). All sulphur compounds in the feed will be converted into hydrogen
sulphide at reforming conditions, and hydrogen sulphide will chemisorb on the nickel surface.
The Ni/H2S-chemisorption is well-understood from surface science. The monolayer of
chemisorbed sulphur may be considered as a two-dimensional sulfide with ca. 0.5 S-atom per Ni-
atom. The sulphur coverage below saturation is determined by the H2S/H 2 ratio and temperature
(Alstrup et al., 1983).
Os = 1.45-9 .53-10-5:"f +4. 17-1O-5:"fin(H2S/H2) (25)
The expression is not valid for Os close to zero and to 1.0. Figure 9 shows sulphur coverages in
a tubular reformer calculated for various sulphur contents in the feed. The curves reflect the
impact of temperature and hydrogen partial pressure, both being highest at the exit of the
reformer tube. Also, Figure 9 demonstrates that there is no fixed limit of sulphur content in the
feed below which poisoning will not occur (Rostrup-Nielsen, 1984a). In practice, well-designed
hydrodesulphurization systems will result in sulphur contents below about 10 ppb in the dry
reformer feed.
In the operating reformer, sulphur poisoning is a dynamic phenomenon, and the pore diffusion
restrictions in the catalyst particles have a complex influence on the gradually developing sulphur
profiles through the tube. This can be simulated in a computer model (Christiansen et aI., 1980)
giving axial profiles in the tube as well as radial gradients in the pellets as function of time.
Also, it has been possible to establish a computer model which determines the effective activity
of a sulphur poisoned pellet from the radial sulphur profile (Bak Hansen et aI., 1991).
2.4.7. Carbon Formation. Steam reforming involves the risk of carbon formation by the
decomposition of methane and other hydrocarbons or by the Boudouard reaction (reactions (7) -
(10». Reactions (7) - (8) are catalyzed by nickel (Rostrup-Nielsen, 1984a). The carbon grows as
a fibre (whisker) with a nickel crystal at the tip. The methane or carbon monoxide is adsorbed
dissociatively on the nickel surface (Alstrup, 1988). Carbon atoms not reacting to gaseous
molecules are dissolved in the nickel crystal, and solid carbon nucleates at the non-exposed side
of the nickel crystal, preferably from the dense (111) surface planes. Reaction (10) results in
pyrolytic carbon encapsulating the catalyst.
Carbon formation may lead to breakdown of the catalyst, and the build-up of carbon deposits
and degraded catalyst may cause partial or total blockage of some tubes resulting in development
of "hot spots" or hot tubes. The uneven flow distribution will cause a self-accelerating situation
with further overheating of the hot tubes. Therefore, carbon formation cannot be tolerated in
263
tubular reformers. The important problem is whether or not carbon is formed and not the rate
at which it is formed.
Sulphur
Coverage
1.0
Sulphur
0.8 Level ppm vol.
0.6
0.4
0.2
o ~--------------------~--------------
o 20 40 60 80 100
% of Reformer Tube Height
Figure 9. Sulphur Coverage of the Nickel Surface of a Reforming Catalyst at various Sulphur
Levels. Ammonia Plant Reformer (Rostrup-Nielsen, 1984a).
It is important to explore the limits of the steam reforming reaction. When these are known,
it is possible to establish a safe design basis for optimum conditions. For reforming of methane,
there are three different carbon limits to consider (Rostrup-Nielsen, 1988b).
Limit A corresponds to conditions in the reformer where kinetics allow methane to decompose
into carbon instead of reacting with steam, even if thermodynamics predict no carbon formation.
Carbon formation is then a question of kinetics, local process conditions and reformer design.
With proper reformer design, industrial operation at H 2 0lCH4 = 1.0 - 1.1 depending on pressure
is possible (Rostrup-Nielsen, J.R. 1988c).
Limit B is dictated by thermodynamics. Carbon will be formed if the equilibrated gas shows
affinity for carbon. The limit is a function of the OIC, HIC and inertlC ratio of the gas as well
as pressure.
Limit C is a result of controlled sulphur passivation of the reforming catalyst as practiced in
the SPARG process (see section 2.6.2).
2.4.8. Metal Dusting Corrosion. A given gas will have potential for carbon formation by the
(exothermic) Boudouard reaction (reaction (7» below a certain temperature, the Boudouard
temperature, TB, at which the Boudouard reaction is at equilibrium. When TB is high, i.e. when
the partial pressure of CO is high, the reaction may be catalyzed by hot metal surfaces. It is thus
important that a gas with a high T B does not come into contact with a metal surface with a
temperature below, but close to TB • In an operating reformer, the catalyst outlet temperature will
always be above TB (because carbon would otherwise be formed on the catalyst). A temperature
drop in the reformer outlet system or in the cooling channels of the heat exchange reformer
264
could, however, bring the product gas below To, i.e. into an area where carbon may be formed
on the metal surface.
At most conditions, Fe-Ni-Cr alloys are protected against carburization by an oxide layer.
However, if this film is destroyed, a catastrophic corrosion can occur (Grabke, H.I. et aI 1987).
The corrosion starts by pointwise attack, probably by carburization at defects in the oxide layer.
The corrosion products can easily be eroded and holes are formed in the material similar to
pitting. This type of corrosion is called "metal dusting". Very often, it is observed in a narrow
temperature gap.
2.5. REFORMING OF HIGHER HYDROCARBONS
2.5.1. Reactivity. Higher hydrocarbons give rise more easily to carbon formation than does
methane, and special catalysts containing alkali (Rostrup-Nielsen, 1984a) and (Ridler et aI., 1989)
or based on active magnesia (Rostrup-Nielsen, 1984a) and (Rostrup-Nielsen, 1975) are required
for reforming of naphtha and similar feedstocks.
Carbon can be formed via the whisker mechanism as for methane (reaction (9)), but it may also
be formed by thermal cracking of the hydrocarbons (reaction (10)) taking place above 600-650°C.
In fact, a steam reformer without a catalyst would operate like a pyrolysis furnace (steam cracker)
for ethylene production.
Operation at H20/C = 2-3 is possible for tubular reforming of liquid hydrocarbons depending
on feedstock characteristics, catalyst and reformer design (Rostrup-Nielsen, 1988c).
2.5.2. Olefins. Oletins are the most critical higher hydrocarbons with respect to carbon
formation. The rate of carbon formation is several orders of magnitude higher than for other
hydrocarbons. Oletins are normally not present in the feedstock, but they could easily be formed
by thermal cracking of higher hydrocarbons in over-heated preheaters (reaction (9)), or even by
oxidative coupling of methane in presence of air in the feedstock (see section 4).
With the pre-reformer, this problem has been eliminated, and it is possible to use a high
preheat temperature (650°C or above) without the risk of carbon formation (Rostrup-Nielsen,
1988c).
2.5.3. Adiabatic Pre-reforming. By adiabatic reforming, all higher hydrocarbons are converted
to methane and carbon oxides by reaction (1)-(3) at conditions where carbon formation does not
occur. The key operating parameters are the inlet temperature, the amount of hydrogen recycle,
the steam to carbon ratio, and the catalyst activity. Actual design conditions depend on the type
of feedstock. Typical operating temperatures are in the range of 380-500°C (Rostrup-Nielsen,
1988c and (Davies et aI., 1967).
For natural gas containing only minor amounts of higher hydrocarbons, operation at a steam
to carbon ratio as low as 0.25 has been demonstrated. For heavier feedstocks such as naphtha,
operation at a steam to carbon ratio of 1.5 is industrially proven. Pilot tests have been carried out
at a steam to carbon ratio of 1.0 with product recycle (Rostrup-Nielsen et aI., 1979).
In adiabatic pre-reformers, it is possible to process naphtha with a tinal boiling point up to
220°C and an aromatic content up to 30%. It may be possible to process even heavier feedstocks
depending on the operating conditions. During the operation of an adiabatic pre-reformer,
progressive deactivation takes place, mainly by sulphur poisoning. This phenomenon causes the
temperature profile to move in the flow direction (Davies et aI., 1967).
265
2.6. CO 2-REFORMING
2.6.1. General. The increasing interest for C\-chemistry has created a need for synthesis gas with
low H2/CO ratio. This can be obtained by adding CO2 to the reformer feedstock (reaction 4). The
Hz/CO ratio in reaction (4) is 1, whereas the H2/CO ratio is 3 when using steam (reaction (1».
The use of CO2 instead of steam represents no significant change in overall reaction kinetics.
However, the presence of CO z in the feedstock results in more critical conditions for carbon
formation because of lower H/C ratio (Rostrup-Nielsen, 1988c).
The ratio of Hz/CO in the reformer exit gas can be estimated by thermodynamic calculations.
The results of the calculations may be presented in an equilibrium chart for a given pressure,
Figure 10.
The selection of process parameters is limited by the potential for carbon formation. The curve
in Figure 10 shows the thermodynamic carbon limit (carbon limit B, section 2.4.7) considering
the deviation of the carbon structure from ideal graphite observed on catalysts. For O/C and H/C
ratios on the left side of the curve, there is thermodynamic potential for the formation of carbon.
It is obvious that operation on the left side of the carbon limit curve would result in more
economic conditions (lower steam and CO2-addition for a given Hz/CO ratio). The conventional
processes are limited by the carbon limit curve.
HIe H,oleH,
~p
/ 2.0
c~:
1.0
Ole
Figure 10. Carbon Limit Diagram, 6 bar abs. H2/CO ratios in exit gas indicated by dotted lines.
(Rostrup-Nielsen, 1988c).
One solution may be to carry out the reaction over noble metal catalysts, which show little
tendency for carbon formation (Rostrup-Nielsen, 1984a). The mechanism for whisker carbon does
not work, probably because noble metals do not dissolve carbon as do the non-noble metals.
Carbon-free operation has been reported for rhodium and iridium catalysts (Richardson et aI.,
1990) and (Ashcroft et aI., 1991).
A less expensive solution for large scale applications is the use of a partly sulphur poisoned
catalyst on which the sulphur blocks the nickel sites for nucleation of carbon. This is the basis
of the SP ARG-process.
266
2.6.2. Sulphur Passivated Reforming. Sulphur passivated reforming (Rostrup-Nielsen, 1984b) as

practiced in the Topsoe SP ARG process solves the problem of carbon formation and allows
operation on the left side of the carbon limit curve in Figure 10. This is accomplished by
"ensemble control", which means that the sites for carbon formation are blocked, while sufficient
sites for the reforming reactions are maintained. This effect is obtained by adding sulphur to the
process feed.
The progress in surface science has provided a basis for a detailed description of the
phenomena (Rostrup-Nielsen, 1991a). The adsorbed sulphur atom results in a deactivation of the
neighboring nickel atoms. The rate of carbon formation decreases more with sulphur coverage
than does the reforming rate reflecting that the ensemble for the reforming reaction is smaller
than that required for the nucleation of the carbon whisker.
The retarding effect of sulphur is a dynamic phenomenon. This means that carbon may be
formed at certain conditions in spite of sulphur passivation - although at strongly reduced rates
and by a mechanism different from the formation of whisker carbon. Therefore, it was important
to develop design criteria to make sure that the kinetic balance is in favour of no carbon
formation at all positions in the reformer tube. This work was carried out mainly in the full-size
monotube process demonstration plant (Dibbern et al., 1986). The influence of various process
parameters (pressure, heat flux, sulphur content in feed, etc) was studied. It was demonstrated
that the impact of variations in sulphur content in the feedstream on tube wall temperature and
exit gas composition was completely reversible.
It was possible to operate at heat fluxes close to 80.000 kcallm2 /h in spite of the sulphur
passivation. The catalyst temperature increases quickly to above 750-800°C, at which the
reforming rates are sufficient for conversion of methane even at the high load. The high reaction
temperature means that higher hydrocarbons must be converted in an adiabatic pre-reformer to
eliminate the risk for carbon formation by thermal cracking (reaction (10)).
The ensemble control allows operation at (H20 + CO2)1CH 4 ratios close to stoichiometry.
Operation on mixtures of CO 2 and methane without steam is also possible except for the steam
required for prereforming of the higher hydrocarbons in the feed. No steam was needed when
operating on pure methane (C02 /CH 4 = 1.2) in a laboratory reactor. Conversion of CO2 to
CO - by reaction (4) and by the reverse shift reaction (reaction(2)) -of up to 75% may be
achieved.
Table 2 shows a variety of process conditions tested in a full-size monotube process
demonstration unit.
TABLE 2. SPARG Tests in Full-size Monotube Reformer.

O/C 1.15 1.32 1.27 1.15 1.07 1.35 1.48
H/C 6.30 3.71 3.40 3.30 2.97 1.93 2.07
H,oICH. 1.15 0.91 0.96 0.73 0.50 0.35 0.62
CO,lCH. 0 0.59 0.64 0.77 0.80 1.55 1.66
P, exit, bar 1-6 5.6 6 1 1 5.5 14
T, exit, °C 950 900 880 925 935 930 930
The sulphur present in the SPARG product gas inhibits carbon formation and metal dusting
corrosion in the outlet system, even if the operating conditions predict that carbon formation is
267
possible. This is not surprising because a main process in metal dusting (Grabke et aI., 1987) is
the formation of carbon on the free Fe-Ni surface of the construction material. The mechanism
is equivalent to that described for formation of whisker carbon on the reforming catalyst (sect.
2.4.7), and chemisorbed sulphur blocks the nucleation of carbon.
2.7. AUTOTHERMAL REFORMING
2.7.1. Process Conditions. When using oxygen for the conversion of hydrocarbons, it is possible
to achieve high equilibrium temperatures. This allows the use of high pressures (40-50 bar) while
still maintaining a low content of methane in the product gas. The non-catalytic partial oxidation
(fexaco, Shell) requires very high temperature (ca. 1400°C) in order to cope with carbon
formation.
Catalytic autothermal reforming as practiced in the Topsoe process (Nitrogen 1962) solves the
carbon formation problem by using the catalyst for equilibration of the gas. Previous design
practice has involved the use of a high H 20/CH4 ratio in order to maximize hydrogen production.
However, the growing interest in synthesis gases with low H2/CO ratio has lead to a wish to
minimize the steam addition. Industrial operation has proven that the H20/CH 4 ratio can be
reduced to less than 1.4 mol/mol (Lowson et aI., 1990). Recent tests in the Topsoe pilot facilities
have shown that this ratio can be drastically reduced.
Hence, catalytic autothermal reforming offers an alternative to tubular reforming when cheap
oxygen is available.
With CO2 recycle or CO2 import, more CO can be produced essentially by the reverse shift
reaction (reaction (2)). However, CO2-conversion is feasible only when aiming at low H2/CO-
ratios. As an example, an overall conversion of CO2 of ca. 30% is achieved at a ratio CO 2/CH 4
of about 1 in the feed resulting in a Hz/CO in the product gas of about 1.0. This is much lower
than the conversion of CO2 obtained in SPARG reforming.
2.7.2. Selective Oxidation of Methane to Synthesis Gas. It would be tempting to replace the flame
in the autothermal reformer with a catalytic burner provided the catalyst could promote the
selective oxidation (reaction (5)), while avoiding the further oxidation of the products:
CO + 1/2 0 2 = CO2 +68 kcal/mol (26)

H2 + Ih02 = H20 + 58 kcal/mol (27)
Reaction (5) is only slightly exothermic with a heat of reaction comparable to that of the shift
reaction (reaction (2)). With a catalyst selective for the selective oxidation, it would be possible
to produce synthesis gas suitable for e.g. methanol synthesis at low temperature without the large
heat production and heat recovery required in using present reforming technology. With such a
catalyst, it might be possible to establish more economic flow schemes.
However, attempts so far have been in vain, since it is extremely difficult to eliminate the
oxidation of CO and H 2. A recent study (Ashcroft et aI., 1990) indicated that this was achieved,
but as Table 3 shows, the data are close to thermodynamic equilibrium taking reaction (1) - (3)
into account.
268
TABLE 3. Selective Oxidation of Methane to Synthesis Gas

(Ashcroft et al ., 1990), Temp. 777°C, Catalyst: Pr2Ru207
P, bar ah8 1 1 20
CH./Oz/Nz 211/0.5 21110 61110
Experiment
CH.-conversion, % 94 89 23
CO-selectivity, % 98 94 81
Hz/CO 2.02 2.09 2.20
Equilibrium
Refonningl8hift
CH.-conversion, % 93.8 90.3 25.3
CO-selectivity, % 97.6 96.1 88.6
Hz/CO 2.01 2.01 2.03
3. Products made via Synthesis Gas
3.1. AMMONIA
3.1.1. State-of-the-Art Technology. Ammonia synthesis gas is produced by a series of process

steps comprising hydrodesulphurization, primary and secondary reforming, high and low
temperature shift conversion, carbon dioxide removal, and methanation. A flow diagram of the
front-end of a very energy efficient version of this process (Dybkjaer, 1990) is shown in Figure
11. It represents the "state-of-the-art" for this technology. After hydrodesulphurization, a
prereformer is provided to reduce the load on the tubular reformer. High preheat temperatures
are used in such a way that the heat available in the waste heat section of the primary reformer
is recovered down to a low temperature for preheat of natural gas, reformer feed, process air,
and combustion air. Heat downstream the reforming section and the shift section is recovered for
production of high pressure steam. All heat down to less than 100"C - except for the heat used
in the reboiler in the CO2-removal unit - is used for high pressure steam production.
HOS Prereformer Primary secondary Shift Methanatlon

Reformer Reformer Conversion
Carbon
Dioxide
Combustion Air
Fuel Gas
Heat Recovery for
Steam Production Process
Condensate
Figure 11. Synthesis Gas Manufacture in "State-of-the-Art" Ammonia Process Front-end

(Dybkjaer, 1990).
269
Using this process scheme, integrated with an efficient synthesis loop and an efficient
steam/power system, net energy consumption as low as 6.50 Gcal/t of ammonia can be obtained
for a stand-alone ammonia plant at a cooling water temperature of 30°C (Dybkjaer, 1990).
3.1.2. Heat Exchange Reforming. In the state-of-the-art process, the amount of heat available
downstream the secondary reformer at temperatures above 450"C corresponds to about 60% of
the duty required for primary reforming. Therefore, it is tempting to consider using this heat for
the primary reformer in a heat exchange reformer (Dybkjaer, 1990), (Kitchen et a1., 1990) and
(Topsoe, 1979). If heat exchange reforming is introduced in parallel with the tubular reformer
without any changes in operating parameters on the process side, the size of the tubular reformer
can be reduced to about 40%. The effect of the introduction of heat exchange reforming on the
overall balances is thus a reduction in the fuel requirement for the fired reformer. All high level
waste heat is, however, absorbed in the heat exchange reformer, and the remaining waste heat
will only allow production of medium pressure steam which is mainly used as process steam.
There will, therefore, not be enough steam available for compressors, etc., and the plant becomes
dependent on import of energy as illustrated in Table 4. It is seen that the scheme based on heat
exchange reforming power is only competitive with respect to energy consumption if the imported
energy can be produced with an efficiency of more than 35 %.
TABLE 4. Comparison of Energy Consumption in "State-of-the-art"

Process and in Process with Heat Exchange Reforming. All figures
per t NH3 (Dybkjaer, 1990).
"State-of-the-art " Heat Exchange
Refonning
Refonner Feed, Gcal 5.25 5.25

Refonner Fuel, Gcal 1.40 0.40
Total Natural Gas Consump- 6.65 5.65
tion 3.0 -
HP Steam Production, t - 1.8
MP Steam Production, t 540 110
Power from Steam, kWh 575 555
Total Power Consumption, 35 445
kWh
Net Power Consumption, kWh
If the secondary reformer is operated with an excess of process air (about 50% above the
stoichiometric amount), or if the process air is enriched to an 02-content of about 30%, then the
sensible heat in the product gas from the secondary reformer is sufficient for the primary
conversion of natural gas in a heat exchange reformer, meaning that the fired reformer can be
eliminated. Such schemes require, however, extra installations, either for production of enriched
air or for removal of excess N2 from the synthesis gas, and they suffer of course also from the
reduced efficiency of the steam production described above.
Process schemes based on heat exchange reforming are mainly of interest in special situations
(Dybkjaer, 1990) where energy, especially process feed, is very expensive, or where cheap
power - in the form of imported electric power or power generated from excess steam or from
other installations - is available to supplement the insufficient amount of power available from
waste heat from the ammonia plant. It must thus be analyzed in each individual case whether a
process based on heat exchange reforming is competitive.
270
3.2. HYDROGEN
The most important use of hydrogen is for hydroprocessing in the petrochemical industry, but
hydrogen is also used for hydrogenation in the chemical and food industries and for reduction in
the metallurgical industry.
After the development of pressure swing adsorption (PSA) units in the 1970's, it became
possible to operate the steam reformer in hydrogen plants at lower steam to carbon ratios. Before
then, high steam to carbon ratios were required in order to limit the amount of methane in the
product hydrogen. Decreasing the steam to carbon ratio below a certain level makes it impossible
to use conventional iron-chromium high temperature shift catalysts due to the risk of the Fischer-
Tropsch reaction (Hoejlund Nielsen et aI., 1982). Instead, copper-based or copper-promoted shift
catalysts may be used (Dybkjaer, 1981 and (Boegild Hansen et aI., 1990).
Steam export, which is often undesirable in hydrogen plants, can be minimized by adiabatic
pre-reforming which allows high preheat temperatures of the reformer feed, and by preheating
of the combustion air to the reformer burners.
Hydrogen plants for fuel cells should have no steam export (Stahl et aI., 1985 and
Rostrup-Nielsen, et aI., 1991b). The heat produced by the fuel cell is sufficient for raising
process steam. Therefore, heat exchange reformers are the preferred choice. The concept shown
in Figure 5 was developed for this application.
3.3. METHANOL/SYNFUELS
For methanol production, a composition of the synthesis gas corresponding to a value of the
stoichiometric module (H2-CO)/(CO+C02) slightly above 2 is desirable, but in some processes
large excess of hydrogen is accepted. Surplus hydrogen is then recycled to the reformer as fuel.
If the module is below 2, the formation of by-products (higher alcohols, etc.) becomes excessive.
Most new large methanol plants are built in areas where low cost natural gas is available. If
the synthesis gas is produced by the conventional one-step process, with a steam reformer only,
the module will always be around 3 with natural gas as feed. Process studies (Soegaard-Andersen,
1989) have shown that for capacities above 1000-1500 tId it is economical to adjust the module
to the optimum value by adding an oxygen-fired autothermal reformer downstream the steam
reformer as shown in Figure 12. This two-step reforming process (Dybkjaer et aI., 1985) is
similar to the well-known process lay-out with a primary and secondary reformer used in
ammonia plants.
The additional investment required for the oxygen plant and autothermal reformer in the two-
step reforming process is more than balanced by the savings in the primary reformer and
synthesis gas compressor. Furthermore, the total energy consumption is reduced, typically from
7.5 to 7.0 Gcal/t when using two-step reforming instead of the one-step process. The latter figure
corresponds to an efficiency (LHV) of 68 %.
An alternative lay-out is the use of an autothermal reformer only, eliminating the steam
reformer. This process lay-out will always give a module below 2, making an adjustment of the
module necessary. The lay-out may be attractive if the capacity exceeds 3000 tId methanol and
the feedstock is natural gas.
In the two step process, the fired steam reformer might be replaced by a heat exchange
reformer. The hot synthesis gas from the autothermal reforming would then be cooled in the heat
exchange reformer, supplying the heat of reaction for primary reforming of hydrocarbon as
shown in Figure 13 (Topsoe, 1979). When the feedstock is lean natural gas the heat available in
the process gas matches the heat required for primary reforming; with heavier feedstocks, the
271
heat requirement for primary reforming increases and a system with parallel heat exchange
reforming and fired reformer - or adjustment of the synthesis gas module - becomes necessary.
In all cases, only medium pressure steam can be produced. This requires import of electric power
to the plant for the large compressors. Integration of synthesis gas production at relatively high
pressure and a low pressure synthesis loop could eliminate the need for synthesis gas
compression. Large amounts of power would, however, still be needed for gas circulation in the
synthesis loop and for oxygen production and compression.
Steam Autothermal
Reformer Reformer
Process Steam UP Steam to Turbines
Boiler Feed Water
Make-up Ga.
Heat Recovery
from Methanol
Synthesis
Figure 12. Synthesis Gas Manufacture in Methanol Plant. Two Step Reforming.
However, future high efficiency gas turbines or future low pressure methanol syntheses may
require the use of heat exchange reformers.
The considerations for methanol production are valid also for manufacture of synfuels. The
manufacture of synthetic gasoline by the Mobil MTG (Yurchak, 1988) or Topsoe TIGAS process
(Topp-Joergensen, 1988) proceeds via methanol or dimethyl ether as intermediate. Diesel can be
manufactured by the Fischer-Tropsch synthesis followed by hydro cracking of the wax product
(v.d. Burgt et al., 1988). Slurry bed Fischer-Tropsch processes for diesel may operate at a HiCO
ratio slightly lower than for methanol synthesis (Dry, 1988).
3.4. CO-RICH GASES
Carbon monoxide is an important intermediate in the synthesis of many chemicals, e.g.

isocyanates, acetic acid, polycarbonates and oxo-alcohols. Carbon monoxide is sometimes the
only desired product, but in most plants, a co-production of hydrogen is required. The hydrogen
product can either be a pure stream or mixed with the carbon monoxide (e.g for
hydroformylation).
In order to maximize the carbon monoxide production in a steam reformer, it is preferable to
operate at the lowest possible steam to carbon ratio, pushing the equilibrium of the shift reaction
272
(reaction (2» to the left. A lower steam to carbon ratio decreases the conversion of methane
(reaction (1» in the reforming reaction. In order to compensate for the lower conversion of
methane, the reformer pressure can be decreased or the reformer outlet temperature increased.
A decrease of the outlet pressure will necessitate compression of the synthesis gas, which is
undesirable due to the associated investments and operating costs. Instead, the outlet temperature
should be increased to about 950"C maintaining a pressure of 15-25 bar. The temperature increase
also has the advantage of pushing the equilibrium of the shift reaction towards carbon monoxide.
A reformer designed for such operating conditions is illustrated in Figure 4.
The selection of process lay-out and conditions in a carbon monoxide plant depends not only
on the H2/CO ratio, but also on the availability and unit prices of feedstocks and utilities.
When carbon dioxide import is available at low cost and a low H2/CO ratio is required, CO2-
reforming should be considered. This means the use of the SPARG process (section 2.6.2)
operating at the left side of the carbon limit curve (Figure 10). If a synthesis gas with a HiCO
ratio of below 1 is produced by conventional reforming, H20/CH 4 ratios of about 2.5 and a
COiCH4 ratio of 3-4 inlet the reformer are required (Figure 10). This leads to a large fuel
requirement in the reformer and to a very large CO2-removal unit and CO2-compressor.
A comparison (Vannby, 1991) of the economy of SPARG (C02 at no cost) versus conventional
reforming for the production of synthesis gas with a HiCO ratio = I, shows a reduction of
energy consumption of 19 % and investment savings of 17 %.
As an example, Sterling Chemicals, Texas City, USA, installed the SPARG process in an
existing reformer (Hanson and Stal, 1991), (Stal et aI., 1991). The HiCO ratio was decreased
from 2.8 to 1.8 by changing the H20/CH4 ratio from 1.85 to 0.9 and the COiCH 4 ratio from
0.38 to 0.54. This allowed Sterling to stop producing methanol, while continuing producing
syngas for its other products (acetic acid and oxo-alcohols) as illustrated in the flowscheme in
Figure 14.
HERMES
(Heat Exchange Reforming
for Methanol Synthc"i ... )
Feed
20 11 :====~- (Lean Natural
Ga~ + Steam)
L....._ _ Methanol
- - - Synthe . . L....
"'---'-\ Ga,
21 12
!l
11
2l
I I
22
1)
~s~ ~,/
Figure 13. Production of Methanol Synthesis Gas. Two step Reforming with Heat Exchange
Reformer (Topsoe, 1979).
273
, - - - - - CH4 Fuel
CO
HZ-CO
'-----,------'--- H2
NG
Figure 14. Sterling Chemicals; Plant Lay-out after Modification.

(Hanson et al., 1991).
When CO2 import is not available, the optimum process choice is "Advanced Reforming",
operating close to, but on the right side of the carbon formation curve, and with an outlet
temperature of about 950·C. This is illustrated by comparing three different process lay-outs
(Vannby, 1991) in Table 5.
Partial oxidation is operated without steam addition, but it has the disadvantage of being
dependent on supply of oxygen at elevated pressure. Conventional reforming is carried out at a
relatively high steam to carbon ratio of 2.5 and a reformer outlet temperature of 850·C or lower.
It is necessary to recycle all the CO2 in order to limit the feed consumption, giving an H2/CO
ratio of 3.0 inlet the cold box. Advanced reforming is carried out at a low steam to carbon ratio
of 1.35 and a high reformer outlet temperature of 950·C. At these process conditions, it is not
necessary to recycle CO2, In all three lay-outs, the optimum CO2-removal process has been
chosen, and the separation of H2 and CO takes place in a cold box. Excess H2 from the cold box
is used as reformer fuel.
The partial oxidation process has the lowest consumption of natural gas, but is penalized by the
consumption of oxygen. The relatively low oxygen price implies that there is a large nearby air
separation plant, delivering oxygen at elevated pressure. If a dedicated oxygen plant is to be built
the oxygen price would be considerably higher. Even though the consumption of natural gas feed
is lower for conventional reforming than for advanced reforming, the total consumption of feed
+ fuel is higher. Conventional reforming has a higher consumption of electricity due to the
requirement of CO2-recycle. When comparing the processes, it is clear that "Advanced
Reforming" is the most favourable (Vannby, 1992).
274
TABLE 5. Manufacture of Synthesis Gas with H 2 /CO= 1 (after Gas

Separation). Comparison of Various Technologies (Vannby, 1991).
Process Partial Conventional Advanced

Oxidation ReConning ReConning
Production fy:ures:
- H2 , Nm'/h 9,300 9,300 9,300
- CO, Nm'/h 5,000 5,000 5,000
- Steam Export, tlh 10 8 7
CODSllmlltion flI:ures;
- Natural gas feed + fuel,
Gcallh 48.4 55.1 51.8
- Electric power, kW 1600 1) 2500 1) 1700 1)
- Oxygen, t/h 5.05 0 0
Ollerati!!l: Costs: (M USD-

Iy) 6.20 7.05 6.63
- Natural gas 2) 0.64 1.00 0.68
- Electric power 3) 2.02 0 0
- Oxygen 4) -0.80 -0.64 -0.56
- Steam credit 5)
8.06 7.41 6.75
Total
110 115 100
Relative investment
I) Including CO2 -removal

and cold box
2) 16 USD/Gcal
3) 0,05 USDIkWh
4) 50 USD/t
5) 10 USD/t
4. Alternatives to Steam Reforming Technology. "Direct" Conversion.
4.1. SELECTIVITY
The oxidative conversion of methane into methanol or ethylene has attracted much interest as an
alternative route to convert natural gas into useful products (Hutchings et aI., 1989).
2CH4 + O2 = C2H4 + 2H20 + 66 kcal/mol (28)

CH4 + Ih02 = CH30H + 30 kcallmol (29)
The key question is selectivity, i.e. to minimize the losses by CO2 formation and the
consequently high heat of reaction.
+ 191 kcallmol (30)

275
The selectivity should be obtained at a sufficiently high conversion per pass to minimize the
recycle of non-converted methane.
The conversion into methanol has, so far, shown very small yields « 5%), whereas yields for
oxidative coupling appear to approach a ceiling of 25% per pass, irrespective of catalysts and
process conditions (McCarthy et a1., 1990). Typical selectivities for oxidative coupling of
methane to ~-hydrocarbons are 80-85% (of which 40-50% as ethylene). The ethane product has
a value comparable to that of the feed, but it can be converted into ethylene with an ultimate yield
of 81 % by pyrolysis (steam cracking) (Albright et a1., 1983).
When assessing the industrial potential, the results for "direct" methane conversion should be
compared with those proven for the "indirect" technologies via synthesis gas.
For comparison, the MeOH synthesis has a conversion per pass of ca. 40% with a selectivity
of 99.8 % resulting in a single pass yield of ca. 40 %. The ultimate yield of 94 % is obtained by
a recycle of unconverted synthesis gas in a recycle ratio of 3-4 vol/vol.
Figure 15 shows simplified flow schemes of the two alternatives. The indirect route to methanol
is based on steam reforming followed by methanol synthesis. The process consumes ca. 7 Gcal/t
corresponding to a thermal efficiency of 68 %. The synthesis gas route may also lead to gasoline
by further conversion of methanol via the Mobil MTG-process (yurchak, 1988) or by the Topsoe
TIGAS process (Topp-Joergensen, 1988).
Methanol Synthesis
C·atom %
H.O
CH, 79 CH3 0H 76 C3 +
21 CO. 24 CO.
Fuel
Direct Oxidation
o. r~
~ i----~...
...;.CH....:.:......--'*....,..
41Co=
34 Co~27 C. =
2S CO.
Figure 15. Indirect and Direct Conversion of Natural Gas. Simplified F1owsheets.
The synthesis gas route also consumes methane as fuel in contrast to the direct route. The fuel
is converted into carbon dioxide which represents a loss. However, Figure 15 illustrates that the
two routes have almost the same CO2 production which may be taken as a rough measure of the
process efficiency.
In other words, a direct methane conversion process should have a CO2-yield substantially
lower than 20 C-atom % in order to represent a break-through compared to the indirect route.
276
4.2. HEAT BALANCE
One argument in favour of the direct oxidative conversion of methane is that steam reforming
requires a large heat input which is only partly recovered in the synthesis - but at lower
temperatures. This argument is misleading.
The indirect routes are self-sufficient in energy and have no steam export. The direct route has
a heat production comparable to that of the TIGAS process, but only part of the heat may be
required for down-stream processes and recycle, whereas the rest must be exported as steam.
Figure 16 illustrates the internal heat recovery for a methanol plant. The excess heat available
for steam and preheat shown in the diagram is used for product purification.
)II
Saturator 048
Purge < 0.90 <-

Preheat > 1.02 1.02 ) Preheat
Steam r 0.26 II
06' Steam
KII
~ 2!j [(
067
) II I
Preheat
~~
7.23
Natural gas
) ) 9.35
Front end
665
Synthesis gas
110.28
) 22.17
)
11 0 .46
4.77
.74
Product
Loss
reforming
Methanol
section
synthesis
section
Figure 16. Energy Flow Diagram for a Methanol Plant.
Most of the heat produced in the reforming route (88 %) is recovered from the waste heat of
the flue gas from the reformer furnace and from the hot effluent of the secondary reformer. In
the synthesis loop, 60% of heat of reaction is recovered, the rest being lost by condensation of
methanol. Other heat losses include the heat of the reformer flue gas and cooling water. The total
heat losses amounts to 15% of the heat added to the two-step reforming process plus the heat of
reaction in the synthesis.
The direct route has a large heat production of which almost 60% is used for preheat of feed
to 800"C. A major fraction of the steam is available for export. In addition, the direct route has
a higher oxygen consumption than the indirect routes.
4.3. TEMPERATURE CONTROL
The heat transfer surfaces in a reforming based process can be designed at the maximum heat
fluxes determined by the metallurgy of the equipment. The direct oxidation routes suffer from
the problem that the heat recovery must take place simultaneously with a strict temperature
control in order to ensure maximum selectivity. This makes it difficult to use a simple cooled
277
tubular reactor. The heat transfer must be high enough to eliminate development of a hot spot
corresponding to the adiabatic temperature rise.
One method to assess the potential for run-away is to estimate the maximum allowable tube
diameter to keep the reaction heat in balance with the heat transfer (Froment et al., 1979).
Obviously, the design diameter will be lower than the critical diameter, typically by a factor 0.6.
A calculation was carried out (Dautzenberg et al., 1991) for typical yields (Figure 14), an
operating temperature of SOO·C, inlet pressure 5 bar, a residence time of O.5s and assuming a
recycle ratio of 3.9 as for the methanol synthesis. At these conditions, the adiabatic temperature
rise is 570·C. Because gas cooling is the only realistic alternative given the high reaction
temperatures involved, the overall heat transfer coefficient will be .s.200 kcal m·2 K l h· l .
The calculation shows that the tube diameter should be less than 20 mm. This corresponds to
a required length of almost 4 km tube/t C2-productlh. The calculations are very sensitive to
pressure. Lower pressure results in too high pressure drop. Higher pressure results in even
smaller tube diameter to cope with temperature run-way.
For comparison, the Fischer Tropsch ARGE process and the methanol synthesis are running
in boiling water reactors with a tube diameter of ca. 40 mm. The required tube length is 7.5 and
1 km/t productlh for the two syntheses, respectively.
The temperature control of the oxidative conversion of methane can of course be achieved by
diluting the reactants. This can be done by increasing the recycle ratio, which however will make
the complicated separation system downstream the reactor very expensive. As an alternative,
dilution can be accomplished by addition of steam (Leyshon et al., 1991), but this will spoil the
process economy. These arguments lead to the selection of a fluidized bed.
One elegant solution for heat removal is to combine the oxidation with the endothermic
pyrolysis of recycled ethane (Edwards et al., 1991) and (Quang et al., 1991).
As an example, the "Oxco" process (Edwards et al., 1991) shown in Figure 17 is based on a
fluidized bed reactor with oxidative conversion of methane (reaction (2S» taking place on a
CO 2 H20
-
C 2 + Alkanes
CH./CO/H 2
Diesel
Recycle CH.
1--------1 I
Methanation.
I CO
2 Gasoline
gas
Figure. 17. Simplified Flowscheme of the OXCO-process (Edwards et al., 1991).

278
narrow zone at the bottom inlet, whereas the pyrolysis of recycled ethane proceeds in the oxygen-
free zone at the top. The fluidized bed is able to ensure almost isothermal conditions thus
coupling the heat production of the oxidative coupling (54 kcallmol CH4 ) with the heat
consumption of the pyrolysis of ethane (33 kcal/mol C2H6)'
However, this process requires that the higher hydrocarbons be separated from the process feed
and this represents a severe penalty to the process economy.
In conclusion, the chemistry of the direct oxidative conversion of methane may well be
exciting, but the process engineering requirements (Dautzenberg et aI., 1991) and (Fox et aI.,
1990) still represent a severe obstacle before these routes may become economic alternatives to
the indirect process via synthesis gas.
The authors wish to thank Jens-Henrik Bak-Hansen, Helge Holm-Larsen, Thomas S. Christensen,
and Richard Vannby for assistance in preparing this manuscript.
NOTATION
Ci Molar concentration of component i (kmollm3)

Ci.eq Equilibrium molar concentration of i (kmol/m3)
Cp Heat capacity (kcal/kg/K)
~ Equivalent particle diameter (volume basis)
d, Inner tube diameter (m)
~,. Equivalent particle diameter (surface basis)
Deff Effective diffusion coefficient (m2/h)
Der Effective radial diffusivity (m2/h)
F Conversion (kmol/h/kmol feed)
F 0 Mass flow rate (kg/h)
G Mass velocity (kg/m~)
H Heat transferred (kcal/h/m3 bed)
.toH Heat of reaction (kcallkmol)
ki Intrinsic rate constant, volume basis (h'I)
Ie. Effective rate constant, volume basis (h'I)
~ Chemical equilibrium constant for steam reforming
M Mole weight (kg/kmol)
p Pressure (bar abs.)
Pi partial pressure of component i (bar abs.)
PeH Peclet number for heat transfer (peH = GCpd/A.r)
PeM Peclet number for mass transfer (PeM = Gd/Q/Der)
q Heat flux (kcallm2fh)
Q Duty (kcal/h)
QR Reaction quotient for steam reforming
r Radial distance in tube (m)
ry Effective reaction rate, volume basis (kmol/h/m3)
rw Intrinsic rate per unit catalyst weight (kmol/h/kg)
R Radius of tube (m)
Ri Inner tube water
Ro Outer tube water
279
s Stoichiometric coefficient
S Specific heat transfer area (m2/m tube)
Sp External surface area of catalyst particle (m~
SV Space velocity (Nm3/m 3 bed/h)
T Temperature (K)
Tc Catalyst temperature (K)
Tf Fluid temperature (K)
Tm Melting point (K)
Tw Tube wall temperature (K)
TR Catalyst temperature at tube wall (K)
11 T ref Temperature approach for steam methane reforming (K)
u, Superficial velocity (m/h)
U Overall heat transfer coefficient (kcallm2/h/K)
Vp Volume of catalyst particle (m3)
x Mole fraction
z Axial distance (m)
E Void fraction of catalyst bed
"1 Effectiveness factor
IIg Gas density (kg/m3)
(J Sulphur coverage
Aer Effective radial conductivity (kcallm/hr/K)
O/w Wall film heat transfer coefficient (kcallm2/h/K)
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OXIDATIVE COUPLING OF METHANE FOR THE UTILIZATION OF NATURAL GAS
M. BAERNS
Chair of Chemical Technology and Reaction Engineering
Ruhr-University Bochum
P. O. Box 10 21 48
D-4630 Bochum 1
Germany
ABSTRACT. Oxidative coupling of methane (OCM) to ethane, ethylene and minor amounts of higher
hydrocarbons besides the undesired carbon oxides occurs in the presence and absence of catalysts
between 700 and 900°C. High coupling selectivities are achieved when using catalysts consisting of cer-
tain reducible metal oxides but particularly in the presence of basic materials. Homogeneous noncatalytic
and catalytic gas-phase kinetics of the oeM reaction are dealt with. Catalysis and respective catalysts are
discussed. Finally, reaction and process engineering aspects are considered.
1. Introduction
Natural gas has received wide-spread attention during the last decade as a source for liquid
fuels and chemical feedstocks but also from an environmental point of view. In the following,
the reasons and implications of this interest and the objectives of present research and devel-
opment work and of this contribution are dealt with.
Large deposits of natural gas, which is mainly composed of methane, are found at many
locations throughout the world; often it can be easily transported from the source to the con-
sumer via pipelines. There exist, however, also situations where this does not apply. Not all
the available and produced natural gas is utilized. Vast quantities are frequently flared particu-
larly in remote areas where natural gas might be also associated with the production of crude
oil but from where its transport in gaseous form is impossible. It has been recognized during
the last decade that flaring is not acceptable from an environmental point of view. In order to
save the value of such natural gas and to utilize it large marked efforts are being made to trans-
form it into liquid hydrocarbons or at least more valuable products like ethylene which are
more easy to transport or to convert further to liquid. This intention is even more applicable to
the large resources of natural gas which are available worldwide and which eventually will
outpass crude oil as a hydrocarbon resource in the long-range future (see Figure I, [1]). There
are various means to achieve this objective. Well proven technologies are natural gas transfor-
mation to syngas which may then be either converted to methanol or by Fischer-Tropsch (FT)
synthesis to hydrocarbons. From methanol gasoline-type hydrocarbons as well as ethylene and
propylene can also be produced catalytically using pentasil-type zeolite catalysts in the MTG
(Methanol-To-Gasoline) and MTO (Methanol-To-Olefins) processes. The MTG process based
on natural gas is successfully operated in New Zealand. A FT plant is presently under con-
283
H.l. de Lasa et al. (eds.). Chemical Reactor Technology for Environmentally Safe Reactors and Products, 283-316.
284
struction at Bintula, Malaysia, by which methane is converted via a three-step chemical process
to gasoline- and diesel oil-range hydrocarbons (Shell Middle Distillate Synthesis, SMDS). All
these processes have in common that various process steps are required to obtain the final pro-
duct (FT-SMDS: ~ syngas ~ waxy hydrocarbons by FT ~ engine fuel by cracking; MTG
and MTO respectively: ~ syngas ~ methanol ~ gasoline or olefins respectively). Against
this background it is the aim of more recent research and development work to convert natural
gas to higher-value products by processes which require less chemical process steps reaction.
When natural gas is used for energy supply, which is presently and certainly also in the future
its main usage, any spillage by leaking has to be avoided. On global-warming grounds, leakage
has to be limited to 3 to 6% according to Rohde [2].
UJ
o+-
L!J
1970 1975 1980 1985

Year
Figure 1. Evolution of proven reserves of oil and gas in the world [1].
Present research and development work in the direct conversion of methane is mainly aimed at
the oxidative coupling of methane (OCM) to ethane and by its dehydrogenation to ethylene.
Although there are also quite significant research efforts to directly produce the oxygenates of
methane i.e., methanol and formaldehyde, no results have become known which may be con-
sidered as a basis for future commercialisation. In a recent economic evaluation by Geerts et
al. [3] it was shown that the direct conversion of methane to methanol is presently not eco-
nomical although expenditure for investment would be less for the direct route (i.e., 113 vs.
123 million US $ for a plant capacity of 400000 tons methanol per year). The poorer perfor-
mance of direct conversion is mainly due to the extra costs for oxygen and the poor utilization
of methane. It appears that assuming a degree of methane conversion of at least a few percent a
minimum overall methanol selectivity of at least 75 % would be required which is far from the
data which have been published . Even less favorable is the direct formation of formaldehyde.
In the coupling of methane, the presence of oxygen is required for thermodynamic reasons
if the reaction is to be carried out at temperatures significantly below 1600 K. This is illus-
trated for the formation of ethane and ethylene:
2 CH 4 = C2H6 + H2 LlG lOOOK = + 71 kJ mol- 1 (1.1)

2 CH 4 = C2H4 + 2 H2 LlG lOOOK = + 80 kJ mol- 1 (1.2)
285
The dependencies of the yields of ethane (eq. 1.1) and ethylene (eq. 1.2) on temperature are
separately shown in Figure 2a. The simultaneous formation of these hydrocarbons is presented
in Figure 2b. Both calculations are based on a total pressure of 100 kPa. When oxygen is
added, the free energies become strongly negative:
2 CH 4 + 0.5 02 = C2H6 + H20 .1G lOOOK = - 121 kJ mol- 1 (1.3)

2 CH4 + 02 = C2H4 + 2 H20 .1GlOOOK = - 305 kJ mol- 1 (1.4)
-1
100-(a)
'!. 1 - - __~c-
% r- -- c~He -__ -cc--~

2
0.1 - _ ~~ -,,"_- --
-- - 1----- ----
1~~__~-L__~-L__~~
0.01 1
10001200140018001800200022002400 10001200140016001800200022002400
T/K T/K
(a) non-simultaneous reaction of methane to (b) simultaneous reaction of methane to ethane

ethane and ethylene. and ethylene.
Figure 2a and b. Dependence of thermodynamic-equilibrium yields of ethane and ethylene from methane
on temperature at a total pressure of 100 kPa.
These reactions occur even in the absence of a catalyst in the gas phase, although selectivity is
low due to deep oxidation to COx. To suppress the total oxidation of methane as well as of the
hydrocarbon products Le., to obtain high C2 + selectivities, the use of suitable catalysts is
necessary and hence, their further improvement is of prime importance. Besides selectivity also
methane conversion should be high to achieve high C2+ yields by which subsequent separation
efforts are minimized in any process scheme. To reach this goal also the optimization of reac-
tion conditions and of reactor design taking the high exothermicity into account are important
targets. As a basis for reaction engineering work, the kinetics of the OCM reaction are of spe-
cial interest. These reactions are not, however, of a straight-forward nature since homogeneous
gas-phase reactions are strongly interfering with the catalytic reaction. Finally, process flow
sheeting as a means of evaluating the economics of direct methane conversion processes and
particularly the production of ethylene has increasingly received attention during the more
recent past [4].
The present contribution deals with the following subjects with respect to the OCM reac-
tion: homogeneous gas-phase reactions, catalysis and catalyst development, optimization of
reaction conditions, kinetics, and reactor design along with some suggestions on possible pro-
cess flow sheets. Partly, detailed reference is made to results reported in the literature, but
mainly research results from the author's laboratory are considered.
286
2. Non-Catalytic Homogeneous Gas-Phase Reaction [5]
When methane and oxygen are converted in the gas phase at temperatures between 850 and
1150 K, C2 hydrocarbons are formed besides carbon monoxide along with minor amounts of
C3 + hydrocarbons, formaldehyde, methanol and carbon dioxide. The selectivities depend on
the conditions applied i.e., partial pressures of methane and oxygen respectively, as well as
temperature.
Total pressure is less important than the methane-to-oxygen ratio. Some typical results illu-
strating the various relationships are presented in Figures 3a, band 4a, b. From Figures 3a
and 3b it becomes apparent that there is an optimum temperature for maximizing C2 + selec-
tivity. The hydrocarbon selectivity is highest at low oxygen conversion, indicating that forma-
tion of CO is at least partly a consecutive reaction (see Figures 4a and 4b).
Gas-phase conversion of methane and oxygen is accessible to reaction modeling and simu-
lation based on the many occurring elementary reaction steps for which kinetic data are avai-
lable in literature. Such simulations have been carried out applying a reaction system consi-
sting of up to 193 elementary reactions involving 33 species (CH4, ·CH3, ·CH2, ·CH, C2H6,
·C2HS, C2H4, ·C2H3, C2H2, ·C2H, C3HS, i-·C3H7, n-·C3H7, C3H6, ·C3HS, ·CH30 2,
CH302H, CH 30H, CH 20H, ·CH 30, CH 20, ·CHO, CO, CO2, 02, H02·, H 20 2, ·OH, ·H,
H20, ·0, H2, N2). The elementary reactions shown in Figure 5 comprise activation of
methane, non-selective oxidation of ·CH 3 radicals, selective coupling of these radicals, dehy-
drogenation of ethane, and oxidation of C2 + hydrocarbons. Kinetic simulations were based on
two different sets of elementary steps (Models A and B, see Figure 5). Model B is an extended
version of model A, where the formation and reactions of the ·CH 30 2 radicals and its suppo-
sed secondary product CH302H were accounted for.
The experimental data agree rather well with the simulations as is evident from the above
Figures 3 and 4, in which the symbols represent the experimental results while the lines corre-
spond to the simulations. The dependence of ethane and ethylene selectivity on the methane-to-
oxygen ratio at a total pressure of 41 kPa and 1044 K as simulated by the described procedure
is shown in Figures 6 and 7. From the comparison of experimental and simulated results it
turns out that model A is equivalent to model B for temperatures above 1000 K. For lower
temperatures model A gives too high C2 + selectivities. This indicates that the CH30 2 radical
reaction path is important below that temperature.
On the basis of the relationships obtained from such simulations over a wide range of
experimental conditions, the following optimum reaction conditions for maximizing
C2 selectivity can be derived: (1) The reaction temperature should range between 1000 and
1100 K depending on the total pressure and the CH4/02 ratio. (2) The total pressure should be
around 400 kPa. (3) The ratio of methane-to-oxygen should not be less than 7, since otherwise
non-selective reactions become very important.
Recognizing that there are strong similarities between the non-catalytic and the catalytic
oxidative coupling of methane some conclusions can be drawn for catalyst design taking into
account that methyl radicals formed on the catalytic surface by dissociation continue to react
partly or fully in the gas phase after desorption. The primary coupling reaction to ethane is
second order in methyl radicals while the non-selective reactions are only first order in methyl
radicals and in the various oxygen containing species involved. For this reason methyl-radical
concentration should be kept high; this is presumably most easily achieved on or close to the
surface when the rates of methane adsorption and dissociation are fast and the adsorption
287
S(t) 1[%] S(t)I[%]

60 r--=------=------;:::=:::===:::;-l25
o (ZH 6 o CO
o (zH 4 80 o COz
50 o (2- 00 -Model B
-Model B - - Model A 20
--Model A ./
40 ./
/
/
60 15
/
/
30 /
/
/
/ 10
20
40
,8 0
0 I
(0 2 5
10 ' .... 0
.............. 0
0 0
20 i
0
750 950 1050 1150 750 850 950 1050 1150
T I [K] T I[K]
Figure 3a. Dependence of ethane and ethylene Figure 3b. Dependence of COx selectivity on
selectivity as well as total selectivity to C2 + reaction temperature.
hydrocarbons on reaction temperature.
Comparison of experiment (symbols) and simulation (lines) (CH4/0Z/NZ = 10: 1:4; P tot = 410 kPa;
XOZ = 99%).
S(i)1 [%] S(i)/[%]

100,---'---------;======::::;-] 60 rr=====~-------,20
o (zH 6 o (0
o (zH 4 o GO z
o [z_ 50 - Model B
-Model B - - Model A
15
--Model A
40
30 10
20
10
r
(02
5
0
OL---L--__ ~ __ ~ ____ ~ __ ~
o 20 40 60 80 100 00 20 40 60 80
Xo)[%] XO)[%]
Figure 4a. Dependence of ethane and ethylene Figure 4b. Dependence of COx selectivity on
selectivity as well as total selectivity to oxygen conversion.
CZ+ hydrocarbons on oxygen conversion.
Comparison of experiment (symbols) and simulation (lines) (CH4/0Z/NZ = 10: 1: 1.5; P tot = 410 kPa;
T = 1044 K).
288
CH.
CH20
i1
CHO
fl
=r
~
C2H3
i1
C2H2
H
•
C3Ho
li
C3H5
CO C2H
1
CO2
Figure 5. Reaction scheme for the kinetic models on oxidative methane coupling in the gas phase applied
in model A and B.
100
80
SC,H,60
% 40
20
125102040
- [H 4 /0 2 -
Figure 6. Dependence of ethane selectivity, SC2H6, on CH4/02 ratio and on the degree of oxygen con-
version, X02 (T = 1044 K, P tot = 410 kPa, 02/N2 = 1:1.5).
289
50
40
SC,H 4 30
%
20
10
99
125102040
- CH 4 /02-
Figure 7. Dependence of ethylene selectivity, SC2H4, on CH4/02 ratio and on the degree of oxygen
conversion, X02 (T = 1044 K, P tot = 410 kPa, 02/N2 = 1: 1.5).
capacity of the catalytic surface for methyl radicals is high. The rate constant of the second-
order coupling step should be enhanced by the catalyst if it occurs on the surface. Simultane-
ously the catalyst surface should act as a scavenger for those gas-phase radicals containing
oxygen (i.e., primarily HOZ·, ·0, ·OZ) which are initiating non-selective reactions. Further-
more, the catalytic surface should preferably catalyse the reactions of these species with the
hydrogen dissociated from the methane molecule.
3. Catalysis and Catalyst Development
Oxidative coupling may be achieved in two different ways:

(1) Methane reacts with a reducible metal oxide (reagent) which makes the reaction occur
catalytically in the desired direction; the reduced metal oxide is subsequently reoxidized by
gas-phase oxygen (see eqs. 3.1 and 3.2). This mode of operation has been termed "redox"
method.
2 CH 4 + Me(Zn) + ~-° (3.1)
Me(Zn-Z) + 0~=1+ 0.5 0z ~ Me(Zn)+o k (3.2)
(2) Methane and the oxidant (most commonly oxygen) are simultaneously passed over a cata-
lytic solid (catalyst) in order to carry out the coupling reaction; this is the called "cofeed"
method.
catalyst
CH 4 + 0.5 0z • CZ~ + H20 (3.3)
Both methane and ethane can also be oxidized non-selectively to give carbon oxides; ethane
can further react by thermal or oxidative dehydrogenation to ethylene which, in turn, can
undergo total oxidation. These reactions may occur on the catalytic surface but also partly in
the gas phase. The various solid materials used either as reagents or catalysts comprise mainly
290
reducible multivalent metal oxides, irreducible basic metal compounds and rare-earth metal
oxides or their respective mixtures.
Since nowadays work is carried out almost exclusively according to the "cofeed" method,
which is also the author's preference, only this subject is pursued in this paper.
In the oxidative coupling of methane to ethane, ethylene and minor amounts of higher
hydrocarbons (i.e., C2 + hydrocarbons) a large variety of solid metal-oxide materials has been
applied as catalysts; they may be loosely categorized as reducible and non-reducible ones. Only
the former solids can be applied in the redox type of operation. Both types of catalysts can be,
however, applied in the cofeed method in which the oxidant (most commonly oxygen) and
methane flow simultaneously through the bed of solid material acting as the catalyst. Already
in the early stages of the research on oxidative methane coupling it became apparent that
doping reducible metal oxides, e.g. r-alumina supported PbO, with alkali compounds, or
applying alkali and alkaline earths compounds of high basicity as well as their mixtures as
catalysts, or using supports of different acidity and basicity respectively affect the selectivity of
the OCM (for references see [6]). As a general rule it has been observed that decreasing
acidity and/or increasing basicity of the catalyst surface improves C2+ selectivity and reduces
the undesired carbon oxides formation.
These findings have been well documented in various review articles (for references see
[7]). Therefore, only selected results are cited in this contribution to leave space for introduc-
ing more recent results in the area of catalytic oxidative coupling of methane.
3.1 SUPPORTED LEAD OXIDE
One of the early catalytic compounds used was lead oxide supported on different carriers. It
was observed that the selectivity of such catalysts was improved by adding alkali compounds
as is illustrated in Figure 8. Also when using support materials of different surface acidity or
basicity respectively which also exhibit some inherent activity for methane conversion, selec-
tivity was affected (see Table 1). The more basic or the less acidic the support, the higher was
C2 + selectivity. This result is also supported by the surface pK values which were derived by
adsorbing certain probe molecules (Benesi method). These values represent a measure of acid-
ity or basicity and are presented in Table 2; (PK equal 7 is neutral; larger values correspond to
basicity, while lower values point towards acidity). Acidity was in some instances also char-
acterized by the isomerization reaction of cyclohexene to methyl cyclopentane. The respective
results were in agreement with the Benesi method [8].
TABLE 1. Cn selectivity (n 2 2) of PbO catalysts when using supports of differ-

ent acidity/basicity (catalyst size: 3 x 2 mm, T = 1013 K, PCH4/P02 = 8,
PCH4 = 65 kPa).
Catalyst (wt %) Selectivity / %
C2 C3 C4 EC n
PbO (20)/AI203·Si02 20 20
PbO (31 )/r-AI203 53 1 54
PbO (05)/a-AI203 56 2 59
PbO (08)/Si02 56 9 65
PbO (31 )/MgO 65 3 69
291
2-)60 ~y--- - j
A
J
1['
I
0/0
o_-",H,
50
,,:::::~c--r
40
-o- J (0 1
30
i',H,
20
10
-1 "
o 09 42
Figure 8. Effect of Na20 doping of a PbO(22 wt'-%)/yAI203 catalyst on selectivity (T = 1023 K,

PCH4 = 70 kPa, P02 = 7 kPa, W/F = 0.046 g·s·ml- ).
TABLE 2. Selectivity and acid-base properties of various catalytic oxides.
Catalytic oxide SC2+ pKA

wt.-% %
1.5 Li 2O/CaO 73 + 12.2

3.0 Na20/CaO 67 + 9.3
4.5 K20/CaO 67 + 9.3
Si02, kieselgel 15 + 6.8
)'-AI 20 3 3 + 3.3/+ 4.0
AI 20 3 x Si02 1 - 5.6
3.2 ALKALINE EARTH AND ALKALI/ALKALINE EARTH METAL OXIDES
From the above observations it was concluded that basic solids are more appropriate catalysts
than acidic materials. This fundamental assumption was confirmed by the selectivity of the
various alkaline earth oxides (see Table 3). Basicity increases from top to bottom along with
the selectivity; however, the selectivities obtained in the best case are not much better than for
the lead oxide catalyst. From Tanabe's [9J work it is well known that surface basicity increases
by impregnating such oxides with alkali anions. When using such materials as catalysts, selec-
tivity is increased (see Table 4); this may be considered as a very convincing proof that basic-
ity is a very important feature of successful catalysts. It was further shown that the amount of
292
alkali on the surface influences selectivity (see Figure 9). A certain mInImum amount of
roughly 30 % of sodium is required in the case of calcium oxide. The overall amount of
sodium needed to achieve this surface concentration depends on the calcination temperature by
which the redistribution of the alkali compound is determined after impregnation and drying.
TABLE 3. C2 + hydrocarbons selectivity of alkaline earth oxides (T = 1013 K,

P CH4 = 66 kPa, P 02 = 8 kPa, P N2 = 26 kPa; X02 ~ 80 to 90 %).
Oxide BeO MgO CaO SrO BaO
SBET/m 2g- 1 n. dtd. 24 a 37 b 7.6 c 6.3 d 0.1 n. dtd.
SC2+ 1% 22 47 22 47 55 72 70
SC3+ 1% 0.2 1.8 0.1 1.2 3.2 7.6 7.2
a) Prepared from Mg5(OHh(C0 3)4 * 4 H 2O

b) Prepared from Mg(OHh
c) Prepared from CaC03
d) Prepared from Ca(OHh
100
--
~
>..
50
:~
u
<lJ
aJ
VJ
+
N
L.J
-
0 SO 100
surface Na content / at. %

Figure 9. The dependence of C2+ selectivity on the concentration of sodium dispersed on CaO
(T = 1013 K, P tot = 100 kPa, X02 = 80-95%).
6.5 7.1 7.3 8.5

• * o
293
TABLE 4. Selectivity of alkali-compound-on-CaO catalysts (T = 1013 K,

PCH4 = 66 kPa, P02 = 8 kPa, PN2 = 26 kPa; X0 2 ;;e: 80 to 90 %).
Alkali compound Selectivity I %

(mole%) C2 H6 C2 H4 I: C2 I: C3 I: C4 COx
3.0 Li2C03 27 41 68 4.8 4.0 23

3.5 Na2C03 25 42 67 4.6 5.3 22
3.7 K2 C0 3 20 42 62 3.3 5.0 28
2.3 LiOH 30 39 69 5.4 2.7 23
2.6 NaOH 29 34 63 5.2 4.8 26
2.6 KOH 22 43 65 3.8 3.5 27
1.4 Li 20 28 39 67 4.8 3.4 25
1.3 Na20 27 40 67 5.5 5.5 22
1.2 KzO 24 42 66 3.9 2.5 26
3.3. La203 - CaO
Since lanthana, which is a basic oxide, had been shown to act as a catalyst in the oxidative
coupling reaction, it was combined with CaO (also basic) and the catalytic performance of this
composite material was studied [10]. Depending on the method of preparation and the precur-
sor material used, selectivity is differently affected by the overall lanthana concentration (see
Figure 10). When correlating selectivity to the surface concentration of lanthanum, however, a
similar pattern is obtained for all the different types of preparations (see Figure 11).
Acetone/Propylene /10-8 mol

140 rp 14 m1 S
120 12
70
100 10
80 08
so o Fluka O. IAldrlCh
60 06
6 Fluka O. I Alia
40 04
o Jansspn Nit lAId rich
• Janss.n NIt IAlta 20 01
• AldrICh NIt lAlla
30~--~---L----~--~---"
0 00
o 10 40 60 Be lOG 40 60 80 100
(bulk /
La a to,'0 C~~rf /%
Figure 10. Dependence of Cz + selectivity on Figure 11. Effect of the surface content of
overall bulk composition of LaZ03/CaO cata- lanthanum on CZ+ selectivity, acidity (rp, rate
lysts prepared by different methods and using of IPA conversion to propene), and relative
different precursor compounds supplied by diffe- basicity of La-Ca oxide catalysts.
rent distributors.
(Experimental conditions: P CH4 = 93 kPa, P0 2 = 7 kPa, XOZ > 90%, T = 1013 K).
294
According to the previous conclusions it was expected that the maximum selectivity should
coincide with the maximum basicity. This was, however, not true as can be derived from Fig-
ure 11, showing not only selectivity but also the ratio of acetone-to-propene formed from iso-
propanol and the rate of propene formation. This reaction is often used as a probe reaction for
determining acidity and basicity: propene formation is assumed to be indicative for acidic sites
while both acidic and basic sites are needed for acetone formation. The maximum selectivity is
close to the maximum of the propene formation rate. From this it was concluded that besides
surface basicity a certain amount of surface acidity is required for maximizing selectivity. This
is achieved by incorporating the lanthanum cation which may act as a weak acid in the host
matrix.
3.4. MODIFICATION OF BASIC CATALYTIC SOLIDS
Besides the aforementioned acidity and basicity, by which the performance of catalysts for the
OCM reaction are significantly affected, also some secondary factors like oxygen ion mobility
and trace-amount doping may play an important role. To evaluate such effects, which are still
poorly understood, studies are required in which these factors are adjusted in a controllable
way. Two investigations directed towards this goal are referred to in the following section.
3.4.1 On the Effect of Oxygen-Ion Conductivity in CaO-Ce02 Catalysts on C2+ Selectivity. It

is well-known [11-15] that CaO-Ce02 mixed oxides exist at high temperatures within a certain
range of composition as solid solutions with highly mobile oxygen defects. Previous studies
showed that the solubility limit of CaO in the Ce02 matrix is in the range from 15 to 23
mol-% depending on preparation conditions applied and precursor materials used. Like other
fluorite-type solid solutions, ionic conductivity (ajon) in CaO-Ce02 solid solutions varies line-
arly with the CaO content (nCaO) and also with temperature within the composition range of
the solid solution [11-15]:
aj~n Ej
a' = - (nc 0) exp (- - - ) (3.4)
IOn TaRT
The composition corresponding to maximum conductivity is close to the solubility limit. If the
CaO content exceeds the solubility limit, the oxygen-ion conductivity decreases gradually due
to the formation of additional calcium oxide crystallites in which the oxygen ions are much less
mobile [11-15]. For illustration, the relationship between ionic conductivity the CaO content is
given in Figure 12.
Selectivity is shown in Figure 13 as a function of catalyst composition. Pure CaO and Ce02
resulted in C2+ selectivities of 29% and 3.0%, respectively. The addition of CaO to Ce02 has
a marked positive effect on C2 + selectivity of the catalyst i.e., a total oxidation catalyst
(Ce02) is transformed into a partly selective one (CaO-Ce02)' The C2 + selectivities achieved
over the CaO-Ce02 catalysts strongly depend on the CaO content in the catalyst: when incre-
asing the CaO content, C2 + selectivity tirst increased markedly to a maximum value of
ca 55% at a CaO content of around 25 mol-%; on further CaO addition C2+ selectivity
decreased to the value of the pure CaO catalyst. As shown above, oxygen-ion conductivity
depends on the CaO content, a similar pattern is observed for C2 + selectivity. Thus, it may be
tentatively assumed that C2+ selectivity is related to oxygen-ion conductivity i.e., increasing
oxygen-ion conductivity results in an increase in C2+ selectivity. Such a dependence may be
explained by two propositions:
295
01 oz 09 10
&Jr---------------,
Two Phase S
RegIOn 0/0 60
,,
,
L 'I/.. ,
:z:
o ,,
\::) l ,,
, ,,
,
(eOz (el_x(ox Oz-x (00
(x=O) (015 sxsO.23) (x=1) (00 content I mole %
Figure 12. Dependence of oxygen-anion con- Figure 13. Dependence of C2 hydrocarbon selectiv-
ductivity on CaO content at 1073 K (references ity on catalyst composition (T = 1013 K,
see text). PCH4 = 93 kPa, P02 = 7 kPa).
(1) The relationship between surface lattice oxygen anions 02-(s), gas phase oxygen 02(g),
and anion vacancies V0 is described by
(3.5)
Excess electrons e- can be either easily accepted by Ce4 + cations to form Ce3 + cations or
provided by the latter ones respectively. High vacancy concentrations (Vo) shift this reaction
to the left, resulting in the stabilization of Ce4 + ions in the catalyst. Since the total oxidation
of methane which occurs over a pure Ce02 catalyst is at least partly due to the accessible mul-
tiple cationic oxidation states [16, l7], it seems rather reasonable to assume that the presence
of anionic vacancies which are created by incorporating calcium cations into the Ce02 matrix
could favor the reduction of the non-selective surface oxidation through the stabilization of the
Ce4 + state.
(2) It may be reasoned that a catalyst with a high oxygen-ion conductivity can improve the
incorporation of gas-phase oxygen 02(g) into the lattice of the catalytic solid by providing a
high transition rate of any weakly-bound adsorbed oxygen O(a) species into lattice oxygen
species O(s) [18, 19]:
02(g) ~ 02(a) (3.6)
Hereby the concentration of the weakly-bound adsorbed oxygen species which is believed to be
mainly responsible for the non-selective surface reactions is minimized, resulting in an enhan-
cement of C2 + selectivity.
The findings presented above may be summarized by the following conclusions:
(1) A CaO-Ce02 solid solution having a solubility limit of ca 20 mol-% was formed in the
CaO-Ce02 catalyst applied in the present work;
296
(2) It could be shown that the dependence of C2 + selectivity and oxygen-ion conductivity on
the CaO content exhibit a similar pattern i.e., they both have a maximum at around 20 to
25 mol- CaO;
(3) The formation of CaO-CeOz favors the stabilization of the Ce4 + state and provides a high
transition rate of any weakly-bound oxygen species into lattice oxygen, thereby reducing the
extent of non-selective surface reactions of methyl species and Cz hydrocarbons caused by
either the accessible multiple cationic oxidation states or/and the weakly-bound oxygen species,
thus, resulting in an enhancement of Cz selectivity.
From these results on the relationship between C2+ -selectivity and oxygen-ion conductivity
conclusions may be eventually derived for improved catalyst design.
3.4.2 Effect of Zn 2+ Cations Incorporated into the Surface of a NaOH-CaO Catalyst on C2+
Selectivity. It has been observed that C2 + selectivity of a NaOH-CaO catalyst is enhanced by
adding small amounts of Zn 2 + cations i.e., 0.0001 to 0.05 mol-% as is shown in Figure 14.
In the following some suggestions are summarized to explain this phenomenon (a detailed dis-
cussion is given elsewhere [20]).
100
5(2+ catalyst after calclnalion at 1123 K
0/0
• from dried precurser
90
o from drted. pelletIZed and
crushed precursor
80
70
•
0
60 0
50
0 00001 0001 001 0.05 01
at. % Zn 2+
Figure 14. CZ+ selectivity as function of the overall zinc content of the NaOH-CaO catalyst.
In the above-mentioned concentration range of zinc cations a negative shift of the binding
energy of the Zn 2P3/2 peak was observed when carrying out XPS measurements; at higher
concentrations this negative shift disappears. This has to be interpreted as an introduction of
ZnZ+ into the CaO lattice. Although no solid solutions of Zn 2 + in either CaO or Ca(OHh are
known it can be assumed that some CaZ+ cations are exchanged by ZnZ+ in the near-surface
region forming a pseudo solid solution. The amount of zinc introduced in this way should be,
however, very small. Higher amounts lead to ZnO clusters on the CaO surface; any Zn peak
then should show a binding energy similar to bulk ZnO as is the case when using a
Zn(1 mole %)-NaOH-CaO catalyst. A catalyst containing 0.1 mole % of zinc shows both types
of energy peaks in the XPS spectra.
297
The effect of the observed binding energy shift is probably only related to the CaO lattice since
it was also observed for catalysts containing no sodium. Sodium, however, obviously stabilizes
Zn2 + in the catalyst surface. This suggestion is derived from the following observation: the
Zn 2 + peak disappears after calcination of ZnO-CaO samples but stays unchanged for calcined
and reacted samples containing sodium. The observed amount of surface zinc (on the average
0.7 atoms %; Na + Ca + Zn = 100 atoms %), indicates that all or almost all zinc is present
in the near-surface region. (The escape depth of an electron amounts to two monolayers for Na
Is and Zn 2p at 600 eV and to 5 monolayers for Ca 2p at 900 eV [21]).
From the above observation it can be concluded that an increase in selectivity occurs only
as long as there are Zn 2 + cations in the NaOH-CaO surface. This is in agreement with the
experimental observation that at higher zinc concentrations the negative shift disappears which
is presumably due to the formation of ZnO clusters on the surface. Moreover, if zinc is not
present after calcination as well as after exposure to the OCM reaction in the near-surface
region as was observed for the ZnO(O.OI mol- %)-CaO catalyst i.e., without NaOH, no
change in C2+ selectivity was found.
If one would assume that heterolytic splitting of the weakly acidic methane occurs on the
highly basic surface, Zn2 + may act as an electron acceptor from the methyl anion forming
Zn 1 + as a transitional state. Neutral methyl species could then easily escape as radicals from
the surface to the gas phase where they could recombine to ethane. Adsorbed oxygen could
easily be reduced by Zn 1 +; hereby its transformation into lattice oxygen would be facilitated.
This phenomenon might also contribute to a rapid removal of any adsorbed oxygen species
from the surface which are assumed to be responsible for non-selective oxidation.
Summarizing, it may be proposed that incorporating a reducible oxide like zinc oxide in the
near-surface lattice of a NaOH-CaO catalyst leads to an improvement of C2+ selectivity as
long as there are no zinc oxide clusters on the surface.
4. Optimization of Reaction Conditions
As it has already been indicated above, selectivity and hence yield of C2+ hydrocarbons, are
not only affected by the catalytic material applied but also markedly by the reaction conditions,
as it has been shown by many authors, i.e., reaction temperature as well as partial pressures of
methane and oxygen or the ratio of methane-to-oxygen at a given total pressure respectively.
The effects of temperature and of the CH 4/0 2 ratio as well as of the total pressure are illus-
trated for various catalysts in Figures 15a,b, 16a,b and 17. It is obvious that there is an opti-
mum temperature and this relationship can be explained by the higher apparent activation
energy of the selective reaction step compared to the non-selective one (see section 5) and by
the occurrence of non-selective gas-phase oxidation of CH 4, C2H6 and C2H4 at elevated tem-
peratures. The influence of the CH4/02 ratio is affected by the different orders in oxygen for
the primary selective (CH 4 ----+ C2H6) and non-selective (CH 4 ----+ CO 2) reaction steps, while
the order in oxygen is higher for the non-selective step than for the selective one. Details on
the kinetic relationships are presented in section 5.
More recently it has been reported by Heinemann et al. [22] that the pressure of water
vapor influences C2 + selectivity favorably for a specific catalytic system (Ni-Ca-K-O). The
authors observed for such a catalyst which exhibited low activity excitingly high C2+ selectiv-
ities of nearly 100%. For other catalysts this could, however, not be confirmed (see [23] and
Table 5 [40]). Further work is needed to elucidate these phenomena.
298
S( Imole% Y(,/mole%
80 '0 1
•
0 ~.
.~;~e
r
70
60
50
!~
x
40 4
700 750 800 B50 700 750 BOO 850
T I DC T IOC
X la,O, X La,O,
o T,'o/La,O, o
Nb'o'la,O, o T"o, La,O, 0 Nb,o'La,O,
• L,o'La,O, • Zn ,0ILa,O, • Srz.lLa, 0, • L,olLa,O, • Zn'na,O, • Sr'-iLa, 0,
Figure 15 a,bo Selectivity (a) and yield (b) of C2+ hydrocarbons as function of temperature
(X02 > 95%, T = 1023 K, PCH4 = 60 kPa, P tot = 100 kPa) [38]0
Sc,J mole Yc'ol mole 0/0
.---..
%
12~-----------------------,
~.
70
~:::::::::
11
60
.yQ 10
~
I
50
~
40
30
8
5L--L__ __ __-L__
20
~~ ~~ L-~
0 4 6 B 10 12 14 o 4 6 8 10 12 14
CH 4 /0 2 CH 4 /0 2
X La,O, X La,O,
o Ti'oiLa,O, 0 Nb'na,O, o T"-/La,O, 0 Nb '-/La,O,
• L,o /La,O, • Zn '0, La,O, • Sr'-lLa, 0, • L,-lLa,O, • Zn'-lLa,O, .Sr'-'La,Ol
Figure 16 a,bo Selectivity (a) and yield (b) of C2+ hydrocarbons as function of the methane-to-oxygen
ratio (X02 > 95%, T = 1023 K, PCH4 = 60 kPa, P tot = 100 kPa) [38]0
299
80
Scl/%
•
10 o1 bar
~oo 1000 1100 1200

T1K
Figure 17. Effect of temperature on C2+ selectivity at 100 and 400 kPa using a La203-CaO catalyst
(La: 27 at%, Ca: 73 at%, CH4:02:N2 = 10:1:4, X02 > 95%) [39].
TABLE 5. Effect of water vapor in the feed on performance of two different

catalysts (Ptot = ca 100 kPa, P CH4 = 30 kPa, Paz = 10 kPa, PH20 = 0 to
60 kPa, P N2 as balance to 100 kPa, F tota! = 1.3 mIls).
Catalyst T PH20 X/% SI% PH2

K kPa O2 CH 4 C2H 4 C2H6 C2 + CO CO2 kPa
AI) 1023 0 98.4 27.9 18.4 18.3 39.6 9.3 50.9 2.03
A 1023 60 98.4 26.3 19.0 15.7 37.2 6.7 56.1 2.77
B2) 1023 0 98.3 22.3 25.2 17.8 43.9 0.2 55.8 0.19
B 1023 60 33.9 5.6 11.2 31.5 43.4 1.9 54.6 0.04
1) La20TCaO (200 mg)

2) PbO/y-A1203 (500 mg)
5. Kinetics
As already outlined above, the OCM reaction consists of surface-catalyzed and non-catalytic
reaction steps occurring in the gas phase; the latter type of reactions was dealt with in the
above section 2. Within the present section (1) kinetic results obtained for the primary catalytic
reaction steps which lead to the formation of ethane plus ethylene and carbon oxides from
methane are presented, and (2) suggestions are put forward of how to account for both the
catalytic and non catalytic homogeneous gas-phase reactions occurring simultaneously.
300
5.1 CATALYTIC OCM REACTION [24]
There is general agreement that at first in the OCM reaction, methyl species are formed, which
can either recombine to ethane or react further with oxygen in an equilibrium reaction to per-
oxy radicals which are finally oxidized to carbon oxides. If this reaction scheme was valid and
methyl radical formation could be the rate determining step in both competitive reaction steps,
the same kinetic isotope effects should be expected for the formation of carbon oxide as well as
of hydrocarbon. This is, however, not true as can be derived from Table 6. For ethane forma-
tion C-H bond splitting is obviously the rate determining step while this step does not affect
the overall rate of COx formation. That is to say, C2 hydrocarbon and COx are formed via dif-
ferent intermediates and rate determining steps as was also suggested earlier by Nelson et al.
[25].
TABLE 6. Primary kinetic isotope effects for the oxidative methane coupling to carbon oxides
and C2 hydrocarbons over a NaOH/CaO catalyst.
kH/kD
T/K
COx C2 H2/D2 calcul.
933 O.99±O.O6 2.18±O.13 1.45±O.13 1.95

973 1.04±O.O6 1.9l±O.1O 1.46±O.12 1.91
1013 1.02±O.O5 1.60±O.O9 1.37±O.15 1.87
To describe the kinetics of the OCM reaction quantitatively, rate equations for the primary
reaction steps i.e., the formation of COx and of ethane plus ethylene were determined (these
two hydrocarbons were lumped since ethylene is formed from ethane only). To derive rate
equations a micro-catalytic-fixed-bed reactor was operated differentially in such a way that
only small conversions of the key reactants were obtained, allowing to determine reaction rates
which could then be correlated with the prevailing reaction conditions (for further details see
[24]).
Carbon oxide formation. The rate of carbon oxide formation was shown to be O.5th order in
both methane and in oxygen [26] (for illustration see Figure 18a and b):
R = k J pO.5 pO.5 (5.1)
COx CH4 02
On the basis of this kinetic relationship it was suggested that dissociatively adsorbed methane
reacts with surface oxygen to the carbon oxides. The surface-oxygen coverage is assumed to
depend on its gas-phase partial pressures by a square-root relationship. The rate determining
step for COx formation is presumably the reaction between an adsorbed CH 3 species and the
surface oxygen species:
RDS
CH3(surf) + O(surf) ---.. CH30(surf) ~ ~ ~ COx (5.2)
Since no C-H bond is broken in the reaction between CH3 and 0, no kinetic isotope effect
should be observed, which, in fact, agrees with experimental evidence (see above Table 6).
301
8 • 1033 K
• 1033 K
5 • 1013 K
• 1013 K
.. 993 K .. 993 K
4 o 973 K 6 o 973 K
o 953 K o 953 K
3 " 933 K ... 933 K
4
2
2
100 200 300

~P[H,/PQ
Figures 18a and b. Dependence of carbon oxide formation rate on methane and oxygen partial pressures.
Hydrocarbon formation. The hydrocarbon formation rate is first order in methane, while it
passes through a maximum with respect to oxygen partial pressure. With increasing tempera-
ture this maximum is shifted to higher oxygen partial pressures and the inhibiting effect is
reduced [26]. Accounting for these relationships the following two kinetic equations which are
applicable for two different ranges of temperature were derived assuming Langmuir-Hinshel-
wood-type adsorption:
Modell: The number of catalytic sites active in methyl radical formation depends on dissocia-
tively adsorbed-type oxygen (T > 1013 K)
k P~
C2,t CH4 02
R = (1 +~)2
(5.3)
C2
°2
Model 2: Different from Model 1 given it is assumed that the number of sites depends on oxy-
gen partial pressure in the gas phase (T < 933 K)
k b2 P P
C2,t CH 4 02
R = + b2 P )2
(5.4)
C2 (1
°2
At temperatures above 1013 K the rates of hydrocarbon formation could be well described by
Modell, whereas at temperatures below 933 K the experimental values could be well descri-
bed by Model 2 (see Figures 19a and b). Based on the above results and considering the kine-
tic models and the kinetic isotope effect (see Table 6), the rate determining step for hydro-
carbon formation was suggested to be the formation of methyl radicals by reaction of molecu-
lar methane with an oxygen species as defined by Models 1 and 2 involving C-H bond rupture:
302
IT=1033 KI IT = 933 K I
20
1,0 I
I
0,5
5 10 5 10 15 20
Pa/ kPu
Figures 19a and b. Application of Models 1 and 2 for the rate of hydrocarbon formation.
(5.5)
It should be emphasized that the reaction scheme proposed above i.e.,
(5.6)
does not take into account of any consecutive reactions of ethane and ethylene to COx although
this is a requirement if higher degrees of conversion are considered. Moreover, COx formation
consists of two competitive steps as it has been recently observed in our laboratory: one origi-
nating from deep oxidation of methyl species and the other from decomposition of formalde-
hyde which is formed as a short-lived intermediate from methyl species. A more complete
kinetic scheme comprising additional steps is shown in section 6.2.
5.2 COMBINED CATALYTIC AND HOMOGENEOUS GAS-PHASE REACTIONS [5a]
A model by which both the catalytic and non-catalytic steps of the OCM reaction are com-
bined, and by which the various reaction pathways leading to the final products can be kineti-
cally described, is outlined. A similar proposal has been recently presented by Lunsford [41].
Its performance is illustrated by simulating (1) activity i.e., conversion versus contact time,
and (2) selectivity versus degree of conversion, and (3) comparing the results with experimen-
tal data obtained for a PbOI'Y-AI203 catalyst. The model used consisted of 182 homogeneous
303
gas-phase reactions and 7 catalytic-surface reactions. The kinetics of the homogeneous reac-
tions are based on [Sa]; (for further details see also [5b]).
Basis of Simulation. It is basically assumed that the primary catalytic reaction step is the for-
mation of methyl radicals which further react either on the catalytic surface or in the gas
phase. The rate of catalytic methyl-radical formation was set equal to the rate of methane con-
sumption. A power-law rate equation, valid for temperatures around 1020 K as reported earlier
[27], was applied.
(5.7)
This rate equation is in agreement with a suggestion by Krylov and coworkers [28] who pro-
posed an Eley-Rideal-mechanism based on experimental work carried out with a similar cata-
lyst as applied in this work. Their suggestions on the mechanism was adapted to derive the
following reaction steps participating in the formation of methyl radicals which then recombine
in the gas phase.
R-1: 0z(g) +2s --+ 20-s (5.8)

R-2: CH 4 (g) + O-s --+ CH 3(g) + HO-s (5.9)
(s = active surface site)
Regeneration of the active surface sites is described by:
R-3: CH4(g) + HO-s ----.. CH3(g) + HzO(g) + s (5.10)
To account for the formation of total oxidation products the following reasoning was applied.
The PbOII'-Al z0 3 catalyst leads to only low selectivities of CO whereas COz is the main total
oxidation product. Neither CHzO nor CH30H was, however, detected. From these experi-
mental findings it may be concluded that total oxidation of CH 4 , CHzO, CH 30H and CO to
COz proceeds on the catalytic surface since CO would be the predominant total oxidation pro-
duct in homogeneous gas-phase reactions. Thus, the following reaction scheme for the total
oxidation paths of CH4 via methyl radicals is suggested:
R-4: CH 3(g) + O-s --+ CH 30-s (5.11)

R-5: CH 30-s + O-s --+ CHzO(g) + HO-s + s (5.12)
R-6: CHzO(g) + O-s --+ CO(g) + HzO(g) + s (5.13)
R-7: CO(g) + O-s ---+ COz(g) +s (5.14)
The total number of active sites per reactor volume was derived from the catalyst surface in
this volume. The total number of active sites was set equal to the amount of oxygen removable
from the catalyst surface (see e.g. [29 to 31]). For different methane coupling catalysts (SnOZ,
Li/MgO, SmZ03) this number was found to be 8.1'10-5 to 1.39.10-3 mol/g at temperatures
between 873 K and 1080 K. For the present work an average number of 3'10-4 mol cm- 3
(converted to the gas volume of the bed of catalyst particles) was chosen since no data were
available for the PbOI-y-Alz03 catalyst.
304
The formation of higher hydrocarbons as well as the dehydrogenation of ethane was assumed
to proceed in the gas phase only. For the latter reaction this was experimentally proven for
temperatures above 973 K [32]. The dependencies of oxygen conversion on contact time and of
product selectivities on oxygen conversion were calculated using the above mentioned model
for conditions for which experimental data were available. The procedures of simulation and of
fitting of the rate constants of the various surface reaction steps is documented in [Sa] and will
be described elsewhere [42].
S(i) 11%) S(C2+) 1 1%)

60 --------
-l
Cl:J 80
0
50
0
40 _model 60
•
'l{; 0
0 0
• D .·0• \
o ethane
o ethylene
30 • ethane
o ethylene 40
6. ethane
• ethylene
20
IF~
20
10
~O
oL-_~ __ - L_ _~_ _L-_~
0
o 20 40 60 80 100 0 20 40 60 80 100
X(02) 11%) X(02) 11%)
S(i) 11%)
60,------''--'---- -----~ 10
X(02) 11%)
Figures 20a-c. Dependence of selectivities on oxygen conversion; comparison of experimental data

(symbols) and simulation (lines) (CH4/02/N2 = 10: 1:4; T = 1020 K; P tot = 100 kPa).
305
Results. The experimental data which were partly already reported [33, 34] and which are
partly unpublished hitherto [35, 36] and the simulation results are compared in Figures 20a-c.
Agreement is especially good at oxygen conversions below 50 %. At higher conversions the
C2H4/C2H6 ratio and COx selectivity are overestimated by simulation, although the deviations
are almost in the range of the reproducibility of the various experimental data. The simulated
oxygen conversion as function of contact time also agrees well with the experimental data (cf.
Figure 21).
0.1 1
mica!) / It [g'a/mll
Figure 21. Dependence of oxygen conversion on contact time l1lcat/V; comparison of experimental data
(symbols) and simulation (lines) (CH4/02/N2 = 10:1:4; T = 1020 K; P tot = 100 kPa).
Sensitivity analyses [5a, 37] showed that the model is not sensitive to reactions R-3, R-5 and
R-6 although they are important from a mechanistic point of view and cannot be neglected for
this reason. The rate determining surface steps are reactions R-l, R-2 and R-4; also the total
number of active sites is a decisive factor. If other site numbers were used lower selectivities
were obtained. Sensitivity is less affected by the rate constant of reaction R-7 than by those of
the other reactions; this rate constant has, however, a marked influence on the CO/C02 ratio.
It should be mentioned that methane is not exclusively activated to CH 3 ' on the catalytic sur-
face but equally in the gas phase under the applied reaction conditions.
Finally, it should be mentioned that the simulation procedure applied for the PbO/y-AI203
catalyst might lead to quite different results for other types of catalysts.
6. Reactor Design and Flow Sheeting
As pointed out in Section 1, research and development work on the catalytic OCM reaction is
mainly carried out in the "cofeed" mode although a significant amount of development work
has been also accomplished in the "redox" mode by ARCO. It appears, however, that work at
ARCO has been terminated. For both types of processing catalytic fixed-bed and fluidized-bed
reactors have been applied in bench-scale and mini-pilot-plant studies. Steep axial and radial
306
temperature gradients occur in fixed-beds due to the large exothermicity. From this point of
view fluidized-bed reactors look more promising; they have been recently used by various
groups working in the field (see e.g. [43 to 48]). An obstacle to the use of fluidized-bed reac-
tors might be in some instances the poor fluidizability of various catalysts which have shown
good performances in fixed-bed reactors. Therefore, the development of catalyst-preparation
procedures with respect to fluidizability remains of continued concern.
Against the described background it is the intention of this contribution to deal with the
following three subjects:
(1) Results on fluidized-bed-reactor performance when using a La20rCaO catalyst fluidizable
over a wide range of operating conditions up to 400 h without any problems.
(2) Evaluation of the applicability of fluidized-bed-reactor modeling for the OCM reaction as a
means of reactor simulation and scale-up. (It should be emphasized that the study of items (1)
and (2) was not aimed at investigating the best possible catalyst from the point of view of
maximizing selectivity or yield but to illustrate the general pattern of relationships and the
methodology of modeling).
(3) Introduction of potential flow sheets which have been reported for carrying out the OCM
reaction to produce essentially ethylene.
6.1 CATALYTIC PERFORMANCE OF A CATALYTIC FLUIDIZED-BED REACTOR [49J
Methane conversion (X CH4) was in the order of 12 to 25 % depending on the reaction condi-
tions applied (see Figure 22). Since the methane coupling reaction is carried out at CH4-to-02
ratios higher than 4 the availability of oxygen limits the degree of methane conversion for
stochiometric reasons. The lowest oxygen conversion of 81.5 % was measured at 973 K for an
inlet partial pressure of oxygen of 14 kPa, above 1033 K it was complete for P0 2 :::;; 10 kPa.
Therefore, an increase of oxygen partial pressure leads to higher methane conversion as long
as no undesired deep-oxidation reaction takes over. Conversion rises with temperature due to
the increase of reaction rates but also as a consequence of the increase in selectivity.
C2 + selectivity (SC2+) depends on temperature as is shown in Figure 23; it passes through
a maximum located between 1073 K and 1113 K depending on the inlet partial pressure of
oxygen. An increase in oxygen partial pressure shifts the maximum to higher temperatures.
For all temperatures C2+ selectivity increases with decreasing oxygen partial pressure.
The increase of C2 + selectivity with increasing temperature in the lower temperature range
is caused by the higher activation energy of the selective primary reaction step to C2 hydrocar-
bons compared to the non-selective steps to COx. The decrease in selectivity within the high
temperature regime can be explained by enhanced total oxidation and steam reforming of the
C2 products. The negative effect of oxygen partial pressure on selectivity is ascribed to the dif-
ferent kinetic orders in oxygen for the selective and non-selective primary reactions. The order
in oxygen was lower for the selective route compared to the non-selective steps (see section
6.2, Table 7, and also section 5.1).
The C2 + yield which can be derived from the plots of selectivity and methane-conversion
versus temperature first rises with increasing temperature due to an increase in C2 + selectivity
and hence, in CH4 conversion. With further increasing temperature the yield drops. This is
caused by the decrease in C2+ selectivity due to non-selective catalytic and homogeneous gas-
phase reactions. The yield increases with increasing oxygen partial pressure due to the incre-
asing methane conversion which overcomes the decreasing selectivity (see also above). With
307
increasing oxygen partial pressure the maximum is shifted towards higher temperatures. (For
further details see references [45,50]).
Sc 2 / %
60 •
25 ._.-
.-
"..,.." ...,.
_ . 0_0-0
- . 0-
50
.""'0.-.~o-
--
20 0 0 .-.-
/.,.,.,.,"- ~.-
-
/0 ._.-. • _
._ l:>_~t:s.
40
l:>_l:>-l:> 6
• 14 kPa • 14 kPa
15 _l:>- 0 12 kPa o 12 kPa
_ . - . - • 10 kPa • 10 kPa
._.-,;-. l:> 8 kPa 30 l:> 8 kPa
- • 6 kPa • 6 kPa
10+----.---,,---.----.--~
680 720 760 800 840 880 680 720 760 800 840 880
Tn T1"(
Figure 22. Effect of temperature and oxygen Figure 23. Effect of temperature and oxygen
partial pressure on methane conversion. partial pressure on C2+ selectivity.
Experimental conditions: La203(27 atom %)/CaO, PCH4 = 60 kPa, ulumf = 4.
6.2 MODELING OF THE OCM FLUIDIZED-BED REACTOR [49]
As a basis for reactor modeling, assumptions had to be made on fluidized-bed hydrodynamics.

Four different choices were considered: the model of Davidson and Harrison (D&H) [51], the
bubble assemblage model (BAM) [52], the model of Kunii and Levenspiel (K&L) [53] and the
counter-current backmixing model (CCBM) [54]. The D&H, K&L and CCBM models were
modified to account for steep concentration gradients measured close to the distributor. There-
fore, the hydrodynamic parameters applied in these models were height dependent and dis-
cretized as in the BAM model. In the D&H, BAM and K&L models the gas flows through the
emulsion phase with minimum fluidization velocity. Furthermore, the models could be option-
ally modified assuming plug flow (PF) of the gas in the distributor zone (first segment) or by
describing the mass transfer in this region according to the concept of Behie and Kehoe (B&K)
[55]. The models are described in more detail with respect to the OCM reaction elsewhere [57].
The chemical kinetics applied for the OCM reaction are based on the reaction scheme pre-
sented in Figure 24. Power-law and hyperbolic rate equations (6.1) to (6.3) were applied in the
various models (no mechanistic meaning should be, however, ascribed to the rate equations).
Kinetic parameters derived from differential and integral operation of a micro-scale fixed-
bed reactor are presented in Table 7 [56]. For simplicity it was assumed that, however, gas
phase reactions are slow at the temperatures considered compared to catalytic reactions. There-
fore they were neglected.
308
I: non-selective oxidation
2: oxidative coupling
3: formaldehyde decay
4: ethane oxidation
5: ethane dehydrogenation
6: ethylene oxidation
7,8: steam reforming
co
Figure 24. Kinetic reaction scheme for reactor modeling.
rj = leoj exp(-E/RT) ~C P~2 (j = 1, 3-6) (6.1)
rj = leoj exp(-E/RT) ~C P~
2
° (j = 7, 8) (6.2)
r2 = (6.3)
0.5 2
(1 + K exp(-AH/RT)P )
°2
TABLE 7. Kinetic parameters of rate equations 6.1 to 6.3. Reactions numbered according to Figure 24.
Reaction leo E m n K -AH

No mol!(gsPa-(m + n) kllmol Pa- 0 .5 kllmol
1.07*10-9 82.4 0.5 1.5

2 1.93*10-5 108.9 0.8 0.5 2.73*10 16 240.5
3 2.25*10- 8 75.0 1 1.1
4 7.88*10-5 93.7 0.5 0.7
5 3.10*10+ 1 176.2 0.5 0.13
6 2.14*10- 8 101.2 1 0.5
7 5.00*10- 13 150.0 I
8 4.83*10- 4 150.0 0
Model discrimination was done comparing simulated and 41 experimental data sets. The mea-
sure of model accuracy was defined as the sum of squares of relative errors of prediction for
SC2+ and XCH4' The bubble assemhlage model assuming plug flow (PF) in the horizontally
distributor zone (BAM +PF) was best (for details see [49]). A comparison between results of
simulations obtained with the BAM + PF model and experimental data is shown in Figures 25
and 26. C2 + selectivity is very well predicted; the conversion of methane is also predicted
quite well, however, a tendency to underestimate the conversion was observed. The standard
deviations for the prediction of SC2+ and XCH4 amount to 7 and 8 % respectively. It should
be emphasized that the simulations were done without any tuned parameters.
309
x~~ 1%
26
55
24
22 50
0
20 45 0
18 oWJ
1@a;P 40
16 0
35
14 OtP~
12 30
~t:D
10 25
10 12 14 16 18 20 22 24 26 25 30 35 40 45 50 55 60
X~~/% Sex p 10/0

(,.
Figure 25. Comparison of experimental and Figure 26. Comparison of experimental and
simulated values for methane conversion at vari- simulated values for C2 + selectivity at various
ous conditions applying the BAM(PF) method. conditions applying the BAM(PF) method.
In conclusion it may be said that fluidized-bed-reactor modeling is feasible and that it should
be applicable for scale-up studies and hence, economic evaluations of the process. Work is
presently underway for predicting the optimum experimental conditions for further improve-
ment of the reactor performance with respect to C2+ selectivity and yield.
6.3 PROCESS SCHEMES
Various process schemes for converting methane either to ethylene or ethylene plus gasoline
have been reported during the past few years. A provisional flow sheet for the production of
ethylene (see Figure 27) along with an estimation of production costs for an ethylene capacity
of 350.000 metric tons p.a. was published by Preuss and Baerns [57]. Production of ethylene
appeared only economic at low natural gas prices (see Figure 28).
L="-l:::=~_____~=~LPG
Figure 27. Process scheme for catalytic oxidative coupling of methane to ethylene [57].
310
Ethylene
Production Costs
500
US $It
450
400
3S0
300
W~
2S0
200
SO 100 1S0 200 250
Methane price US $1 t
Figure 28. Ethylene from catalytic oxidative coupling of methane. Production costs vs price of natural
gas (period of reference: 1985/86) [57].
More recently Edwards et al. [44,58] as well as Cameron et al. [47,59] have presented flow
sheets in which ethane is dehydrogenated in the oxygen-free zone of an OCM fluidized-bed re-
actor (see Figures 29 and 30); also a fixed-bed reactor has been suggested by Cameron. This
might possibly be considered as an improvement compared to the above process scheme
(Figure 27). Cameron et al. refer to production costs of 435 to 540 US $ per metric ton of
ethylene for a plant having a capacity of 600.000 tons p.a. [47]. These costs are comparable to
the above given values (see Figure 28).
GASOLINE
CH4 RECYCLE CH..
Figure 29. CSIRO/BHP process concept for producing transport fuels from natural gas by oxidative cou-
pling of methane [58].
311
Methanalor
l'\alUral
G",
Gasoline
and
Diesel
Figure 30. IFP process for the oxypyrolysis of natural gas [47, 59].
C02 to ATM
I
Untreated Gas Feed Gas
f---+ Propane 1780 BPD
132 MMSCFD Fractionation

t---. Butane 800 BPD
~ Condensate 1300 BPD
Recycle Gas
Air
REDOX ~ Water 20.000 BPD I
C02 ATM
I
Olefin Product
'------ I---
Conversion Fractionation
I High Octane Gasolin e

12.000 BPD
Figure 31. ARea process scheme for the production of high-octane gasoline from natural gas by oxida-
tive coupling of methane and subsequent olefin oligomerization [60].
312
Different from the above "cofeed" schemes is the "redox" scheme which has been suggested by
researchers from ARCO [60]. Its advantage is certainly the use of air instead of pure oxygen
which is usually applied in the "cofeed" processes for reasons of reducing separation expendi-
tures (see Figure 31).
All process schemes have in common that ethylene can also be oligomerized to higher
hydrocarbons of the gasoline range. It is anticipated that process design will become more reli-
able within the next future when more detailed information becomes available on improved
catalyst performance and when the basis is laid for a rational reactor scale-up.
7. Outlook
The present contribution has shown that still further fundamental work is required for obtain-
ing a better understanding of the catalysis of the OCM reaction which will eventually lead to
improved design and hence, performance of catalysts. Moreover, a better knowledge of the
kinetics of the various reaction steps occurring on the catalytic surface and in the homogeneous
gas phase is needed both, for fundamental and applied reasons. Such kinetics will contribute
(1) to design optimum functions of the catalyst to achieve high C2 + selectivities and yields and
(2) to better reactor design and scale-up.
Acknowledgement. Thanks are due to all of the author's associates who contributed in numer-
ous ways to this contribution - The research work was funded by the European Community
(Contract Nos. EN3C-0023-D and JOUF-0044-C).
List of Symbols
A(a) adsorbed molecule A

A (g) gas phase molecule A
A(s) surface lattice ion A
A (surt) surface molecule A
bi adsorption constant of oxygen according to model i
LiG free energy of reaction
LiH enthalpy of reaction
E activation energy
h hour
j reaction index
k reaction rate constant
K adsorption constant
kO frequency factor
m,n reaction orders
meat mass of catalyst
n amount of substance
n.dtd. not determined
OCM oxidative coupling of methane
O"ion ionic conductivity
p partial pressure
313
P tot total pressure

R gas constant (8.3141 mol-1K-l)
RA rate of formation of A
RDS rate determining reaction step
rp rate of iso-propanol conversion to propene
s active surface site
S selectivity
SBET surface area (determined by BET-method)
Ssim selectivity (simulation)
T temperature
u gas velocity
umf minimal fluidization velocity
V gas flow (reaction conditions)
V0 anion vacancies
wt-% weight-%
X conversion
Y yield
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49 Mleczko, L., Rothaemel, M., Andorf, R. and Baerns, M., 'Fluidized-Bed-Reactor Per-
formance for the Catalytic Oxidative Coupling of Methane to C2+ Hydrocarbons', sub-
mitted as contribution to "Fluidization Conference 1992".
50 Andorf, R. and Baerns, M. (1991), 'Oxidative Coupling of Methane in a Catalytic
Fluidized-Bed Reactor', Stud. Surf. Sci. Catal. 61, 517.
51 Davidson, J.F. and Harrison, D. (1963) Fluidised Particles, Cambridge University
Press, Cambridge.
52 Kato, K. and Wen, C.Y. (1969), 'Bubble Assemblage Model for Fluidized-Bed Catalytic
Reactors', Chern. Eng. Sci. 24, 1351.
53 Kunii, D. and Levenspiel, O. (1969) Fluidization Engineering, J. Wiley & Sons, New
York.
54 Fryer, C. and Potter, O.E. (1978), 'Countercurrent Backmixing Model for Fluidized
Bed Catalytic Reactors. Applicability of Simplified Solutions', Ind. Eng. Chern.
Fundam. 11, 338.
55 Behie, L.A. and Kehoe, P. (1973), 'The Grid Region in a Fluidized Bed Reactor',
AIChE J. 19, 1070.
56 Schweer, D. Durjanova, Z. and Baerns, M., unpublished data.
57 Preuss, U. and Baerns, M. (1987), 'Chemical Technology of Natural Gas - Its Present
State and Prospects', Chern. Eng. Technol. 10, 297.
58 Edwards, J.H., Do, K.T. and Tyler, R.I. (1989), 'The Oxidative Coupling of Methane
to Higher Hydrocarbons - Process Concepts and Reaction Engineering Aspects', in
Preprints of 3B Symposium on Methane Activation, Conversion and Utilization,
PACIFICHEM 89, Honolulu, Hawaii, USA, p. 169.
59 Mimoun, H., Robine, A., Bonnaudet, S. and Cameron, C.I. (1990), 'Oxypyrolysis of
Natural Gas', Appl. Catal. 58, 269.
60 Sofranko, J.A. and Jubin, J.C. (1989), 'Natural Gas to Gasoline: The ARCO GTG
Process', in Preprints of 3B Symposium on Methane Activation, Conversion and Utili-
zation, PACIFICHEM 89, Honolulu, Hawaii, USA, p. 165.
DYSPROSIUM OXIDE FOR OXIDATIVE COUPLING OF METHANE
ORRAN ALTIN, ISIK aNAL, TIMUR DOOU

Department of Chemical Engineering
Middle East Technical University
Ankara-TURKEY
J.B. BUTT
Northwestern University
EVANSTON IL 60108, U.S.A.
ABSTRACT. In this study, the catalytic activity of dysprosium oxide, Dy,o, , for the oxidative coupling
of methane to higher hydrocarbons was investigated. Experiments were conducted under co-feed mode of
methane and oxygen in the temperature range of 700' to 800"C. The ratio of partial pressures of methane
to oxygen was changed between 5 to 40 keeping the methane partial pressure constant at a value of 18.2
kPa with helium dilution. The results indicated 95% C,+ selectivity (C,H.+C,H,) at low oxygen
concentrations. Both the C, + selectivity and C,H.lC,H, ratio showed an increasing trend with higher
temperatures. The optimum temperature was found to be 750"C. At this temperature, conversion of
methane was 38 % and the yield of c,+ was 8.32, at a ratio of PcH4 /P o, of 5.
1. Introduction
Methane is the most abundant component of natural gas which is a raw material for future liquid
fuel and chemical production industries. Oxidative dehydrogenation and subsequent coupling of
methane to ethane and ethylene is a simple, energy-efficient reaction scheme to use methane as
a precursor for ethylene.
Keller and Bhasin (1982) reported that the catalysts containing the simple oxides ofPb, Bi, Sn,
Tl, Gd or Mn were the most active catalysts for the formation of Cz + hydrocarbons
(C2H4 +C2H 6) with selectivities over 50%. Hinsen and Baerns (1984, 1986) reported that PbO
on SiOz carrier was one of the best catalysts with respect to the Cz + selectivity (72 %), but its
catalytic activity was low. Work by Ito and Lunsford (1985) and Ito et.al. (1985) reported that
7 wt % Li-promoted MgO showed high activity with a 50% selectivity at a 38% conversion of
CH4 in the presence of oxygen. Jones (1985), Sofranko et. al. (1987), and Jones et. al. (1987) also
investigated catalytic activity of Mn, In, Ge, Sn, Sb, Bi and Pb oxides. These metal oxides gave
selectivities between 10 to 50% under cyclic redox mode in which oxidized catalyst was reacted
with methane in the absence of oxygen to form coupling products and reduced catalyst was
reoxidized with air in a separate step. Otsuka and co-workers (1985, 1986a, 1986b, 1986c) tested
317
H.!. de Lasa ef al. (ed,.), Chemical Reactor Technology for Environmentally Safe Reactors and Products, 317-323.
© 1993 Kfuwer Academic Publishers.
318
many metal oxides and concluded that the oxides of rare earth elements showed higher C2+
selectivities. Among the metal oxides tested, Sm20 3 was the most active and selective catalyst for
the formation of Cz + compounds (selectivity 93 %).
In addition to these studies on catalyst screening, there are some reported kinetic data using
Sm20 3 (Otsuka and Jinno, 1986) and Li/MgO (Ito et.a1., 1985). Moreover, it was reported that
in the presence of suitable catalysts, co-feed of methane and oxygen gave higher selectivity and
conversion (yield) than cyclic redox mode.
Despite the interesting results obtained in the oxidative dehydrogenation of methane approach,
the use of the oxidative coupling reaction remains limited because of the low methane
conversions and high temperatures required.
The goal of this study was to investigate single step conversion of methane to higher
hydrocarbons over dysprosium oxide at different temperatures and at different partial pressures
of oxygen.
2. Experimental
The dysprosium oxide (DY203' 99.9% pure) in the form of powder was obtained from Ventron
Alfa Products. The surface area of the catalyst was 3.48 m2/g obtained by means of BET method
using nitrogen adsorption at 77 K. The crystalline structure of the catalyst, which was examined
by the X-Ray Powder Diffraction analysis method, was found to be the simple cubic form. The
apparatus for testing the catalyst was a conventional differential tubular reactor. It was made of
a quartz tube with an internal diameter of 9.3 mm. Methane and oxygen were fed to the system
with helium carrier. Ceramic balls with a diameter of 6 mm were used in the inlet section of the
reactor. The reactor was connected directly to the gas chromatograph-mass spectrometer system
(Figure 1). The gas chromatograph system consists of thermal conductivity and flame ionization
detectors.
['''.
0.
MS-3A
Flowmeter
0,
Quartz Wool
ElectriC FlIneC8
Filter MS-3A Flowmeter

He
TCD
FID
catalyst Bed
Ceramic
Flowmeter Preheaters
Filter
Figure 1. Reaction scheme for oxidative coupling of methane.

319
Five grams of catalyst were tested in the quartz reactor under a total flow of 125 ml/min and
a total pressure of 1 atm. The conditions for catalyst testing were chosen as follows: T=700 ·C,
750 ·C, and 800·C, PcH4 =18.2 kPa (constant), P02=0.45-9.34 kPa while the rest of the gas
composition was helium.
3. Results and Discussion
In this study, the effect of oxygen partial pressure and temperature on the catalytic activity of
dysprosium oxide were investigated. Three different temperatures and six different partial
pressures of oxygen were studied. In general, the products observed in the reaction were: CzH6'
C2H 4 , CO, CO2 , H2, H20 and to a lesser extent higher hydrocarbons. Oxygenated products, such
as, CH 3 0H and CH20 were found in only trace amounts. Early studies demonstrated that the
oxidative coupling of methane to form Cz + hydrocarbons was a high temperature reaction and
temperatures in excess 600"C were required to observe selective products.
Figure 2 shows that the rate of production of C2+ products increases by increasing the
temperature from 700"C to 800·C. On the other hand, a significant difference is not observed
between 750"C and 800"C. As Oz partial pressure is augmented, the rate of production of Cz +
increases up to 4 kPa. After this value, no further increase is observed in the rate of Cz +
formation.
40
M
I
36
~
T-750 ·C
1 32
/)
C 28
CO2
~ 0
] 24
20
§ C2+
16
Je
+
12
C2H4
'0
jI! 4 C:2H6
~
2 3 4 5 6 7 8 9 10
po • .KPa
Figure 2. Effect of oxygen concentration on the rate of formation of Cz+ products.
The effect of oxygen concentration on the selectivity is illustrated in Figure 3. Selectivity

higher than 90% Cz+ is obtained at 750·C and low oxygen partial pressures. As expected, Cz+
selectivity decreases with an increase in the amount of oxygen. As shown in Figure 3, at
320
P02=0.45 kPa, Cz+ selectivity was 91.20%. However, at 9.34 kPa, the selectivity of Cz+
products decreased to 21.90%. Also, CO2 selectivity augmented from 8.70% to 78.1 % by
increasing the partial pressure of oxygen in this range at 750"C.
100
90
80
70
.~ 60
j 50
40
;I.
30
20
10
0
0 2 3 4 5 6 7 8 9 10
P • kPa
O.
Figure 3. Effect of oxygen on the selectivity of C2+ at 750°C
As expected, higher methane conversions are obtained as oxygen partial pressure increased.
On the other hand, selectivity of the desired products is reduced (Figure 4).
100
90
T=750 C
80
3 70 ~
I>
+
70 U'"
l! 60 60 l!
6~ 50 50 ~
>
~
u
40
30
40 M
30 $
'I'
20 20 'I'
10 10
0
2 3 4 5 6 7 8 9 10
P(02) I<Pa
Figure 4. Effect of oxygen on conversion and selectivity at 750"C

321
At P02=0.45 kPa, the conversion of methane was 3.76%, increasing to 38% at 9.34 kPa of
oxygen partial pressure. In this case however, the selectivity is reduced.
One of the most important parameters which indicates the effectiveness of a catalyst on
oxidative coupling is the yield. In Figure 5, the effect of oxygen concentration on the yield is
illustrated. The yield values showed an increasing trend with higher partial pressures of oxygen
at low oxygen concentrations. Furthermore, in the partial pressure range of oxygen between 4.5
and 9.5 kPa, the yield did not show a significant dependence on oxygen concentration. The
highest yield value was about 9.5 at 800"C.
15
14
13 T=750 "C
12
11
+
(II 10
()
9
~ e
)2 7
!! 6
>-
5
* 4
3
2
1
0
0 2 3 4 5 6 7 6 9 10
Figure 5. Effect of oxygen on the yield of Cz+.
In Figure 6, it can be observed that at higher reaction temperatures, CZH6 selectivity decreases,
but at the same time CZH4 selectivity increases (Figure 6) for a oxygen partial pressure of 0.45
kPa.
100
90 °C2+ 0
o
60
70
~
"
60
"C 2 H.
~ 50 "
~ 40
* 30
+
t.H4
+
20
10
0
650 700 750 600 650
Terro:>erature. t
Figure 6. Effect of temperature on selectivity of Cz+ products at lowest oxygen content.
322
Moreover, as shown in Figure 7, the ethylene to ethane ratio showed an increasing trend from
0.4 to 1.6 at higher oxygen partial pressures. It was also found that the reaction temperature is
a significant factor on this ratio. As illustrated in Figure 8, the C:zH4/CzH6 ratio showed an
increasing tendency with temperatures between 700-800·C. It has to be pointed out that data
reported in this figure correspond to the lowest oxygen partial pressure used (0.45 kPa).
2.00
1.80
T=750 't
1.60
Q 1.40
:i 1.20
~ 1.00
I!
!
(II
0.80
+
()
0.40
0.20
2 3 4 5 6 7 8 9 10
Figure 7. Effect of oxygen on the ratio of ethylene to ethane.
1.00
at maxim.m selectiVity for C2+

0.80
0
~ 0.60
~
(II
~ 0.40
~
0.20
0.00
650 700 750 800 850
Terrperatue. C
Figure 8. Effect of temperature on the ratio of ethylene to ethane.
4. Conclusion
Results of this work indicates that dysprosium oxide gives high selectivities, over 90%, at
yields lower than 10%. As mentioned before, oxygen concentration and temperature are
323
important factors affecting the activity of the catalyst. Detailed kinetic studies are needed to
explain in more detail the results of Figures 2 and 3. It can be concluded that oxygen partial
pressures should not be greater than 4.5 kPa, otherwise undesired reactions occur. Also, reaction
temperature should be kept at around 750"C to have a high C2 + selectivity. Furthermore,
increases in oxygen partial pressure and temperature result in higher ratios of C2H 4 /C 2H 6 • This
result suggests that ethane is dehydrogenated to ethylene in the gas phase. However, further
increase of oxygen partial pressure appears to favour further oxidation of methane to CO2 ,
ACKNOWLEDGEMENT: Financial support from NATO and TUBiTAK is gratefully

acknowledged.
REFERENCES
Bytyn, W., and Baerns, M., (1986) "Supported PbO catalysts for the Oxidative Coupling of
Methane. The effect of Surface Acidity of the Support on C2 + selectivity" Appl.Catal., 28,
199.
Hinsen, W.B. and Baerns, M., (1984) "Oxidative Dehydrogenation and Coupling of
Methane", 8th International Congress on Catalysis Proceedings, voU., 581-592.
Ito, T. and Lunsford, J .H., (1985) "Synthesis of Ethylene and Ethane by Partial Oxidation of
Methane over Lithium-Doped Magnesium Oxide", Technology, 721-722.
Ito, T., Wang, J.X., Lin, C.H. and Lunsford, J.H., (1985) "Oxidative Dimerization of
Methane over Lithium-Promoted Magnesium Oxide Catalyst", LAm.Chem.Soc., 107,
5067-5068.
Jones, C.A., (1985) "Hydroxilated Magnesia Support", U.S.Patents 4,517,398 Atlantic
Richfield Co.
Jones A.C., Leonard, J.L, and Sofranko, AJ., (1987) "The Oxidative Conversion of
Methane to Higher hydrocarbons over Alkali-Promoted Mn/Si0 2 ", J.of Catalysis, 103,
311-319.
Keller, E.G. and Bhasin, M.M., (1982) "Synthesis of Ethylene via Oxidative Coupling of
Methane", Journal of Catalysis, 28, 33-51.
Otsuka, K., Jinno, K., and Morikawa, A., (1985) "The Catalysts Active and Selective In the
Oxidative Coupling of Methane", Chemistry Letters, 499-500.
Otsuka, K., and Jinno, K., and Morikawa, A., (1986) "Active and Selective catalysts for the
Synthesis of C2H4 and C2H 6 via Oxidative Coupling of Methane", J.of Catalysis, 100,353-
359.
Otsuka, K., and Nakajima T., (1986) "Partial Oxidation of Methane Over Rare Earth Metal
Oxides Using N20 and O2 as Oxidants", Inorganica Chemica Acta, 120, L27-L28.
Otsuka, K., and Jinno, K., (1986) "Kinetic Studies on Partial Oxidation of Methane over
Samarium Oxides", Inorganica Chimica Acta, ill, 237-241.
Sofranko, J.A., Leonard, IJ. and Jones, C.A., (1987) "The Oxidative Conversion of
Methane to Higher Hydrocarbons", Journal of Catalysis, 103, 302-310.
ULTRAPYROLYSIS OF HEAVY OILS: REACTION KINETICS
AND REACTOR TECHNOLOGY
F. BERRUTI and L.A. BEHlE

Department of Chemical and Petroleum Engineering
The University of Calgary, Calgary, Alberta 12N lN4
Canada
ABSTRACT. This contribution covers recent progress on heavy oil pyrolisis considering the following
topics: reaction mechanisms, pyrolysis of mixtures, and reactors for kinetic studies. Furthermore, a review
concerning ongoing studies on the kinetics of heavy oil ultrapyrolysis/upgrading along with a description
of the new generation reactors under development at the University of Calgary, Alberta is also presented.
1. Introduction
Pyrolysis, thermal pyrolysis, thermolysis, thermal cracking, non-catalytic cracking, and

gasification are all terms which refer to approximately the same generic reaction: the scission and
recombination of molecules due solely to the provision of sufficient thermal energy to allow the
reactions to proceed, in the absence of oxygen.
The pyrolysis of hydrocarbons in general and light hydrocarbons in particular has long been
a reaction of commercial importance. For years, pyrolysis has been implemented in refineries
as a primary method for producing gasoline from heavier petroleum fractions. More
important, though, is the application of hydrocarbon pyrolysis for the production of olefins, the
basic feedstock for the petrochemical industry. Economically, this is one of the most important
reactions used industrially since the mid-1950's. Various feedstocks have been employed to meet
the olefin demand in the world. In Canada and United States most olefin production plants are
usually ethane- or propane-based, in view of the abundant natural gas reserves. In contrast,
Europe and Japan have traditionally relied on naphtha as a feedstock. However, because of the
predicted limited future supply of light feedstocks, producers have begun to shift to heavier
feedstocks (gas oil, residual oil and even the whole crude itself).
In Canada, a significant interest exists in the development of new and efficient, economical and
reliable methods of exploiting the remaining energy resources. In particular, because of the vast
existing resources in the form of heavy, or high molecular weight, hydrocarbons (so-called heavy
oils or tar sands bitumens), there is an urgent need to develop efficient means of upgrading these
to lower molecular weight feedstocks, which can be handled and utilized in the manner of the
lighter, conventional hydrocarbons. Present methods used industrially for upgrading heavy oils
include fluid coking and delayed coking. These technologies reject typically 17 and 25 percent
of the feedstock as coke and other non-usable byproducts, respectively (Schumacher, 1982). At
present, large amounts of coke are stockpiled because of potential hazards to the environment
(sulphur and heavy metals content) in economically disposing of them with current technology.
Thermal cracking of heavy hydrocarbons, under specific operating conditions, may constitute an
efficient and economical upgrading method.
325
H.I. de Lasa ef al. (eds.J. Chemical Reactor Technology for Environmentally Safe Reactors and Products. 325-352.
326
1.1. CLASSIFICATION OF PYROLYSIS PROCESSES
Bergougnou and co-workers (Mok et al., 1984; Graham et al., 1986; Berg et aI., 1986) have
developed, in the course of their work on the pyrolysis of wood, cellulose and hydrocarbons, a
terminology to deal with the increasing severity of the thermolytic pyrolysis processes. Slow
pyrolysis is defined as a process which takes place at temperatures less than 500°C, in which the
feedstock is heated at low rates « 2 °C/s), and in which the reactant resident times are measured
in the scale of minutes to hours.
Flash pyrolysis is defined as that set of processes in which the heating rate is greater than
2°C/s, for which the maximum temperature is in the range of 400 to 600°C, and the residence
times of the vapour reagents and products range up to 2 s.
Fast pyrolytic processes incorporate heating rates of 200 to lOsoC/s, temperatures higher than
600°C, and short vapour residence times « 0.5 s).
Ultrarapid pyrolysis, or ultrapyrolysis, constitutes that class of processes capable of heating
rates greater than 1()5°C/s, with residence times between 10 and 800 ms, and conducted at
temperatures up to 1000°C. In general, what differentiates processes operating under each of
the above categories is the resulting product spectrum. The slower, less severe processes yield
a relatively greater proportion of undesirable byproducts (e.g. coke). Figure 1 illustrates a
generic pyrolytic reaction pathway, including the speed of the reactions involved. On the basis
of the above classification, it can be expected that fast pyrolysis processes, and in particular
ultrapyrolysis, can take advantage of the differences in the rates of the competing reactions to
maximize the yield of desirable light products.
S<"ssioniCoupling
Feedstock - - - - - - - - -... Products

(Fast)
7
(Slow) /
Cor<J<>nsa"on
1
BTX Intermediaries
' '00' "",,,.,.MI".

Coke
Figure 1. Generic pyrolytic reaction pathway (Rebick, 1983)
1.2. HEAVY OIL PYROLYSIS MECHANISMS
The thermal pyrolysis of hydrocarbons in general can be characterized as a set of fragmentation

and recombination reactions which occur in series and parallel. Any given reaction, in
accordance with the generally accepted free-radical chain mechanism produces either final product
or feedstock for further reaction.
327
The free-radical mechanism involves several reaction types: (1) Initiation - the introduction of
free radicals into the reaction system. In pyrolysis, the reaction is initiated thermally with a
probable homolytic cleavage of a carbon-carbon bond. (2) Propagation - a series of reactions that
converts reactants to products while leaving the radical concentrations unchanged (radical
decomposition and isomerization, hydrogen transfer and radical addition). (3) Termination - the
combination or disproportionation of radicals to give stable products (Rebick, 1983).
The two major parallel reaction pathways competing for the feedstock are the (desirable)
hydrocarbon recombination reactions, which result in lighter products of interest, and the
(undesirable) coking reactions, which yield carbon from light hydrocarbon feedstocks and highly
naphthenic structures from heavier feedstocks.
As a result of the parallel nature of the product yielding and coking reactions, any thermal
hydrocarbon pyrolysis process constitutes an economic balance between feedstock sacrificed to
byproduct coke and the measures necessary to minimize this loss.
Although hydrocarbon pyrolysis has been a subject of intense research over the past 100 years,
heavier compounds (CIO +) have largely been excluded from study. Rather, most studies have
been restricted to light paraffins such as ethane, propane and butane. This is primarily due to
the fact that pyrolysis is a non-selective process. Thus, as heavier and heavier hydrocarbon
reactants are pyrolysed, the complexity of the product mixture increases dramatically. It was not
until the widespread application of sophisticated analytical techniques, such as gas
chromatography and gas chromatography-mass spectrometry, that it became possible to identify
and quantify the vast products of heavier hydrocarbons pyrolysis.
Typical heavy hydrocarbon feedstocks, such as naphtha, gas oil and vacuum gas oil, are
composed of hundreds of compounds, ranging from n-paraffins to naphthenes to aromatics. In
order to properly understand the pyrolysis of these heavy feedstocks from a scientific point of
view, one must first understand the pyrolysis mechanisms of the pure components which make
up the complex mixture. Following this, interactions between the major components types
should be studied and only after this stage has been successfully completed, should the whole
feedstock be studied.
1.3. PYROLYSIS OF HEAVY HYDROCARBON MIXTURES
The pyrolysis of hydrocarbon mixtures cannot be adequately described by a simple additivity rule
based on the results of the pyrolysis of the forming hydrocarbon groups. Significant interactions
exist, likely due to the free-radical reaction mechanisms, and must be considered (Froment et aI.,
1977). Interactions have been reported in a few studies dealing with light hydrocarbons mixtures
and the observations should be transferable to heavier feedstocks (Rebick, 1983). In general,
it has been found that components that pyrolyse according to similar mechanisms have little effect
on each other, whereas components with different cracking rates interact so that the more
refractory inhibits the pyrolysis of the more reactive, while the latter accelerates the pyrolysis of
the former. While minimal interactions have been observed in paraffin-paraffin mixtures, the
presence of olefins inhibits the rate of conversion of paraffins (phenomenon that can become
significant at high conversion levels). Pyrolysis studies of paraffin-aromatic interactions are
virtually nonexistent in the literature. However, the general rule of the interactions between more
and less refractory components is still expected to apply. The interaction of different aromatic
species is expected to generate large amounts of undesirable multi-ring polyaromatic components.
The results of only a few investigations on heavy oil cuts have been presented (Hirato et al.,
1971; Kumar and Kunzru, 1985; Depeyre et aI., 1989; Kavianian et al., 1990). Since the
original oil feeds consist of a large number of compounds, it is impossible to consider a
328
comprehensive model involving all the elementary reactions involved. The composition of the
oil has to be simplified by considering a limited number of fractions or functional groups.
Among the recent studies on the modelling of the kinetics of heavy hydrocarbon pyrolysis, there
are two that are typical and represent the modelling procedure.
The first was presented by Kumar and Kunzru (1985) for modelling of naphtha pyrolysis. In
this study, it is assumed that naphtha could be represented as a pseudo-pure compound and the
primary decomposition represented by a single reaction with the initial selectivities determined
experimentally. Based on the experimental results, the primary reaction is represented by a first
order reaction for the whole range of conversions and the initial selectivities are assumed to be
constant. The secondary reactions are also represented by molecular reactions and only important
secondary reactions that can occur between the various primary products have been accounted
for. A sixth-order Runge-Kutta-Verner method was used by these authors to solve a set of
reactions which include 22 reactions and 14 components. The predicted and experimental product
yields were compared and the rate constants adjusted, by trial-and-error, to minimize the
deviation between the predicted and experimental values. The major limitation of this approach
is that the initial selectivities are to be determined experimentally.
The second recent study was reported by Depeyre et al. (1989) for the modelling of thermal
steam cracking of an atmospheric gas oil. Since atmospheric gas oil consists of a large number
of hydrocarbons, they divided the original sample into four families. Each family was
represented by one representative component such as n-hexadecane for paraffins, isohexadecane
for isoparaffins, CI3H26 for naphthalenes and C15 H34 for aromatics. In order to reduce the number
of reactions involved, those that did not playa significant role in the system, all the olefins with
carbon number above five and paraffins larger than propane were considered negligible. The
proposed model consisted of 138 reactions, 18 molecular species and 24 radical species.
2. Reactors for Kinetic Studies
The proper design of commercial pyrolysis reactors requires a suitable expression for the intrinsic
rate of the reactions. As intrinsic rate equations cannot yet be predicted, especially for the
ultrapyrolysis regime, experimental data is required. This data is best obtained from bench-scale
laboratory reactors, rather than from pilot plants or commercial-scale units. In laboratory scale
pyrolysis reactors, the design and operating conditions can be chosen to reduce or eliminate the
effects of mass and heat transfer, contaminants and catalytic surfaces from the observed
measurements, thus allowing for the development of accurate expressions. It is most
advantageous if the laboratory reactor is operated isothermally (in space and time), so that the
temperature can be considered as an independent variable. Also, the pressure should be ideally
kept constant.
2.1. BATCH REACTORS
In a batch reactor, the reactant is placed in a close vessel and pyrolysed under constant volume
conditions. After each run, the reactor is opened to permit quantification and analysis of the
products. Temperature is generally maintained constant by means of an electric furnace or a
liquid thermostat. Batch reactors are generally fairly large to permit a sizable sample and to
minimize reactor surface effects (Mulcahy, 1973).
The large size of many reactors used has lead to the existence of dead spaces and, in particular,
a non-uniform temperature throughout the reactor.
329
Even if the above problems can be resolved, batch reactors can measure with accuracy the
intrinsic rates of slow pyrolysis reactions. For faster reactions, the time required to heat the
sample up to reaction temperature and then cool it down becomes an appreciable fraction of the
total, and thus the accuracy with which data can be obtained becomes progressively poorer. If,
however, the temperature history is well-defined, the non-isothermal data can be corrected using
the "equivalent reaction time" concept (Hougen and Watson, 1947), which can provide, in some
cases, a reasonable accuracy. The equivalent reaction time is the time required at a reference
temperature to produce the same conversion as that obtained in the actual non-isothermal
operation.
2.2. FLOW REACTORS
For fast reaction times, it becomes necessary to utilize flow reactor systems, if accurate data is
required for kinetic studies. In steady-state and with turbulent flow conditions, temperature and
compositions, and consequently the rate of reaction, vary with axial location only, but not with
time.
The main problems related to the use of the tubular-flow reactor are caused by the deviations
from ideal flow conditions, entrance and exit effects, heating and cooling rates and effects of heat
of reaction on the temperature profiles and on the temperature difference between the reactants
and the reactor wall. The heat transfer limitations can be very significant if the reactor diameter
is not very small and if temperatures above 600°C are employed. Another problem arises from
the difficulty in the evaluation of the actual reaction time, because of the increase in volume of
the reacting mixture with temperature and conversion.
If the temperature variations as a function of axial location can be predicted, the "equivalent
reactor volume" concept (Hougen and Watson, 1947; Froment et aI., 1961) can be applied to
convert the data to a pseudo-isothermal basis. According to Hougen and Watson (1947), the
equivalent reactor volume is defined as that volume which, at a constant reference temperature,
would give the same conversion as the actual non-isothermal tubular reactor. The reference
temperature has frequently been taken as the arithmetic mean of the process gas temperatures
in the last 40% of the reactor (Van Damme et aI., 1975).
2.3. PULSE-MODE UNITS
Pulse-mode units belong to one of the following subgroups: shock-tube, laser, arc, filament-
resistive heating and high frequency induction heating. Although the temperature rise times of
the shock-tube, laser and arc pyrolysis units are shorter than other units, the determination and
verification of the equilibrium pyrolysis temperature is a serious problem. In shock-tube reactors,
there is an error of 5 to 10% in determining the residence time and temperature determination
is quite inaccurate (Bradley and Frend, 1971). In laser, arc or plasma jet pyrolyzers, the reaction
temperatures are very approximate. Since the pyrolysis temperature and residence time are the
key variables in the study of reaction kinetics, these units should not be used for quantitative
work.
The filament pyrolyzers use a filament of platinum and the reactant sample is directly applied
onto the platinum foil. An older technique involved an applied voltage at the ends of the
platinum foil resulting in an increase in the temperature due to resistive heating. A variation of
the technique developed by Levy (1967) is based, in principle, on applying relatively high voltage
to the terminals of the filament and rapidly decreasing its magnitude to the normal level, thus
performing a "voltage sweep". This results in a rapid rise of the filament temperature to
330
approach pyrolysis temperatures without reaching the melting point of the filament. Some
disadvantages to filament units include the effect of filament geometry on the heat dissipation and,
therefore, the generation of large temperature gradients along the filament (Levy, 1966).
Moreover, carbon dissolution in the platinum foil changes its characteristics (Jennings and
Dimick, 1962) and the changing resistivity of the filament changes the equilibrium temperature
of the filament.
Induction heating in a Curie Point Pyrolyser is a pyrolysis technique that consists of application
of high frequency induction heating to a sample in contact with a ferromagnetic conductor (Simon
and Giacobbo, 1965). Originally designed as an analytical device for the characterization of
complex non-volatile substances, such as polymers, complex biomaterials and even bitumens, this
device has only been recently discovered as a research tool ideal for the kinetic study of fast
pyrolysis reactions. The temperature of the conductor rises in a few milliseconds to its maximum
temperature, known as the Curie Point Temperature, and then remains constant. The Curie Point
Temperature is the temperature at which the ferromagnetic material loses its ferromagnetism
to become paramagnetic, and is dictated by the composition of the metal itself. When a
ferromagnetic material (nickel-iron-cobalt alloy) is placed in an induction coil and the coil is
energized with direct current, the material becomes magnetized. When the polarity of the current
is changed, the magnetic poles are reversed. If the polarity of the coil is changed rapidly,
hysteresis heat, due to ohmic resistance, is generated very quickly in the ferrous material, which
will cause the metal to very rapidly reach a temperature at which it loses its magnetism and the
temperature is maintained constant, until the high frequency energy is switched off at the end of
a pre-set reaction duration. By selection of the appropriate ferromagnetic alloy, a wide range of
conductor temperatures, and therefore of pyrolysis temperatures, can be obtained. The great
advantage of this technique over other pyrolysis systems is that the final temperature (Curie
Point) depends only on the ferromagnetic metal used and is independent of any fluctuations in
experimental conditions (Buhler and Simon, 1970). Also, catalytic effects have not been
observed when using ferromagnetic conductors of different compositions (Jones and Moyles,
1961) or by coating the conductors with inert materials such as gold (Simon et aI., 1967). Based
on the above observations, pyrolysis under precisely controlled and known conditions can be
achieved. Some experimental work includes studies by Egsgaard and Carlson (1983, 1986),
Rastogi et al. (1988a, 1988b) and Fairburn et ai. (1990).
2.4. THE UNIVERSITY OF CALGARY MICROREACTOR SYSTEM
An innovative micro-reaction system, based on the Curie Point Pyrolyser, has been developed
at the University of Calgary and successfully employed for kinetic studies dealing with
ultrapyrolysis of various hydrocarbons, including propane, n-hexadecane and heavy oils (Rastogi
et al., 1988a; Fairburn et al., 1990; Tan and Behie, 1991).
The equipment, schematically represented in Figure 2, which has undergone significant
modifications and substantial improvements over the years, is comprised of a glass pyrolysis
chamber (A), a microreactor containing a ferromagnetic wire coated with the sample to be
pyrolysed (B), a two-way, zero volume switching valve (C), a solenoid activated hammer
assembly (D), a commercial Fisher Model 0316 Curie Point Pyrolyser and associated pyrolysis
module (induction coil) (E), a timer control unit (F) and a Gas-Chromatograph coupled to a Mass
Spectrometer as a combined detection system (GC/MS) (G).
The pyrolysis chamber consists of a glass tube designed to contain the microreactor system
during a pyrolysis experiment. The upper part of the chamber is connected with a hammer
assembly through a kolvar tube sealed to the glass. The lower part is designed to hold the
331
microreactor in place and minimize the dead volume through which the pyrolysis products have
to travel before reaching the analytical station. Figure 3 illustrates the detailed design of the
pyrolysis chamber with the microreactor in place.
"ICIIO-SWITCH ---~,q-.,
Hammer System
HA .... E..
A
S£NSOA
AOAPTER
RING --==~'t
8LOCK
CAARI[A •• S
Figure 2. Curie Point pyrolyser with microreactor system
The microreactor consists of a selected ferromagnetic wire, depending upon the desired
reaction temperature, having a diameter of 0.4 mm and 12 mm long, coated with a known
amount of sample to be pyrolysed (a few micrograms), sealed into a glass capillary tube (0.87
mm external diameter) under vacuum. The resulting system is therefore a constant-volume batch
reactor. A schematic of the microreactor is shown in Figure 4.
, 18in.
(metal)
kolvor--------.
Koho/ar /Gloss Seal ~
t.4ccroreQctor
1 84mm
12nvn - - - - - - I
- Pyrex Capilary Ferromagnet~ Wre

25mm (Coated with Sarrpo
Figure 3. Pyrolysis Chamber Figure 4. The Microreactor

332
A three-port, two-way, zero volume high temperature switching valve is located at the base
of the pyrolysis chamber. This valve allows the carrier gas going to the gas chromatograph to
be deviated through the pyrolysis chamber to achieve a number of objectives. These include
the initial flushing of the chamber with inert helium to remove air, to quench the reaction
products after pyrolysis has been achieved and to carry the products through the analytical
system. The direct mixing of reaction products with the carrier gas under the conditions present
in the pyrolysis chamber ensures a very rapid quench with cooling rates in excess of 1050 C/s
(Sundstrom and DeMichiell, 1971). The valve is maintained at a temperature of about 300°C,
high enough to prevent products condensation and low enough to avoid further thermal cracking
to occur.
The hammer assembly, located above the pyrolysis chamber, is used to break the microreactor
after a preset period of time and thus enable the reaction products of pyrolysis to be quenched
by the carrier gas stream and transported quickly to the gas chromatograph. The hammer,
consisting of a rod having a diameter and length such to fit perfectly into the pyrolysis chamber,
is activated by a solenoid and, during the pyrolysis experiment, travels very quickly with a
downward motion into the chamber for a distance so to break the glass encapsulated
microreactor. The hammer assembly is illustrated in Figure 2.
During the pyrolysis experiment, the pyrolysis chamber, containing the microreactor, is placed
inside the Curie Point Pyrolyser module, consisting of a high frequency induction coil surrounded
by an aluminum block provided with a resistance heater, capable of maintaining the complete
assembly at a temperature of about 300°C. The microreactor is positioned within the pyrolysis
chamber at a level which corresponds to the region exposed to the maximum heating intensity,
when the chamber is inserted into the pyrolysis module. The module is connected to the
pyrolyser control unit which supplies the power to the induction coil and controls the temperature
of the module itself. The Curie Point Pyrolyser module is illustrated in Figure 2 with the exact
location of the pyrolysis chamber and the microreactor.
An automated timer control unit has been installed to control and monitor all the operations
involved in each experiment. The timer unit allows to preset the duration of the pyrolysis
experiment. The timer starts up the Curie Point Pyrolyser, it controls and displays the actual
reaction time and, by taking into account the delay caused by the time taken for the hammer to
move to its initial position to the point where it breaks the microreactor glass seal, it starts the
movement of the hammer.
The whole pyrolysis system is set up directly on top of a Hewlett Packard 5890 Gas
Chromatograph coupled with a Hewlett Packard 5970 Mass Spectrometer. The analytical
equipments are controlled by a Hewlett Packard 59970 MS Chemstation where data are stored
and interpreted.
A very rigorous procedure (Fairburn, 1988), developed over the years, is implemented for each
run. This methodology and the above described system have been proven very reliable and
successful in providing the best possible qualitative and quantitative information on the product
distribution derived from pyrolysis of various materials under carefully controlled temperatures
and reaction times. Wires have been utilized in the experimental work having Curie Point
temperatures from 300 to 1000°C and experiments performed with various feedstocks with
carefully controlled reaction times between 50 and 2000 milliseconds.
The microreactor system characteristics have been carefully studied in order to confirm that the
temperature-time profile could really approach the ideal "square wave" shape. A number of
experiments have been performed to study these profiles, utilizing micro-thermocouples (type K;
25 }.tm diameter) spot welded onto each wire, so that oscilloscope traces of the actual profiles,
upon activation of the pyrolysis system, could be obtained (Fairburn, 1988). In all cases, the
333
wires heated to their Curie Point temperature in a nearly first-order manner, without overshoot
or oscillations. The temperature rise time (fRT) was measured for wires having different Curie
Point temperatures (600, 750, 850°C) to be 52, 77 and 91 ms, respectively. To verify that the
sample to be pyrolysed and its surroundings could reach the same temperature, a simplified
computer simulation of the unsteady state heat transfer within the microreactor for the worst case
scenario (i.e. heat transfer by conduction only) was performed by Rastogi et al. (1988b). This
simulation confirmed that, under these conditions, confined micrograms quantities of samples
would reach the temperature of the wire within one degree in less than 0.2 ms. Hence, the TRT
of the sample would be the same as that of the wire.
3. Ultrapyrolysis Reaction Kinetic Studies

Using the University of Calgary Microreactor System
3.1. PROPANE ULTRAPYROLYSIS (RASTOGI ET AL., 1988)
Initial studies, employing the microreactor system, have been conducted using propane as
feedstock (Rastogi et aI., 1988a). The reason for this choice is that much has been published on
this subject and the literature information could be utilized for comparisons. Nanoliters of
propane, carefully enclosed in the micro reactor , have been pyrolysed at four different temperature
levels: 600, 700, 800 and 900°C, with reaction times between 0 and 2200 ms.
Some of the experimental results obtained in this work are illustrated in Figure 5, where the
experimental propane conversion data are plotted versus the reaction time and compared to other
data from the literature and various simulation results (Sundaram and Froment., 1979;
Kershenbaum and Martin, 1967; Layokun and Slater, 1979). The primary products resulting
from the propane ultrapyrolysis have been identified to be methane, ethylene, hydrogen and
propylene and the experimental yield of olefin was significantly higher than that obtained by other
workers, presumably due to the extremely controlled reaction conditions and better quench
system. Based on the postulation of first-order kinetics and on the utilization of a constant
volume batch reactor, the half lives of the reaction were calculated from the kinetic constants at
the four different temperatures (600, 700, 800 and 900°C) to be 14,270, 663, 422 and 88 ms
respectively. A value of 136 kllmol (32.4 kcal/mol) was calculated for the activation energy over
the entire temperature range studied. This initial study confirmed the reliability of the
micro reactor system and that very precise data with known experimental conditions can be
generated for kinetic studies.
3.2. N-HEXADECANE ULTRAPYROLYSIS

(FAIRBURN ET AL., 1990) AND (TAN ET AL., 1991)
The microreactor system proposed at the University of Calgary has been subsequently used to
study the ultrapyrolysis kinetics of n-hexadecane, a gas oil model compound. n-hexadecane
(about 12 p,g per sample) has been pyrolysed at temperatures ranging from 576 to 842°C for
reaction times of 100 to 3200 ms (including the temperature rise time TRT) and pressures in the
range of 1 to 2 atm.
The experimental results indicated a dramatic increase in conversion with reaction time and
temperature. When pyrolysing at low temperature (576°C), only a very low conversion (less
than 9%) was attained for a lengthy reaction time (3200 ms). However, when the pyrolysis
temperature was increased, the reaction accelerated such that more n-hexadecane was converted
334
in a shorter period of time. 87% conversion was achieved with only 500 ms of reaction time at
842°C. The conversion levelled off when the reaction time was extended, at this temperature,
probably due by inhibition caused by propylene/C4'0Iefins, as shown also by other researchers
(Depeyre et aI., 1985).
Reaction Tempt'ra!lIre: 700 C

Temperature Rise TIme = 46 ms
100.0 r---:---:-:----------------,
• experlme_ daIa
- '-FrOfMnt mol rxn almul.
- - - Leyokun rad nm slmut.
c
o
o~otun • Stole< daIa o
data.. .
80.0 -Kerlhenboum . -
f • IkM.*enI and Fromenl
~ • CrynH • Fromenl <lllfa
c • o
.
<3
c
60.0
/// .
..
[
"'
o
0.
40.0
.......-<.
..
o· •
:
" ~ ..
..... • •
20.0 '.. • .~ .. , •
~~.~
O~L----L- _ _ _ L_ _ _ ~ ____ ~ ___ ~
0.0 ,ooo~ 1500.0 2500.0

TIme (milliseconds)
Figure 5. Conversion versus reaction time at 700°C
As pyrolysis temperature has a dramatic effect on conversion, it is not surprising that it can
drastically alter the product distribution as well. Some results, illustrated in Figures 6 and 7,
have been organized so that the products are grouped as follows: hydrogen/methane, ethylene,
other gases (ethane, propylene, propane, butanes and 1,3 butadiene), CS-Cg l-olefins, ClO-C 1S 1-
olefins and aromatics. The Cs+ diolefins, cyclic olefins and cyclic diolefins are not represented;
these compounds make up 2 - 10% of the overall product stream for conversions ranging between
50 and 90%.
As little has been published on the ultrapyrolysis of n-hexadecane at high temperatures, the
results obtained at 842°C deserve a special discussion. These experiments covered a wide range
of conversions (11 % at 100 ms; 92 % at 800 ms) and, consequently, the results shown in Figure
6 display the various stages of the process. At the very short reaction time of 100 ms, the C1-C 3
paraffins and, in particular, the entire range of l-olefins from ethylene through pentadecene are
detected. The ClO-C 1S l-olefins account for more of the product stream than the lighter CS-C g 1-
olefins, indicating that the heavier olefins had not yet decomposed into lighter species. No
aromatics are detected. The conversion is low, under these conditions, and hence the pyrolysis
still very much in the earlier stages, considering 91 ms of TRT. A large increase in conversion
(47%) is achieved by pyrolysing for a longer duration (250 ms). Ethylene and "other gases"
become the dominant products and the CS-C g l-olefins reach a concentration peak. They are
more prevalent than the ClO-C 1S l-olefins which are superseded by an increasing
hydrogen/methane yield. Diolefins, such as 1,3 butadiene, although not shown on the graph, start
to appear. Evidently, this shows that secondary reactions, such as higher olefins decomposition
and dehydrogenation, begin to playa role. At 500 ms, 87% conversion is achieved and a
significantly different product distribution is attained. Hydrogen/methane and aromatics
335
(benzene, toluene and styrene) yields slightly exceed that of the ClO-C IS l-olefins and the ethylene
and "other gases" yields are much higher than those obtained at 250 ms (ethylene yield reaches
28 wt%). Diolefins and cyclic olefins are also more prevalent. In the 800 ms (92 % conversion)
run, the aromatics and hydrogen/methane yields, each approximately 10%, far exceed those of
the l-olefins, with the aromatic yield including complex components such as naphthalene and
methyl-naphthalenes. Between 500 and 800 ms of reaction time, the ethylene yield levels off and
that of the "other gases" starts to decrease. Diolefins, cyclic olefins and cyclic diolefins
constitute about 11 % of the product stream. Under these "longer" reaction times, secondary
products comprise a significant portion of the product, at the expense of more desirable primary
products. This definitely confirms the expectations of the benefits of operating in the
ultrapyrolysis regime.
Figure 7 shows the results of ultrapyrolysis experiments conducted at a constant 500 ms of
reaction time with varying temperature. As expected, the trends are similar to those reported in
Figure 6. At 576°C (3% conversion), the primary products are C.-CIS 1-olefins and C I-C3
paraffins. At 750°C (46% conversion), the CS-C 9 l-olefins are more prevalent than the heavier
l-olefins and the hydrogen/methane and aromatics yields are on an upward trend, showing the
beginning of secondary reactions. At 842°C (87 % conversion), as discussed earlier, the ethylene
and "other gases" yields increase dramatically at the expense of the CS-C IS l-olefins. Under these
conditions (842°C and 500 ms), the ethylene production reaches the peak of 28%.
30 30 --0-- other gases
--
-..- C2H4
~ + other gases ~ -0- H2ICH4
1 ----tr--
1 20 l:J,C2H4
o
CS-C9 1 -olehns
---.-
H2ICH4 20 aromatics
"0 u
Qj J( C5-C9 l-deftns OJ Cl0-C15l-olelms
>= C aromahcs >=
u • C'O-C'5'-<>ieflns "0
~
~
u
"0
a 10 --- •••-:-;-;.'.0 a 10
n: n:
_._.:.:~;~;:::~:~:;~:;=:~~i:=~-~::·::~::::~-:::::;
oL-~~&£~~~~~
oL-~~~--~--~----~
o 200 400 600 800 400 500 600 700 BOO 900
Reaction Temperature (0C)
Reaction Time (ms)
Figure 6. Product distribution Figure 7. Product distribution

(842°C) (500 ms)
At 576°C, the primary products, as given above, prevail even for the lengthy 3200 ms runs
(8% conversion), showing a continual increase in these product yields as the reaction time
proceeded from 100 to 3200 ms. The results obtained at 750°C with reaction times between 100
and 1100 ms, exhibit trends similar to those for 842°C. Within only 250 ms, 27% of the
conversion is achieved and the CS-C 9 1-olefins exceed all other primary products. At 1100 ms
(74 % conversion), the l-olefin yield has levelled off while the ethylene and "other gases" yields
are dramatically increased.
As the reactant in the microreactor is in intimate contact with a metal surface, there may be
some concern regarding possible catalytic effects. Despite the findings of Jackson and Walker
(1971) and Simon et al. (1967), it was deemed necessary to pyrolyse some samples using wires
coated with an inert gold surface. The ethylene, aromatics and hydrogen/methane yields for gold-
336
coated wires have been compared with those obtained with regular wires and no effect has been
noted on the product distribution and conversion.
In all cases, no coke formation has been detected on the wires, on the broken microreactor
glass walls or on the walls of the transfer lines.
A generalized reaction scheme for low pressure n-hexadecane ultrapyrolysis has been
proposed by Fairburn et a1. (1990), based on the experimental work described above.
The reaction rate constants and activation energy for the n-hexadecane ultrapyrolysis have
been determined assuming the overall decomposition to be of the first order. The temperature-
time profile experiments, described earlier, indicated that the reaction temperature was a function
of time, even for the microreactor system, for the first 52-91 ms of the pyrolysis. This has been
taken into account in the calculation of the kinetic constants. Also, the high conversion data
points have been discarded due to the observed inhibition phenomena. The half lives of the
reaction have been calculated at the three temperatures of 576, 750 and 842°C to be 33,000,568
and 129 ms, respectively. The activation energy has been evaluated to be 165 kJ/mol, (39.4
kcal/mol), as expected only slightly higher than that obtained by Rastogi et al. (1988a) for
propane ultrapyrolysis. The kinetic data obtained are plotted in Figure 8 against those of
previous researchers.
100,-------------------,
50
o ~ Zhou dol (1967)

6" Oepcyre "01 (lge5)
-50 +: Aeblck (1981)
x ~ Gfoenen<lyk ~laI (1970)
O· V_ 6 Good (1949)
V" Poochent.ov 8. 6ot'QROV (1958)
• = This Wort!.
-10.0 <--_ _ _ _-"-_ _ _ _---'_ _ _ _---1
0.8 1.0 1.2 1.4
Inverse Temperature (1/Kx10 3)
Figure 8. Comparison of reported kinetic data for n-hexadecane pyrolysis.
The previous studies, all conducted using tubular flow reactors, cover a temperature range of 500
to 850°C. It is important to note that space times (reactor volume divided by the volumetric feed
rate) rather than the true residence (or reaction) times have been reported. In the case of Depeyre
et a1. (1985), the outlet rather than the feed volumetric rate has been used, thus the space times
are possibly significantly underestimated and, hence, the rate constants overpredicted. The low
temperature data of the study by Fairburn et a1. (1990) agrees fairly well with other reported
data, as the importance of an accurate reaction time/temperature measurement is less critical
under those conditions, because of the slowness of the reactions. At the high temperature levels,
the difference between the obtained data and those of Depeyre et al. (1985) can be attributed to
the wrong evaluation of the space time but also probably to a better control of the reaction, with
the use of the micro reactor system. At high temperatures, the conversion observed with a
337
conventional tubular reactor is expected to exceed that attained in the microreactor with a rapid
and effective quench.
Tan et al. (1991) extended the temperature range studied by Fairburn et al. (1990) to 1000°C.
They showed the importance of the Temperature Rise Time (TRT) on the n-hexadecane
conversion at these high temperatures (Figure 9), reporting conversions of 8% and 10%,
corresponding to TRTs of 100 and 125 ms, at 900°C and 1000°C, respectively. Based on these
results, they defined the Effective Residence Time (ERT) in the micro reactor as the time period
at which the exact Curie Point Temperature would yield the same conversion as the actual
reaction for the Total reaction Time (TT). According to this definition
ERT = IT - TRT + ET
where ET is the Equivalent reaction Time in the TRT region, defined as the time at which the
Curie Point Temperature would give the same conversion as the actual reaction at the end of the
TRT. A schematic diagram showing the Effective Residence Time is shown in Figure 10. As
indicated in Figure 9, different wires have different TRT profiles, since variations in the nickel,
cobalt and iron contents affect not only the Curie Point Temperature but also the TRT, with
alloys having higher nickel content showing increased TRTs while higher cobal contents giving
smaller TRTs (Levy et aI., 1972).
l000.-____________________
..
~
60 - - - l000~ wIre
.- - - - - - - 1000
- 900"C wire /1 ."0 750 1RT Prof"lIe ;
Ic <0 TRT Profile

, -.; v
o
'
L
9 ~
~ 500 : Tolol Reoction Tme
v ( ___ .t' / SOO ~ Q. ----- ------.-------------------------)
>
c
° 20 / E ~ 250 f---~-_!!.'~-R~~"!.'!-----)
u
_ _
. /Corwers'on V
~
..
~_t ~
___~_L __ ):
0 0~0------~,00t-------~~----~~
0 50 100 150 200
Total Reaction Time (ms) Total Reaction Time ems)
Figure 9. Effect of TRT on Figure 10. Schematic diagram

n-hexadecane conversion for ERT calculation
The Equivalent reaction Time (ET) can be determined by knowing the appropriate first order
kinetics of the n-hexadecane decomposition for corresponding reaction conversions at the end of
the TRT period in actual runs. The ET has been evaluated to be equal to 25 ms, 18 ms and 12
ms for the three temperatures of 800, 900 and 1000°C, respectively. Therefore, the Effective
Residence Time is:
ERT = IT - 85 + 25 ms at 800°C
ERT = IT - 100 + 18 ms at 900°C
ERT = IT - 125 + 12 ms at 1000°C
A new kinetic expression, applicable to the high temperature range, has then be derived:
k(T) = 2.91x1Q4 exp (-20,405/RT)

338
where the activation energy (20.405 kcal/mol) is lower than that reported by Fairburn et al.
(1990), presumably due to the previously discussed olefin inhibition.
3.3. HEAVY OIL ULTRAPYROLYSIS (TAN ET AL., 1991)
Crude heavy oils are composed by a large variety of compounds, mostly aromatics and alkylated
aromatics with a carbon number from 14 to 25. These heavy aromatic hydrocarbons are very
difficult to characterize, the heavier fractions like asphaltenes being impossible to characterize
in any way. Because of these complexities, it is very difficult and inaccurate to select one or
several pseudo-components to represent the original heavy oil for the purpose of kinetic
modelling. A combination of theoretical and experimental methods must be considered to
develop a suitable kinetic scheme for heavy oil pyrolysis. The approach followed by Tan et al.
(1991) at the University of Calgary, is similar to that pioneered by Kumar and Kunzru (1985),
where the initial selectivity of primary reactions is determined experimentally, using the
previously described microreactor system. Further secondary reactions, based on the primary
products, are then developed, on the basis of theoretical mechanisms and models presented in
the literature. The unimportant secondary reactions are neglected so that the reduced model can
be both representative and computationally efficient.
A large number of runs have been performed using heavy oil samples and the major products
of heavy oil ultrapyrolysis identified are lighter components (methane, ethylene, ethane and
propylene) and some aromatic compounds, such as benzene, toluene and naphthalene.
Figure 11 shows the major product distribution for heavy oil ultrapyrolysis at lOOO°C and
different Effective Residence Times. Also, the reaction conversion, defined as total mass of
detected products per unit original mass on the microreactor wire, is plotted. As expected, the
conversion and yield of methane increase with increasing reaction time. Ethylene, lighter olefins,
benzene and toluene yields pass through a maximum within the reaction time range examined.
This indicates that all of these products are intermediate compounds during the pyrolysis process.
At the shortest reaction time of 137 ms, corresponding to a conversion of 36%, only C[-C4
paraffins and olefins, benzene and toluene are detected. This confirms that the primary source
of the alkane and alkene series in the thermal cracking of heavy oil is through the cleavage of the
benzylic C-C bonds on the aromatic side chains.
100.---------------------------~~,
60/
~
~ 80
~
o Conversion
• Olefin. Yield
~ Ethylene Yoeld
... l;iethane Yield
g 40 a Benzene Yield
• Toluene Yield
o§
Q)
>
c
o
U
387 637 887

Effective Residence TIme (ms)
Figure 11. Variation of conversion and product yields with Effective Residence Time at lOOOOC
339
The effects of reaction temperature and total reaction time (IT) on the conversion and yield of
methane are shown in Figure 12 and Figure 13. The trends are very similar, since methane is the
end product of the hydrocarbon cracking. The reaction conversion at 800 C is much lower,
D
confirming that temperatures below 800 D C are not high enough to achieve a significant cracking
at these short residence times.
l00r---------------------~~ 20r------------------------,
16
o~------~------_+------~ O~------+_------~------~
250 500 750 1000 250 500 750 1000
Toto' Reaction Time (ms) Totol Reoction Tome (ms)
Figure 12. Effect of total Figure 13. Effect of temperature

reaction time and temperature and total reaction time
on heavy oil conversion on methane yields
The influence of temperature and total reaction time on the benzene and toluene yields are
shown in Figures 14 and 15. The maximum in the benzene and toluene yields, observed at
lOOODC, indicates that two opposite reactions might take place: they can be generated through
cyclization and aromatization of lighter olefins and diolefins or, more directly, through
dehydrogenation of naphthenic hydrocarbons, and these can be consumed through reaction with
paraffinic or olefinic radicals to form increasingly more condensed polynuclear aromatics.
10r------------------------,
--~
O~------~------_+------~ ~~5O~-----5OO~-------750~----~,000
250 500 750 1000
Total Reodioo Time (ms) Total Reaction Time (ms)
Figure 14. Effect of total reaction Figure 15. Effect of temperature

time and temperature on benzene yields and total reaction time on toluene yields
Figures 16 and 17 illustrate the variations in the yield of ethylene and lighter oletins (C2-C4)
with reaction temperature and IT. At 750 ms and 900 C, the yields of ethylene and olefins
D
reaches a maximum of 16.6 and 26 wt%, respectively. Decreasing the total reaction time to 500
340
ms causes the olefin yield to drop to 14.7 wt%, whereas increasing the IT to 1000 ms results
in the yield to drop to 13.7 wt %.
To study the coke formation during ultrapyrolysis of heavy oils, a Model 240 Elemental
Analyzer has been employed to analyze the carbon deposited onto the ferromagnetic wire and/or
the glass microreactor walls. The influence oftemperature and total reaction times on the amount
of carbon formed have been studied. The experimental results confirmed that the coke yield
increases sharply with temperature and reaction time. However, at the upper boundary of the
ultrapyrolytic regime, a maximum coke yield of 17 wt% has been observed at 1000°C with a
total reaction time of 1 second. For the same total reaction time, coke yields of 10 wt% and 6.5
wt% have been measured at 900 and 800°C, respectively, sharply decreasing from those values
with a decrease in reaction time. Compared to the above values, industrial pyrolysis processes
produce very high yields of undesirable coke.
20.----------------, ~.------------.
=
o~--~+---~~--~.
500 750 1000
O~---+----+---~
250 500 1000
Totol Reaction Time (ms) Total Reaction rome (ms)
Figure 16. Effect of total Figure 17. Effect of temperature

reaction time and temperature and total reaction time
on ethylene yields on light olefins (C 2-C4) yields
4. Reactor Technology
4.1. CONVENTIONAL INDUSTRIAL PYROLYSIS REACTORS FOR

OLEFINS PRODUCTION
In conventional hydrocarbon pyrolysis, the feed is mixed with steam and then pyrolysed in a
series of multi-tube furnaces. A large excess of steam is generally employed to lower the partial
pressure of the hydrocarbon feed, thus improving the selectivity to olefins and reducing the coke
formation on the reactor wall. The residence time of the mixture is in the order of 350 to 800
ms, while the reaction temperature ranges from about 600°C, at the inlet to the radiant section
of the furnace, to 830 - 870°C at the outlet (Froment, 1981). Typical pressures range from 300
kPa at the inlet to 180 kPa at the outlet. The pyrolysis products, upon exiting the furnace, enter
a multi-tubular heat exchanger where they are rapidly quenched to 600°C in under 15 ms
(Nighswander et aI., 1989) and then further cooled to 350°C before undergoing fractionation.
Complete conversion is generally achieved and ethylene is the major product.
Over the past decade, dramatic improvements in pyrolysis technology have occurred. For
example, the M.W. Kellogg Co. (Houston, Texas) has developed a technology to pyrolyse a wide
341
variety of feeds, from ethane to vacuum gas oil, at high temperatures (greater than 750°C) and
very short residence times (less than 100 ms) (Leftin et aI., 1976) with significant increases in
ethylene yields, at the expenses of undesirable products such as off-gases (hydrogen and methane)
and highly aromatic heavy compounds. However, coke build-up still plagues this technology.
4.2. NON-CONVENTIONAL REACTOR TECHNOLOGY
The trend in pyrolysis over the last decade has been toward higher temperatures and shorter
residence times. In the case of utilization of heavier hydrogen-deficient feedstocks, short
residence time is the prime means of maximizing olefin and minimizing coke yields.
A number of recently developed processes for olefins production, operating at short reaction
times and high temperatures, but also concerned with the rapid heating of the feed and quenching
of the products, have been described.
The Advanced Cracking Reactor (ACR) is an autothermal reactor where hydrocarbon feed and
diluent are mixed with oxygen in order to partially oxidize the hydrocarbons and provide the heat
for the pyrolysis reaction. High temperatures and very short contact times are achieved before
a rapid direct quench by oil injection (Kearns et aI., 1979).
Recent industry advances have been reported such as the Quick Contact (QC) reaction system
of the Stone and Webster Eng. Co. (Gartside, 1989). The QC system consists of a new fluidized
solids unit which combines patented mixing and separation devices to produce a dilute phase
reaction system capable of operating at short residence times (200 ms) and plug flow.
Hydrocarbon pyrolysis has been also recently applied to upgrade heavy oils and bitumens to
a less viscous product, having characteristics similar to conventional crudes. Engelhard Minerals
and Chemicals Corporation (New Jersey, USA) has recently introduced the Asphalt Residual
Treating (ART) process, which upgrades heavy feeds by high temperature (> 525°C) and short
contact times « 2 s) pyrolysis in a fast fluidized bed (Bartholic, 1984). The process seems to
vaporize the lighter fractions with little or no conversion and converts the high-boiling fractions
into lighter liquids, coke and gases. The ART process has been proven in commercial test units
ranging from 7000 to 55000 barrels/day (Logwinuk and Sloan, 1985). Although the operating
conditions of the ART process are not quite in the uItrapyrolytic regime, the operation at even
shorter contact times « 1 s) and presumably higher temperatures, appears to be the long term
goal of a very promising technology.
In Canada, two major research and development programmes are being conducted at the
University of Western Ontario and at the University of Calgary.
A mini-pilot plant is being employed at the University of Western Ontario to study the
U1trapyrolysis of heavy oils, after encouraging results have been obtained utilizing cellulose,
wood and lignin as feedstocks (Graham et aI., 1986). The process, operating in the ultrapyrolysis
regime (residence times from 100 to 500 ms and temperatures from 550 to 850°C), utilizes a
novel gas-solid contactor divided into three sections: a thermovortactor, where preheated
feedstock comes in intimate contact with hot nitrogen gas, thus achieving high heating rates; a
reaction section, where the reaction occurs in a tubular flow isothermal reactor for a
predetermined time; and a cryovortactor, where cold nitrogen comes in intimate contact with the
reaction products, thus achieving a rapid quench. The results obtained in a series of runs
employing Alberta heavy oils show the typical trends to be expected in the ultrapyrolysis of heavy
oils: upgraded liquid yields ranging from 93 to 34%, decreasing with temperature; gas yields
from 3.5 to 50% increasing with temperature; and, even more important, solid coke yields in the
range of 8 to 10%, over the temperature range studied. The major gas components have been
identified to be CS-C 6 olefins, ethylene, propylene, methane and butene-I. Preliminary analysis
342
on the liquids indicated reduced viscosity, sulphur and nitrogen contents and nickel and vanadium
contents (Vogiatzis et aI., 1988).
4.3. REACTOR TECHNOLOGY DEVELOPMENTS AT THE UNIVERSITY OF CALGARY
At the University of Calgary, an extensive research programme has been devoted to the study of
novel reactor configurations capable of operating conditions suitable for the ultrapyrolysis
reactions.
4.3.1. The Spouted Bed with Draft Tube. The first reactor configuration considered has
been the spouted bed with draft tube. The spouted bed has been defined as "a bed of
particles contained in a vertical hopper and agitated by an air (or other fluid) jet entering
at the base through a single nozzle" (Lefroy and Davidson, 1969). First developed by
Mathur and Gishler (1955) for the low temperature drying of agricultural grains, other
processes for which this technology has since been applied include crystallization,
blending, cooling, coating and granulation of solids (Mathur and Epstein, 1974). More
recent advances include gasification, carbonization and various pyrolytic processes
(Epstein and Grace, 1984; Bridgwater, 1985).
The nature of thermal cracking reactions, discussed extensively in the previous
paragraphs, necessitates the incorporation of several features into the design of an
effective ultrapyrolytic reactor. Firstly, the reactor must be capable of high temperature
operation. Secondly, the contact times of gases within the reactor at the reaction
temperature must be very short, in the range of hundreds of milliseconds. These two
criteria further imply the necessity of extremely high heat-up rates (lOS°C/s) within the
reactor. As discovered by Uemaki et al. (1970), each of these criteria can be satisfied
with the spouted bed operation.
Expanding upon Uemaki's idea, Stocker (Stocker et al., 1986; Stocker, 1987), at the
University of Calgary, studied the effectiveness of a spouted bed with the inclusion of
a centrally located nonporous draft tube. This particular configuration takes advantage
of the same beneficial characteristics associated with conventional spouted beds, yet
enables improvements of expected product distributions by limiting the residence time
distribution of reactant gases. This is achieved by maintaining strict control through the
restriction of spout gas divergence into the annular region surrounding the jet.
The presence of the draft tube in the reactor allows to achieve other desirable features.
In conventional spouted beds, the spout Get) is in continuous contact with the annular
solids over the entire height of the bed and, to achieve a stable operation, it must be able
to support the surrounding annular bed. To provide this support, the spout must be at a
greater pressure than the annulus. Because of this pressure difference, there is
continuous percolation of gas into the annular region and, if the bed is too deep, the
spout can easily collapse. The bed height at which this transition occurs is termed the
maximum spoutable height (Mathur and Gishler, 1955). The presence of the draft tube
removes this limitation.
A typical spouted bed reactor with draft tube is illustrated in Figure 18.
The distance between the spout jet inlet and the base of the draft tube is termed
"entrainment region", since this corresponds to the area within the bed where there is
343
transfer of solids from the annular region surrounding the draft tube to the spout region,
where the reaction occurs.
Fountain ReglOfi
Dc----ot
Draft Tube
'[ Annulus
'"
1 e
1
Figure 18. Spouted bed reactor with draft tube
Extensive experimental work has been conducted to study the gas and particle flow
characteristics in a 20 cm diameter, 1.2 m tall semi-cylindrical acrylic unit (Muir et al.,
1990). Sand particles, having a mean diameter of 1 mm have been utilized to study the
effects of spouting gas velocity, draft tube diameter and length of the entrainment region
on the solids circulation rates achievable. Typical results obtained in this work are
illustrated in Figure 19.
700 .
. . .
N~
= 0.023 = 0.138
i_
~ Ddt m. e m
~
co 600 ~----.
c
I
·--i
.-0.105m
....~ 500
~-.
z
0
,~ .=O.OBm
~
:>
~ t
j-----
u
0::
• = 0.06 m
0
'"
0
::J
JOO
• •
0
200
'" 10 15 20 25 .30 35 40
SPOUT NOZZLE VELOCITY U 9 (mi.)
Figure 19. Solids circulation rate as a function of spout nozzle velocity for various
entrainment lengths
344
Visual observation of the entrainment region, with the use of a high speed video
camera, has allowed a careful interpretation of the trends in the results. In particular,
the solids circulation rates have been correlated with the size and stability of the jet,
forming over the entrainment region. Also, non-uniformities of the solids distribution
within the spouting jet have been studied.
Stoker et al. (1990) have described the work related to the hydrodynamic and thermal
modelling of a high temperature spouted bed with draft tube. A non-isothermal, axi-
symmetric, three-region (spout, annular and fountain) mathematical model has been
developed and utilized to investigate the key features of the reactor configuration, related
to the application for ultrapyrolysis reactions. A key result of this computer simulation
is shown in Figure 20: very high heating rates are achievable over the entrainment
region, able to satisfy the requirements of the ultrapyrolytic regime.
10'
10'
~
'"
~
~
'"
a:: 10'
en
c
.,.,
-+='
I 10'
10'
10-' 10' 10·
Axial Distance from Inlet 1m)
Figure 20. Heating rate variation with axial position
The modelling results confirmed the experimental findings by Stocker et al. (1989),
where a spouted bed with draft tube pilot plant has been utilized for ultrapyrolysis of
propane. The applied study confirmed the outstanding features of the reactor
configuration.
Eng et al. (1989) extended the modelling work to dynamic situations, where the reactor
responses to changes in operating conditions could be predicted. In particular, the model
has been utilized to study the dynamic heat transfer characteristics of the system and,
based on the results, a control strategy has been proposed.
A 1 barrel/day (159 L/day) pilot plant has been constructed and operated for
ultrapyrolysis of steam atomized Alberta heavy oil. Successful results have been
obtained and an upgraded oil of reduced viscosity (280 mPa s at 25°C) has been
produced.
Experiences with the pilot plant at very high temperatures (above 600°C) have
indicated some limitations of the above described spouted bed reactor configuration.
Firstly, the maximum spoutable height decreases with increasing temperature, as
345
observed also by other researchers (McNab and Bridgwater (1977); Wu et al. (1987)).
As the operating temperature is increased to high levels, for operation in the
ultrapyrolytic regime, the maximum spoutable height can become smaller than the
entrainment region, separating the inlet nozzle from the base of the draft tube. When
such condition arises, the bed collapses and becomes inoperable. On the other hand, a
decrease in length of the entrainment region, in order to accommodate higher
temperatures, would decrease the maximum solid fluxes that can be achieved and,
therefore, the high heat-up rates required by the operation. Besides, at these high
temperatures, an increasing gas bypassing from the spout to the annulus has been
observed along the entrainment region itself, thus compromising the limitation in
residence time distribution of the vapour phase.
4.3.2. The Spout-Fluid Bed with Draft Tube. Modifications of the original design have
been studied in detail. One modification has been the implementation of the spout-fluid
bed concept. By replacing the base of the spouted bed with a gas distributor, auxiliary
gas can be introduced into the annular bed of solids. Introduction of this auxiliary gas
increases the pressure surrounding the entraining jet creating a crossflow of part of this
gas into the jet itself, thus limiting the amount of spout gas bypassing. This crossflow
also serves to carry more solids into the entrainment zone, resulting in an increased
solids loading in the draft tube and increased solids circulation fluxes. A schematic
representation of the spout-fluid bed with draft tube is shown in Figure 21. Experimental
work has been conducted at room temperature to study the characteristics of this
modified pyrolyser and typical results are shown in Figure 22. The findings revealed a
drastic increase in solid fluxes with the introduction of auxiliary air, reaching values
around 1000 kg/m2s, and significant reductions in spouting gas bypassing.
T- - - - I Annulus
Draft lib!
1
h
Figure 21. Spout-fluid bed with draft tube

346
.,
E 1100,-----------------,
'- 1000 • a~8.0L/S

l- ~
..."
900
.--.~ f=6.6L/S
:~:L/S ~~
800
~
... 700
z
af=2.3~.~
.---.--'-.---.
o 600
~:0 500
u af = 0.0 Lis •
Q:
U 400
Vl
§ 300~-~--._-~--._-~-~
~ 10 15 20 25 30 35
SPOUT NOZZLE VELOCITY U 9 (m/s)
Figure 22. Solids circulation as a function of spout nozzle velocity for various auxiliary
gas rates (Ddt = 0.023 m; e = 0.08 m)
Visual examination of the flow characteristics, at room temperature, with the use of the
high speed video camera still shows a certain degree of instability of the entrainment
region, although dramatic beneficial features of the modified reactor are clearly evident.
These flow instabilities and, in particular, a typical axial and radial non-uniformity of the
flow are expected to be magnified under high temperature conditions, thus limiting the
stable operability of the reactor to a narrow range of conditions.
4.3.3. The Internally Circulating Fluidized Bed. To improve further the design of a
reactor suitable for operation in the ultrapyrolytic regime and on the basis of the above
described experimental observations, a novel reactor has been recently proposed. This
improved version, called Internally Circulating Fluidized Bed (ICFB), has been designed
and two prototypes (a cold semi-cylindrical acrylic unit as well as a cylindrical hot pilot
plant) have been constructed and extensively operated.
In the ICFB, the injected feedstock, the fluidizing gas and fine solid particles
vigorously mix and rise through a central column (riser). At the top, the solids are
quickly separated from the gas phase (in a conventional fountain or by use of an
impinging device) and returned, through an annular bed, fluidized by introduction of an
auxiliary gas stream, to the riser, through a number of orifices bored on the side wall at
its base, thus establishing a circulation pattern. This circulation pattern has been proven
to offer beneficial features superior to both the spouted bed with draft tube and the spout-
fluid bed with draft tube. Figure 23 illustrates the conceptual design of the ICFB.
Extensive research, utilizing the acrylic unit, has been conducted to study the solids
circulation features, as functions of fluidizing gas velocity, auxiliary gas velocity, riser
diameter, orifices diameter and particle size. The experimental results obtained show
that the solids circulation rate increases sharply and linearly with increasing the auxiliary
annular velocity, with increasing the orifice opening size and with decreasing the
particle size. Changes in the riser fluidizing velocity and riser diameter do not affect the
347
solids circulation rate. Gas bypassing studies have shown that no riser gas bypassing
occurs into the annular region under any operating condition. Visual examination of the
flow characteristics throughout the unit demonstrated the outstanding features of the
design. At the base of the riser, impinging horizontal jets of solids are formed, carried
into the riser by a portion of the auxiliary gas introduced into the annulus. These jets
mix very vigorously with the riser gas, carrying the reagents, thus establishing an area
with extremely high heat and mass transfer rates. Above the mixing region, a very
uniform two-phase mixture is formed and carried through the entire length of the riser.
Some solids circulation rate data are illustrated in Figure 24 .
.
II
~f--- particle
deflector
annulus
...... - - l - - - - riser
orifices
auxiliary fluidizing
gas gas
Figure 23. Internally Circulating Fluidized Bed (ICFB)
Experiments are being carried out, in parallel, utilizing the pilot plant, capable of
operating up to temperatures around 900°C. Preliminary experiments have shown that
a very stable and controllable operation can be easily achieved at high temperatures. The
pilot plant is being utilized for Alberta heavy oil upgrading under contract with Colt
Engineering Co. and Can met.
348
900 spout flow

(slj.)
~
., 800 0-0
2.41
C'I
E 700
.......
0'" 600
x
;;::
.,.," 500
0
E 400
.,
L-
V
300
ii
200
100
0.0 0.1 0.2 0.3 0.4 0.5 0.6
Auxiliary superficial velocity (m/s)
Figure 24. Solids circulation fluxes as functions of auxiliary annular velocity, riser spout
flowrate and particle size (3 orifices 11 mm dia)
5. Conclusions
A review of the kinetics for heavy oil ultrapyrolysis/upgrading have been presented along
with a discussion of the reactors used to obtain the kinetics. Although hydrocarbon
pyrolysis has been a subject of intense research over the past 100 years, heavier
compounds (CIO +) have been excluded from the majority of studies. Ongoing research
at the University of Calgary is aimed at increasing the understanding of the mechanisms
responsible for heavy hydrocarbon pyrolysis. A consequence of the ongoing research has
been the development of an innovative micro-reactor system based on the Curie Point
Pyrolyser. The micro-reactor system has successfully allowed evaluation of the intrinsic
kinetics for various hydrocarbons, including propane, n-hexadecane and heavy oils.
Extensive research has also been conducted in the area of innovative reactor technologies
for achieving the critical operating conditions necessary to maximize yields and
selectivities.
6. Acknowledgements
The authors gratefully acknowledge the continuing support from the Natural Sciences and
Engineering Research Council of Canada, in terms of both operating and equipment
grants, the Alberta Oil Sands Technical Research Authority (AOSTRA), Imperial Oil
Ltd., Can met and Colt Engineering Co.
349
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Stocker, RK. (1987) 'Ultrapyrolysis of propane in a spouted bed reactor with a draft
tube', Ph.D. Dissert., University of Calgary.
Stocker, R.K., Eng. J.H. and Behie, L.A. (1990) 'Hydrodynamic and thermal modelling
of a high temperature spouted bed reactor with a draft tube', Can. J. Chern. Eng., 68,
302-311.
Stocker, RK., Eng., J.H., Svrcek, W.Y. and Behie, L.A. (1989) 'Ultrapyrolysis of
propane in a spouted bed reactor with draft tube', AIChE J., 35, 10, 1617-1624.
352
Sundstrom, D.W. and DeMichiell, R.L. (1971) 'Quenching processes for high
temperature chemical reactions', Ind. Eng. Chern. Proc. Des. Dev., 10, 1, 114-122.
Sundaram, K.M. and Froment, G.F. (1979) 'Kinetics of coke deposition in the thermal
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BUBBLE COLUMN REACTORS: SOME RECENT DEVELOPMENTS
M.P. DUDUKOVIC and N. DEVANATHAN

Chemical Reaction Engineering Laboratory
Washington University
One Brookings Drive
St.Louis, MO 63130, USA
ABSTRACT. Gas sparged bubble columns and slurry reactors are used extensively in the production of
fuels, fuel additives and chemicals. Their performance (e.g., selectivity, conversion, etc.) depends to a
large extent on the degree of backmixing of the liquid phase. Our objectives are: 1) to briefly review our
current understanding of bubble columns, 2) to outline a relatively novel experimental technique, based on
computer aided tracking of a single radioactive particle (CARPT), for evaluation of recirculation and
backmixing of the liquid phase, and 3) to discuss the information obtained by CARPT in bubble columns.
It is shown that most often a single liquid recirculation cell prevails, that eddy diffusivities in the axial
direction are order of magnitude higher than in radial. The potential of the technique for use in fluidized
beds, ebulated beds and slurry systems is outlined.
1. Introduction
Bubble columns, cylindrical vessels of large diameter with gas-liquid flow, are widely
used in the process industry as absorbers, strippers and chemical reactors for gas-liquid
and gas-liquid-solid reactions. Typical processes conducted in bubble columns include
hydrotreating and conversion of petroleum residues, fermentation (production of ethanol
and mammalian cells), biological waste water treatment, flue gas desulfurization and
particulate removal, Fischer-Tropsch and methanol synthesis (Fan, 1989). Bubble
columns are also used to carry out chemical reactions (Shah, et ai., 1982) such as
polymerization (production of polyolefins), oxidation (adiponitrile synthesis),
hydrogenation (saturation of fatty acids) and chlorination (production of aliphatic and
aromatic chlorinated compounds). Normally, bubble columns operate with a reactor
length to diameter aspect ratio greater than five and with the superficial gas velocity
which is at least an order of magnitude greater than the superficial liquid velocity. This
distinguishes a bubble column from a gas-lift operation where the superficial gas and
liquid velocities are of the same order of magnitude. Typical ranges of superficial
velocities for bubble column operation are 1 to 30 cm/s for the gas phase and 0 to 2 cm/s
for the liquid phase. The gas phase is sparged into the liquid phase in the form of discrete
bubbles using a gas distributor. The columns can operate either in cocurrent upflow,
countercurrent or semi-batch (batch liquid phase) modes. When operated as a slurry
reactor or a three phase fluidized bed, catalyst particles are suspended in the liquid by the
action of the rising gas bubbles. A three phase bubble column operating with small
particles (terminal settling velocity of the particle in liquid less than 7 cm/s) is frequently
referred to as a slurry reactor; and a column operating with large particles (terminal
353
H.I. de Lasa et al. (eds.), Chemical Reactor Technology for Environmentally Safe Reactors and Products, 353-377.
354
settling velocity less than 50 cm/s) is termed as a three phase fluidized bed (Fan, 1989).
The flow of solids may be continuous or batch; the direction of flow upward or
downward.
Coils or other internals may be inserted into the bubble column to promote heat
transfer. In addition, the columns may be sectionalized by a baffle system or perforated
plates to inhibit liquid phase backmixing or bubble coalescence. Simplicity of operation,
lack of moving parts, ease of removal of heat and low operating costs are major
advantages of bubble columns as reactors or fermentors.
Due to the widespread use of bubble columns in the process industry, their scale-up
and design aspects have been the subject of considerable research. The numerous
literature in this area has been summarized by Shah et al. (1982), Deckwer and Schumpe
(1987) and Fan (1989). These reviews reveal that presently our understanding of bubble
columns is far from complete. Basic hydrodynamics, mixing, mass and heat transport
phenomena are not described based on first principles. Scale-up is founded on
empiricism and remains a major problem. Current design procedures involve several
stages of pilot plant experimentation using equipment of different scale, which is
expensive and time consuming. In order to insure future competitiveness in chemical
processing and biotechnology, large scale-up factors will be required.
In addition to scale-up difficulties, there are a number of problems related to the stable
operation of a bubble column associated with hydrodynamics. For example, consider the
important commercial application of bubble columns in hydroprocessing of petroleum
resids, heavy oils and synthetic crudes. Hydrodynamic cold flow and hot flow studies on
the Exxon Donor Solvent coal liquefaction process (Tarmy et aI., 1984) showed that
much of the literature correlations for the hydrodynamic parameters (holdup, interfacial
area and dispersion coefficients) obtained with cold flow units, at ambient conditions, are
not applicable for commercial units operating at relatively higher pressures. In addition,
the flow pattern in commercial units was considerably different. In the hydroprocessing
of petroleum residues by the H-Oil and LC-Fining processes, refinery operations have
experienced problems with nonuniform distribution of gas and liquid reactants across the
distributor, maintaining stable fluidization and preventing temperature excursions (Beaton
et aI., 1986, Fan, 1989 and Embaby, 1990). Catalyst addition, withdrawal and elutriation
have also been identified as problems in these hydrotreaters.
The accurate design and scale-up of bubble columns is, in part, contingent upon the
ability to describe the non ideal flow of the liquid phase. The gas flow pattern and gas
holdup profiles induce global liquid recirculation. Consequently there is considerable
mixing of the liquid phase. The assumption of complete backmixing is often made, but as
shown recently by Myers et al. (1987), this can lead to greatly oversized designs, if high
conversions are desired, or to inaccurate designs in the case of complex kinetics.
Quantitative description of liquid mixing requires a complete understanding of liquid
recirculation. Recirculation also has an important influence on bubble coalescence, gas
backmixing and heat transfer to immersed tubes.
2. Bubble Column Modeling
In design, scale-up and scale-down, it is necessary to quantify the effect of various

variables on reactor performance (e.g., conversion, selectivity, volumetric productivity,
etc.). This is accomplished by utilizing the reaction engineering methodology in
developing a reactor model. Such a steady-state model (Figure 1) often contains a
description of the reactor idealized flow pattern on the left hand side (LHS) of the
chemical species and energy conservation laws i&. as input-output terms, and the rate
355
(kinetic tenn) and/or interphase transport rates as source-sink tenns on the right hand side
(RHS) of the conseIVation equations. The RHS (Figure 1) contains the local kinetic rate
modified, if necessary, by local transport effects (e.g., effectiveness factor approach).
LHS RHS
Feed, Q Q
~
- -...... lh(Tb ) = f(-t.H Rj) Tlj Rj(~b,Tb)
To, ~o' Po
Tl = f (KINETICS, TRANSPORT)
Figure 1. Typical Reactor Model

The above approach has been applied to bubble columns. For example, the LHS
of the species mass balance in the liquid phase in general takes the following fonn (in
cylindrical coordinates assuming axial symmetry):
ac ac a
L(c) = -u--v-+-(D -)+--(Dr-)
ac 1 a ac (1)
ax ar ax x ax r ar r ar
This is a fonn of the general dispersion model in which the axial, Dx, and radial, Dr,
dispersion coefficients (which arise from time averaging of the instantaneous equations)
are functions of position. Due to complexity and uncertainty in parameters this fonn has
not been used. Instead, various degrees of simplification are applied. Usually, v = 0, u =
u(r) and constant Dx and Dr are assumed leading to the uniform dispersion model. Often
a constant axial velocity independent of radius (plug flow) is assumed leading to the
dispersed plug flow model. Frequently radial uniformity is assumed in addition to the
above, resulting in the axial dispersion model. Numerous correlations for the axial
dispersion coefficient for the liquid phase are reported in the literature (for summary see
Torvik (1990) and Shah et al. (1982». Standard textbooks (e.g., Levenspiel, 1972;
Froment and Bischoff, 1990) simplify the flow pattern description even further by
assuming plug flow or complete backmixing of the liquid. The models based on these
extreme simplifications are useful in a limited number of situations. For reaction systems
that contain a distribution of characteristic reaction times, a more detailed description of
mixing is essential. Both the global liquid flow pattern (e.g. recirculation) and the local
mixing, especially in the distributor region, must be described. The axial dispersion
model is inadequate for such situations.
Some attempts have been made to depart from the axial dispersion model. Myers
et al. (1987a,b) presented a phenomenological model for liquid backmixing in churn
turbulent bubble columns. They develop their mixing cells-slug exchange model (Figure
2) based on the facts that the radial gas holdup profile causes liquid recirculation and that
large and small bubbles are present. Model parameters were related to physical
obseIVations and available holdup and axial dispersion coefficient correlations. The latter
was related to the slug-cell exchange coefficient. Predictive abilities of the model in
scale-up were not tested. Phenomenologically, this model describes well the flow and
mixing pattern postulated by Zehner (1982) and Hochman and McCord (1970). A review
of various available models that could be adopted to bubble columns was presented by
Wasowski and Blass (1989).
356
Series of N Well-Mixed Cell Regions
Figure 2. Mixing Cell-Slug Exchange Model (Myers, 1986)
Recently Torvik (1990) and Torvik and Svendson (1990) conducted an extensive
modeling study of gas-liquid and gas-liquid-solid systems. Basic conservation equations
were applied to mass, momentum and chemical species in each phase. The source terms,
resulting from time averaging, were approximated with available constitutive equations.
Closure was accomplished using the k-E turbulence model for single phase flow. The
model did not account for coalescence-redispersion and utilized the isotropic turbulence
assumption. The model predictions have not been tested sufficiently to judge its
reliability in scale-up.
In summary, it is fair to say that a general model for bubble column design and scale-
up has not been developed yet. Reliable prediction of the effect of changes in physical
properties, reactor dimensions (e.g., diameter and length), operating variables (i.e.,
superficial gas and liquid velocities), and design variables (e.g. distributor design) on
reactor performance is not possible. To reach this goal it is necessary to improve our
understanding of many phenomena and quantify numerous variables such as: i) gas
bubble formation, growth and detachment at the distributor, ii) bubble coalescence and
redispersion in the distributor region, iii) gas-liquid mass transfer in the distributor
region, iv) bubble coalescence in the column, v) bubble behavior in the disengagement
zone, vi) gas holdup distribution, vii) gas and liquid velocity distribution, viii) local
mixing in the liquid phase induced by bubbles. Here we focus our attention on
description of liquid hydrodynamics with the emphasis on describing the global liquid
circulation pattern, liquid backmixing and turbulence.
3. Liquid Hydrodynamics in Bubble Columns - Previous Studies
3.1 FLOW REGIMES
From visual observations it is well known that three flow regimes can be distinguished in
bubble columns. Homogeneous bubble flow occurs at low gas superficial velocities ( < 5
cm/s) and is characterized by minor bubble-bubble interactions and narrow size
distribution of small bubbles. This regime can be extended to higher gas velocities and at
higher pressures by the use of flexible spargers (Rice et aI., 1981). Chum-turbulent flow
is encountered at higher gas velocities ( > 5 cm/s) and in larger diameter columns. A
bimodal bubble size distribution is characteristic of this flow regime. The dynamic
disengagement technique (Vermeer and Krishna, 1981) can be effectively used to identify
357
churn-turbulent flow. Slug flow is found only in small diameter columns ( < 10 cm) and
is characterized by bullet shaped bubbles which extend over the whole tube diameter.
While attempts have been made to quantify flow regime transitions, firmly established
criteria are not available. The flow map of Shah et aI., (1982) is often cited and presented
in standard texts but its origin and generality are questionable. It most likely represents
the air-water system at atmospheric pressure. It should be noted that besides the pressure
effect on bubble-churn turbulent transition (Krishna et aI., 1991), an increase in liquid
superficial velocity also shifts the transition to higher gas velocities. Hence, the existing
flow maps cannot be used reliably for either high pressure bubble columns or for gas lift
reactors.
3.2 LIQUID RECIRCULATION
Phase recirculation or gulf streaming is commonly encountered in gas fluidized beds,

bubble columns and spray columns (Rietema, 1982). The circulation is driven by the
difference in density between the gas and liquid (or solid and gas) and it arises due to
radially non-uniform holdup profiles. The effect of column size (diameter and height),
distributor and internals design, physical properties of the two-phase system and
operating conditions (e.g. superficial velocities) on liquid recirculation is not presently
well understood. Since liquid recirculation affects mixing (through convection),
interfacial transport (through bubble coalescence) and heat transfer to immersed tubes, it
needs to be quantified.
i&",!/rn If\\\ 1m/

:Vj; W V)/l'W;
T
@~ 1T ~.® 1
c:...
(rm (<<)) ((0)~ ~tO
~
l!fj
~ ~\g
- D ___
a) b) c)
Figure 3. Multiple Circulation Cell Models [a) Joshi and Sharma (1979), b) Van Akker and
Rietema (1979), c) Joshi (1980)].
Prediction of liquid recirculation based on the early inviscid models of Freedman
and Davidson (1969) and Whalley and Davidson (1974) is only applicable to shallow
tanks stirred with gas plumes. Extending the so-called principle of minimization of
maximum vorticity to tall columns, lead Joshi and Sharma (1979) to conclude that
multiple circulation cells of height equal to column diameter are present (Figure 3a).
358
Since, it is physically impossible for streamlines of adjacent cells to oppose each other
(Van den Akker and Rietema, 1982), this model was modified to allow for assisting
streamlines (Figure 3b) which assures alternating sense of rotation in the cells along the
column. This model, however, predicts that axial centerline velocity alternates in
direction along the column which is contrary to experimental observations. Moreover, in
such a flow pattern, inter-cell interaction is minimal and hence significant inter-cell
concentration and temperature gradients can develop which are not observed in bubble
columns. Joshi and Sharma (1982) modified the model further (Figure 3c) by engulfing
the circulating cells into an overall liquid circulation pattern. Turbulence measurements
of Lubbert (1983) provided evidence for existence of multiple recirculation cells as did
the work of Chen et al. (1989) on two dimensional bubble columns. However, there was
no evidence that these cells are fixed in space. It seems more likely that they consist of
travelling secondary vortices. These large travelling vortices, and the exchange from
their wakes with mixed cells, represent the basis for the Myers et aI., (1987a,b) mixing
cell-slug model. The mixing mechanisms of this model correspond to the rise of liquid
with the slugs, backflow of liquid and mixing between the two regions (Figure 2). The
distinction between these two simplified physical pictures of liquid recirculation and
mixing is important. Multiple circulation cell models may mislead the practitioners to
assume little interaction between cells and attempt scale-up in terms of the tanks-in-series
model (since mixing cell is assumed to equal column diameter). In contrast the slug-
mixing cell model, with strong cross-mixing, brings forth the realization that liquid is
nearly completely backmixed (i.e., one has a single CSTR behavior). Tracer studies
confirm almost complete liquid backmixing (Myers, 1986).
The available experimental evidence (Ueyama and Miyauchi, 1979) indicates that
liquid always rises in the center of the column and descends near the walls. This led to
the development of models for the single axial liquid velocity profiles obtained from one
dimensional continuity and momentum equations. Ueyama and Miyhauchi (1979)
proposed such a pseudo homogeneous model for liquid recirculation. The model requires
radial gas holdup profile and eddy viscosity as inputs. Experimentally measured holdup
profiles were used, while eddy viscosity was obtained by matching the predicted and
measured velocities. Variations on this model were proposed by Walter and Blanch
(1983), Yang et aI., (1986) and Clark et aI., (1987). All require the specification of the
gas holdup profile and at least another parameter (e.g. inversion point, centerline velocity,
etc.) as model inputs. Ulbrecht and Baykara (1981) and Ulbrecht et al. (1985) developed
a simpler model by assuming a central plume region of constant velocity and annular
region devoid of gas, with a parabolic velocity profile. The model still contains one
adjustable parameter. Recently, Anderson and Rice (1989) and Rice and Geary (1990)
used turbulence models to close the problem and evaluate the liquid recirculation
velocity. Their models still require the gas holdup profile and a measure of mixing length
as input. A turbulence based model that needs bubble diameter and its radial distribution
as model input was also suggested by Gasche et aI., (1989).
Experimental measurements of liquid velocities in bubble columns are limited. The
average axial velocity profiles were determined by using pitot tubes by Whalley and
Davidson (1975) and Hills (1974). Gas holdup profiles were also obtained by Hills
(1974) using capacitance probes. Durst et aI., (1984) investigated the laminar liquid
circulation in a bubble column at low gas holdup using Laser Doppler Velocimetry
(LDV). This technique cannot be used at higher holdups (Schugerl et aI., 1987).
Buchholz et al. (1982) measured the radial variation of the axial liquid velocity using a
hot wire anemometer. Difficulties associated with using this technique are pointed out by
Torvik (1990). Hilgert and Hofmann (1986) used the ultrasonic Doppler technique for
measurement of axial and radial gas bubble velocities at low gas superficial velocities
359
(low holdup). They also provided a summary of advantages and disadvantages of various
experimental techniques for determination of liquid velocity (Prandtl tube, turbine
anemometer, hot wire anemometer, laser Doppler anemometer), gas holdup (pressure
measurement, gas disengagement, light transmission, electrical conductivity, optical
probes) and bubble size (photography, aspiration, electrical conductivity, optical probes).
None of these techniques is universally applicable and all of those that yield local values
are invasive in character and cumbersome to use.
Measurement of turbulent intensities in bubble columns seems limited to the data of
Zakrzewski et al. (1981), Lubbert (1983), Franz (1984), Yao et al. (1990) and Torvik
(1990). Hot wire anemometry was used for this purpose.
Clearly, there is a need for complete mapping of liquid and gas velocities and
turbulence intensities in bubble columns. Until recently only data of Hills (1974)
reported liquid time averaged velocities and radial gas holdup profiles taken under
identical operating conditions. Yao et al. (1990) present in addition to such data also gas
velocity and turbulence intensity profiles. Some data on radial holdup distribution and
axial liquid velocity in industrial size columns were presented by Kojima et al. (1980) and
Koide et al. (1979).
3.3 MIXING
Liquid phase mixing in bubble columns is due to: i) convective dispersion caused by
nonuniform cross sectional liquid velocity profiles resulting from liquid recirculation, ii)
turbulent eddies, iii) entrainment and shedding of the liquid in the wakes of bubbles, iv)
molecular diffusion (which can be neglected). As discussed earlier, these mixing
mechanisms are lumped into a single effective axial dispersion coefficient which is
usually evaluated from tracer experiments using electroconductivity (Kato and Nishiwaki,
1972) and spectrophotometry (Towell and Ackerman, 1972). Empirical correlations for
the effective axial dispersion coefficient are summarized by Shah et al. (1978, 1982) and
Torvik (1990). Model based expressions for the axial dispersion coefficients were
developed by Ulbrecht and Baykara (1981), Okki and Inoue (1970), Baird and Rice
(1975), Riquarts (1981), Joshi and Sharma (1979, 1980), Miyauchi et al. (1981), Rice et
aI., (1990) and Rice and Littlefield (1987). Rice and Littlefield (1987) and Rice et al.
(1990) reported order of magnitude lower axial dispersion coefficients than predicted by
available correlations. They claim that most of the axial dispersion data in the literature
reflect misalignment of columns, with even 0.5 degree misalignment from the vertical
leading to 2 order of magnitude higher dispersion coefficients. These claims have not
been confirmed by others. Experimental evidence to assess the eddy dispersion
contribution to the overall effective axial dispersion coefficient is lacking. Moreover, it is
questionable whether the axial dispersion model scales up properly and is useful in
predicting reactor behavior.
Recently, Lubbert and Larson (1990) analyzed the local mixing behavior in bubble
columns and in air-lift fermentors utilizing a heat pulse-probe experiment. They
considered the spreading of an originally narrowly distributed clump along the principle
flow direction. Based on theory, the width of the spreading cloud <i.&. standard deviation)
can be described by:
a=~P ~
with ~ = 112 for random walk (diffusion) type mechanism; ~ = 1 for convective
spreading; f3 = 3/2 for isotropic turbulence and f3 = 3/2 + Y with y > 0 for nonstationary
turbulence. In gas -liquid flow the constant K in equation (2) is ..J2i5:for the diffusion
360
mechanism (P = 112). However, K is proportional to the relative bubble velocity for the
bubble wake (convective) mechanism (p = 1), and to the rms turbulent velocity in case of
mixing via turbulent eddies (P > 3/2). Statistical analysis (Nasser et aI., 1990) shows that
for the bubble wake mixing mechanism a ex: t for small times (i.e. over short distances)
and a ex: t1l2 for long times (e.g. over longer distances). Thus, the apparent "diffusion"
behavior is always obtained at sufficiently large distances which is the case with almost
all global tracer measurements. The experiments of Lubbert and Larson (1990) yield B =
0.8 in both the gas-lift reactor and in the bubble column, indicating the same dominant
mechanism of dispersion in the two reactors. The proportionality constant, K, was much
higher in bubble columns which is understandable due to higher relative gas velocity.
The spreading of the particle cloud in the direction perpendicular to the main flow
direction, Or, was found proportional to to.56 , This indicates that eddy dispersion may
be a dominant dispersive mechanism in the radial direction while superimposed on it the
wake mixing mechanism dominates in the axial direction.
Additional studies of backmixing in bubble columns are necessary for quantification of
the dispersion coefficients.
4. CARPT Studies of Liquid Hydrodynamics
4.1 PRINCIPLES
Computer Aided Radioactive Particle Tracking (CARPT) was introduced as a technique

for monitoring the motion of solids in fluidized beds of large (appr. 800 Jim) particles at
the Mechanical Engineering Department of the University of Illinois by Lin et al. (1985).
A unit to study solids circulation in fluidized beds of large particles was also built at
DOE-Morgantown and at the Mechanical Engineering Department at Rorida Atlantic
University. The Chemical Reaction Engineering Laboratory (CREL) at Washington
University extended CARPT use to gas-liquid and gas-liquid-solid systems. Numerous
refinements of the hardware and software for the newer CARPT systems are summarized
by Devanathan and Moslemian (1988), Devanathan (1991) and Yang (1991).
In CARPT a single radioactive particle, dynamically similar to the phase whose flow
pattern it simulates (same solid size and density in fluidized beds, same density as liquid
and fully wettable in bubble columns) is introduced into the system. A number (16 in our
case) of scintillation, sodium iodide, detectors positioned all around the column (Figure 4)
measure the radiation intensity received from the particle during each sampling period
(our sampling frequency was 33 Hz i&. sampling period app. 0.03 sec). The pre-
established calibration curves for intensity of radiation versus distance for each detector
are used in a linear regression scheme to determine the position of the particle at each
sampling period. The 33 Hz sampling frequency represents a compromise. Higher
sampling frequencies assure minimal movement of the particle during a sampling period;
however the intensity of radiation received at too high a sampling frequency is not
sufficient and reduces the accuracy due to the statistical nature of gamma radiation. We
have now achieved 500 Hz sampling frequency on multiple channels, a feat in itself. This
allows us to generate the "instantaneous" data at 33 Hz by averaging the data collected at
higher frequencies which improves the accuracy of tracer position determination.
Once position versus time data are obtained and stored on a PC hard disk, time
differentiation of displacements yields local instantaneous velocities. Ensemble averaged
velocity, rms velocity and other turbulence quantities are computed after acquiring the
data for a sufficient length of time (e.g. several hours) at fixed operating conditions.
361
y
n(~t(~d()r Coordi n;tlcs (CIlI)
Det. X Y '/,
No.
I 15.2 0 6.0
2 0 15.2 6.0
:I 10.8 -10.8 36.3
1 15.2 [) 21.1
[, 10.8 10.8 :1(iA
G () 15.2 51.5
x 7
8
1O.t!
10.8
-1O.t!
HJ.8
(jG.7
(jli.7
9 -15.2 0 6.0
10 a -15.2 6.0
11 -10.8 10.8 .1fiA
12 -15.2 [) 2L1
13 -10.8 -10.8 36.1
H [) -15.2 51.5
o 15 -10.8 10.8 61i.7
Ie; -IOJl -10.8 (j(j.7
Figure 4. Detector Configuration for CARPT (Devanathan, 1991).
4.2 EXPERIMENTAL SET-UP
Figure 4 shows a schematic of the detector positions in the CARPf Facility which
consists of the column, the detector support structure and the signal processing and data
acquisition systcm. The set-up consists of 16 NaI detectors (2.54 x 2.54 cm crystals)
positioned around the bubble column at known locations. The column makes use of a
Plexiglass plenum which can accommodate test sections of various diameters. A stainless
steel porous plate distributor with an average pore size of 40 JIm is sandwiched between
the two sections. A positioning device was fabricated and attached to the top of the
column for calibration purposes. Air to the column is supplied by a compressor and the
flow rate is monitored by three parallel rotameters.
Details of the hardware and software implementations pertaining to CARPf are
described by Devanathan (1991). Briefly, gamma photons striking the detector are
converted to current pulses (one pulse for each incident photon) which are amplified by
fast amplifiers. The amplified pulses are then filtered by a discriminator, Lecroy 16
channel, which removes the noise due to secondary gamma radiation obtained by the
interaction of primary gamma radiation with the column and its contents. A binary pulse
counter counts the pulses which are transferred to the hard-disk of the computer. The
data acquisition system makes use of the modular CAMAC (Computer Automated
Measurement and Control, IEEE-583) high speed data acquisition system in conjunction
with the GPIB (General Purpose Interface Bus) for rapid data acquisition (Devanathan,
1991). Originally, machine language data acquisition programs were used; now, a fast
C-Ianguage version is employed.
362
4.3 DESCRIPIION OF CARPI EXPERIMENTS AND DATA PROCESSING
Our CARPI experiment consists of: i) particle preparation, ii) calibration of detectors at
operating conditions of interest (by positioning the particle at 200 to 300 known locations
and obtaining intensity versus distance curves for each detector. Such calibrations
average out the effects of varying gas holdup, etc.), iii) data collection while maintaining
the system at steady state, iv) data processing; by using prepared programs one obtains
instantaneous velocity components, time averaged velocities, circumferential averages
and turbulence parameters.
The particle was prepared from a 2.38 mm polypropylene sphere. A section was
removed, a scandium cylinder (d = 1 mm, h =0.7 mm) was inserted while leaving an air
pocket also, and a polypropylene plug was replaced. The density of the particle
(polypropylene-air-scandium combination) is now equal to that of water which was used
as working fluid in our experiments. The particle was spray painted with a metallic paint
to make it fully wettable and prevent bubble adherence to the particle. The particle was
then irradiated at the University of Missouri to 250 microcuries of Sc 46 (scandium) with
a half-life of 84 days.
The particle is placed with a specially designed probe at 200 known locations in the
column at each gas superficial velocity of interest, and a calibration curve is obtained for
the distance-intensity relation for each detector. The polynomial fit of each curve is
stored in the computer.
Once calibration is complete, the same gas superficial velocity is maintained, the
particle is released and its position in time is recorded over long time periods.
Figure 5 illustrates the flow of data. TRACK monitors intensities of radiation received
by each detector during each sampling period. With the help of fitted intensity-distance
curves, obtained by calibration (POLY FIT), and of the linear regression scheme
(LOCA TE), the position of the particle is found for each sampling period «(i.e. for each
0.03 sec). From two subsequent positions «position 2 minus position l)/sampling period)
the instantaneous velocity vector (NEWTON) is obtained. The instantaneous velocity,
calculated in the above manner, is assigned to the column compartment into which the
half distance between location 1 and 2 falls. For that purpose a grid is established for the
column in axial, radial and angular direction so that up to 8000 compartments are formed.
This is necessary since each compartment must have a significant number of
instantaneous velocities assigned to it in order for ensemble averaging to be justified.
Such ensemble averaging of the instantaneous velocities for each compartment yields
the time averaged velocities (VELOCITY). By averaging over the azimuthal direction
we take out one dimension and arrive at the two dimensional velocity vector (CIRCVEL)
which can be presented as a plane vector (ONEDVEC). By making the additional
assumption that liquid holdup in a given compartment is proportional to the fraction of
tracer occurrences in that compartment, stream lines can be calculated and presented
(STREAMFN). This is only an approximation and for more accurate determination of
stream lines actual holdup distribution would need to be known from independent
experiments such as computer tomography (CT).
In addition to the ensemble averages, which yield the time averaged properties of gas
induced liquid flow, CARPI allows direct calculation of important turbulence parameters
-;2::;T
such as normaI sresses-PLur,-PLuO,-PLuz
t -;2
an d shearsresses-PLuruO,-PLuOuz,
t -,-,-:-;;---;-
-PL u' r u' z· The fluctuating velocity components U'i in each compartment are readily
363
computed as the difference between the instantaneous, ut ' and the time averaged, ut '
velocity component in that compartment. AlI the necessary correlations are then
Figure 5. Data Processing Software (Devanathan, 1991)
computed and the turbulent normal and shear stresses are evaluated in each compartment.
Moreover, the intensity of turbulence, I = F:In ' and the kinetic energy of turbulence
per unit volume (KE = 1I2PL(u'!+u'!+u';» can now be calculated for each
compartment. Introduction of a simple model of turbulence (e.g. eddy viscosity) alIows
the evaluation of the eddy viscosity as a function of position in the column since the
(3)
required derivatives of the time averaged velocities can be calculated from their
polynomial fits.
Turbulent mixing of a chemical species in the liquid in a bubble column is difficult to
describe based on first principles, unless the assumption of isotropic turbulence is
invoked. Then, the dispersion coefficient at any location ain the column can be
estimated by (Brodkey, 1967):
D( a-) = v,2(-)T
aL (4)
364
where v' is the Lagrangian fluctuating velocity and TL is the Lagrangian integral time
scale. This time scale represents the average time during which turbulence persists at a
point and is a measure of the interval over which v'(t) is correlated with itself. For time
intervals much larger than TL, v'(t) becomes statistically independent of itself, i.e. TL is a
measure of the time interval over which v'(t) remembers its past history. For
autocorrelations that exhibit some negative values, TLcan be calculated from the first
moment of the autocorrelation coefficient, RL(t') (Bendat and Piersol, 1986):
(-'
RLa,t)= v'(t)v (t+ t)
(5a) -:2 (5b)
v'
The crosscorrelation of Lagrangian fluctuating velocities, needed in equation (5b), is

obtained from CARPT experiments by
v' (t)v' (t + t') = -

1
N exp
LV'
N",
1=1
(t)v (t + t') (6)
where Nexp is the number of statistically independent experiments observed in the column
compartment for which the formula is applied. Devanathan (1991) provides the details
regarding the selection of independent experiments.
4.4 RESULTS AND DISCUSSION OF CARPT EXPERIMENTS
CARPI' expcriments were performed with bubble columns of three different diameters
(11.4 cm; 19 cm; 29.2 cm) using air-water. Four superficial velocities, spanning the
range from 2 cmls to 18.4 cmls were used in each column. This covers all flow regimes
from bubble to churn turbulent flow. All runs were done with batch liquid (i.e. zero
liquid superficial velocity). A porous plate distributor was employed.
4.1.1. Liquid Recirculation. One of the objectives of CARPI' studies was to determine
the time averaged liquid velocities and examine whether spatially fixed multiple
circulation cells of height-equal to diameter exist. Figure 6a presents the results of the
smallest diameter column (11.4 cm) at the lowest gas superficial velocity of 2.8 cmls
(bubble flow). The RHS of the figure is the 2D vector plot of time averaged liquid
velocity. The length of the longest arrow corresponds to the maximum liquid velocity of
9 cm/s. The LHS of the figure is the streamline plot. A large liquid recirculation cell
occupies almost three quarters of the column length. Two small circulations are visible in
the distributor region. The sense of rotation alternates in the small cells. Liquid rises up
the middle and flows downward by the wall in the large cell. In this smallest diameter
column a high gas velocity of 18.4 cmls (churn turbulent flow) creates a strong, single
liquid recirculation cell with liquid rising up the middle and descending by the wall
(Figure 6b). The maximum liquid velocity induced by the gas is 53 cm/s. The
azimuthally and time averaged radial liquid velocity is displayed as a function of axial
position at three different radial locations in Figure 7a,b. Throughout most of the column
the average radial velocities are very small and can in the first approximation be taken to
be zero except in the distributor and freeboard region. This implies that a simplified one
dimensional liquid recirculation profile, as discussed in Section 3.2, is applicable to most
of thc column. The magnitude of radial velocities increases with increasing gas
365
z
z
~ ~ I- ' - '
1/1"
~~I
~ I!~
~ II / I ,
, I"
\ 11,/ Ho ~ If.
Ii 'I
1;lll/li
irIilil ~
111. I ~ I •.•
ff, "
8 11,.
\ If, \
I
~ 'I ..
Ho
~ 8 I, •.
II f. \ If, "
$ If. , ~ n ...
g4 Ii(~\
"
Ii I I" I Ii 0
111 ••
§~ \ I ,"
::l fI \ , I t "1
(a) ~o (b)
~~
If, • II , , •
f ~
11'1
~
'1:\\
I;' I
If" •
It.,
111'1
o '. I If I.,
~ '\. I
~ \I n (
o
)
tt ••
~ iI (j,~i\ 1/1 •
~I~,~i)
~ Ir ••
0
5! 0
I~
0
:l :l
o o
o o
o 2 4 IS o 2 " S
Radial Position. em Radial Position. =

Figure 6. Liquid Streamlines and Velocity in the 0.114 m Diameter Column [a) UG =0.028 m/s;
b) UG =0.184 em/s]
o
~~------------------------------, ~r-----------------------------'
R Levels. em R Levels, em
(a) 0.60 0.60 (b)
3.00 3.00
• - 5.40 • - 5.40
o
.,;
~~~ _ _~ _ _~ _ _- L _ _~ _ _~ _ _~~
0.0 10.0 20.0 30.0 40.0 50.0 0.0 10.0 200 30.0 40.0 50.0 60.0 70.0 BO.
Axial Position, em Axial Position, em
Figure 7. Liquid Radial Velocity in the 0.114 m Diameter Column [a) UG =0.02 m/s;
b) UG =0.184 m/s].
366
superficial velocity and is higher in the column center than near the walls.
For the medium column of 19 cm in diameter, the time averaged axial liquid velocity is
shown as a function of radial position in Figure 8. Each figure represents a different gas
velocity, and in each figure different lines correspond to different axial locations. A small
circulation cell in which liquid flows towards the distributor in the middle of the column
and upward by the wall is most pronounced at the lowest gas velocity (2 cm/s) when
bubble flow is observed. At high gas velocities, except for the distributor region and the
top of the column where the gas disengages, most of the column length can again be
represented by a single axial liquid velocity profile with liquid flowing upwards in the
middle of the column and downwards by the walls. Hence, one dimensional modeling of
liquid recirculation seems fully justified.
0 0
~
Z Levels. em
~ Z Levels. em
(a) (b)
5.60 5.25
16.80 18.75
28.00 32.25
~~ 39.20 ~o
So
45.75
S
u
50.40
u'"
59.25
~o .:;.
girl ',;
0
~ ~~0
."
';3 c: .;:;
."
,gO 0-
-' :.:l
d -0
.~ c:i
.~ 0 ><'"
";.0 , .,;'
o o
Io ~ ____L -____ ~ ____ ~
~,I...------'-------'-----~
0.0 3.0 6.0 9.0 oa 3.0 6.0 9.0
Radial Position. em Radial Position. em
0 q
0 0
on
(e) Z Levels. em '" (d) Z Levels. em
6.30 6.30
22.50 22.50
36.70 0 36.70
~;B
u.,
54.90
71.10 ~~ 54.90
71.10
u
.:;.
'8
0
~~
0'"
~~ ;i2
:E ."
;l .~~
:3' :.:l
«i~
._ 0 d
><- '>< ~
.,;' .,;~
,
o c
o o
'7'-------'------'-------1....J 1 I...------'-------'-----~
0.0 3.0
Radial Position,
6.0
= 9.0 0.0 3.0 6.0
Radial Position, em
9.0
Figure 8. Liquid Axial Velocity Profiles in the 0.190 m Diameter Column [Uo Values:
a) 0.02 m/s; b) 0.06 m/s; c) 0.10 m/s; d) 0.14 m/s].
367
In the largest diameter column of 29.2 cm at the lowest gas velocity of 4 cmls (bubble
flow) two circulation cells are observed; the top one, with the typical pattern of up in the
middle-down the wall, being the larger one. At the high gas velocity of 11 cmls (churn
turbulent flow), a single recirculation cell is observed. Gas induced liquid velocity
reaches 52 cmls at the centerline and has a peak of -25 cmls in the wall region. It should
be noted that Yao et al. (1989) also measured axial liquid velocity profiles in a 29 cm
diameter column. At ug = 10 cmls and 1IL = 1 cmls, at 3.5 m above the distributor they
report a liquid centerline velocity of 50 cmls, and the largest measured backflow velocity
(not necessarily maximum value) of -20 cm/s. This is in agreement with CARPT data.
At low gas superficial velocity, Ug, Yao et al. (1989) report larger centerline and backflow
velocities than CARPT data. It is possible that at these conditions (Ug-=' 4 cm/s) the
difference between Yao et al. (1989) conditions of UL = 1 cmls and CARPI' data (UL= 0)
becomes significant.
It is instructive to compare the above findings with the recirculation pattern of solids
(625 to 800 micrometers in size) in a 19 cm diameter fluidized bed obtained recently by
Moslemian et al (1989). At a low multiple of minimum fluidization velocity
(approximately 2.5 Umf with Umf= 30.2 cm/s) a small recirculation cell of solids exists in
the distributor region in addition to the large one above it. At large fluidization velocity
of 178.4 cmls (approximately 9 ume) a single solids recirculation cell exists throughout
the column with solids rising in the middle and falling at the walls. The analogy with
liquid circulation patterns is obvious.
CARPT data allows the computation of the tracer occurrence distribution by dividing
the number of occurrences in a compartment by the volume of that compartment. It is
important to examine this distribution as a function of axial and radial position to ensure
that tracer is not being excluded from some regions of the column. At all gas velocities
the occurrences per unit volume do not show any trend with respect to radial position.
The same is true of axial distribution of tracer occurrences at low gas velocity. However,
at the highest gas velocity a trend is apparent as the tracer occurrence "density" decreases
from 40 in the main part of the column to less than 10 in the disengagement region. This
indicates increasing bubble concentration towards the free surface and hence increased
exclusion of tracer particle. The errors in measurement are therefore larger in the
disengagement zone.
All the data presented here has been azimuthally averaged. However, careful
examination of the original data shows that axisymmetry does not exist (Devanathan,
1991). The azimuthal velocity is nonzero, the averaged axial velocity exhibits a strong
azimuthal dependence in the vicinity of the distributor. The radial velocity shows a
strong azimuthal dependence in the center of the column. Secondary vortices, which
cannot be detected from the azimuthally averaged data presented here, become apparent
by plotting the velocity vectors along different sectional planes within the column
(Devanathan, 1991).
The following conclusions can be reached regarding the mean liquid velocities:
1. Stagnant, multiple circulation cells of height equal to diameter do not exist.
2. Along most of the column, except in the vicinity of the distributor and at the free
liquid surface, liquid recirculation can be described by a single axial liquid velocity
profile. The inversion point is around 0.7 of the dimensionless column radius.
3. A single liquid recirculation cell (up in the middle, down at the wall) exists at high
gas superficial velocities (churn turbulent regime). The same is observed for solids in
fluidized beds operated at large multiples of Umf.
4.4.2. Turbulence Parameters. Turbulence parameters can be obtained from CARPT

data. Clearly, with "instantaneous velocities" being calculated by CARPT based on a
368
33 Hz sampling frequency, and due to the relatively large size of column "compartments",
it is not possible to obtain high frequency information on "micromixing". The lower
frequency information, and the effects of larger scale turbulence, can be assessed.
The Eulerian fluctuating velocities are computed by subtracting from the instantaneous
velocities the corresponding mean values for each compartment. The fluctuating velocity
components are the highest in magnitude in the axial direction, followed by the azimuthal
and radial direction. Instantaneous velocities as high as 100 cm/s are observed. The
mean of the fluctuating velocities is less than 0.035 cm/s in the radial and azimuthal
direction and less than 0.15 cm/s in the axial direction which compares reasonably well
with the theoretically expected value of zero. Frequency plots for various column
compartments indicate that fluctuating velocities are truly random and follow normal
distributions (Devanathan, 1991).
The computed turbulent axial and radial normal stresses and shear stresses increase
with increasing superficial gas velocity. Axial normal stresses are considerably higher
than their radial counterpart and both exceed Reynolds shear stresses. The maximum in
Reynolds shear stress increases remarkably as the gas velocity is raised from 6 cm/s to 10
cm/s and its location is in the neighborhood of the inversion point for the axial velocity
profile.
By extrapolation of the computed autocorrelation coefficient to zero time the square of
the Lagrangian fluctuating velocity can be obtained. The square root of this quantity can
then be compared to the Eulerian rms velocity for the same column compartment. The
two velocities should be equal in case of homogeneous turbulence. Devanathan (1991)
shows that this is not the case in bubble columns but that homogeneous turbulence is
approached at the highest gas velocities in the largest diameter column.
Computations of the Lagrangian integral time scale for different experiments yielded
values in the range of 0.4 to 0.8 seconds for different compartments. These time scales
are not strongly dependent on gas superficial velocity or column diameter. This implies
that the Lagrangian fluctuating velocity is statistically independent of itself beyond about
0.6 seconds i.e. in this interval the particle moves from one eddy (correlated region of
flow) to another.
Turbulence intensity in the axial and radial direction, averaged over the column length,
is presented as a function of radius in Figure 9 for the 19 cm column operated at four gas
flow rates. The intensity is defined as the ratio of the rms velocity in a particular direction
and the maximum liquid centerline velocity. These intensities are considerably larger
than those in single phase flow (e.g. single phase flow axial turbulence intensity rises
from 2% in the center to 12% close to the wall and drops to 0 at the wall). At high gas
superficial velocities the turbulent intensities are independent of gas velocity indicating
churn-turbulent flow.
The turbulent (eddy) dispersion coefficients were computed as the product of the
Lagrangian integral time scale and the square of the Lagrangian rms velocity, as indicated
by equation (4). The dispersion coefficients did not show any systematic variations in the
axial or radial directions. The average dispersion coefficients for the entire column for
each of the three column diameters are shown in Figure 10 as a function of gas superficial
velocity. Also plotted are the predicted axial effective dispersion coefficients based on
three popular correlations. Radial eddy diffusivity is a weak linear function of gas
superficial velocity and increases slightly with increased column diameter. Axial eddy
diffusivity shows a much greater dependence on superficial air velocity in smaller
diameter columns than indicated by correlations for the effective axial dispersion
coefficient. Only in the largest diameter column is its trend and magnitude comparable to
existing correlations. However, direct comparison of the axial eddy diffusivity and
effective axial dispersion coefficient is not meaningful. The former measures turbulent
369
o o
c:i
o
N
r-------------------~ c:i
~ r---------------------,
Uo Values. mls
0 = 0.02
Uo Values. mls
11 = 0.06 0 = 0.02
+ = 0.10 0.06
x = 0.14
• = 0.10
o a 0.14
c:i ~ ____- L_ _ _ _~L__ _ _ _~ c:i ~-----L--____L __ _ _ __LJ
0.0 3.0 6.0 9.0 0.0 3.0 6.0 9.0

Radial Position. em Radial Position. em
Figure 9. One Dimensional Turbulence Intensities in the 0.190 m Diameter Column.
mixing in the axial direction. The latter encompasses the effects of axial and radial
turbulent mixing and of the velocity profile (convective mixing) on mixing in the axial
direction. This may explain the discrepancies observed in Figure lOa. In addition, the
assumption of isotropic turbulence used to compute the eddy diffusivities is apparently
not satisfied in smaller diameter columns. The collected turbulence data requires further
analysis. Again it should be noted that the computed turbulence stresses and eddy
dispersion coefficients have remarkable similarity to those found for solids in fluidized
beds (Moslemian et al., 1989).
4.5 LIQUID RECIRCULATION AND CARPI DATA
CARPI data establishes the presence of a single liquid axial velocity profile throughout
most of the bubble column excluding end effects. It would be desirable to have a theory
(model) that can a priori predict this velocity profile. Unfortunately, the current models
by Rice and coworkers, (1981; 1990), Gasche et al. (1989), Devanathan (1991), cannot
accomplish that since they all require some yet unproven closure schemes. Hence, they
represent model fits not prediction of data.
To illustrate the representation of liquid velocity profiles by the dimensional models
we present data of HIlls (1974) and four models (Devanathan, 1991) for two distinct gas
superficial velocities (Figure 11).
Model I relies on constant eddy viscosity (which is a function of gas superficial
velocity and column diameter) and uses the observed gas radial holdup profiles as input.
Eddy viscosity is chosen to match model predictions and data. Models lIA, lIB rely on
the mixing length concept, the former uses the classical Nikuradzes single phase profile,
the latter relies on Rice-Geary's (1990) use of the bubble diameter as characteristic
mixing length. Both use the measured (Hills, 1974) radial voidage profile as input.
370
1000 1000
D=O.114m D=O.I90m
(a) (b)
~ ~
E 800 E 800
() () .6.
.6.
~
C c
Q) 600 Q) 600
·u
<;::::
'u .6.
Qj
0
~0
400 400
0
~
0
c c -r.'..;:;::'-~-.-
0 0 ---;.-:;;..,--
'iii ·iii
~
200 200 ~'--
Iii .------- Iii ~~~~
Q. ~- .::::..":"------- 0 Q.
en en 0
IS. 0 0 0
0 0 0 0 0
0 5 10 15 20 0 3 6 9 12 15
Air Superficial Velocity, cm/s Air Superficial Velocity, cm/s

800
--
-...
(/) 700 (c) D=O.292 m
N
E
() 600
-"-.-;'--;::;:~';' .6.
...... . ,., . -."4. . . . . . . . . 6.
C 500
Q) 0 Radial Eddy Dispersion
'u .6. ;,'
~
f::. Axial Eddy Dispersion

400
~0 ------
Deckwer et al .. (1974)
0 300 Baird & Rice. (1975)
c Miyauchi et al .. (1981)
0
'iii 200
0 0
Iii 0 0
Q. 100
en
0
3 6 9 12
Air Superficial Velocity, em/s
Figure 10. Measured Turbulent Dispersion Coefficients and Predicted Effective Axial Dispersion
Coefficients in Three Columns: a) 0.114m; b) 0.190 m; c) 0.292 m.
Model III relies on constant eddy viscosity (which is a function of gas velocity and
column diameter) but predicts the power law form of the gas holdup profile. It
accomplishes that by using both gas and liquid continuity equations, and be establishing
that the cross-sectional integral of the slip velocity is a constant multiple of the superficial
gas velocity. The agreement of model III with the velocity data of Hills is excellent as is
its prediction of Hills's measured voidage profiles.
Figure 12 shows the agreement of model III, with CARPT velocity data, while Figure
13 shows the prediction of model III for holdup profile in CARPT experiments, which
was not measured. To measure such time averaged voidage profiles we are now
constructing a gamma ray device for computer tomography (CT). This is important since
the voidage profile drives liquid circulation. Clear/y, simultaneously gathered holdup and
velocity data are needed for verification of two-phase flow models.
371
0 0
co
" (a) (b)
",0 ",C!
EN
--.. 0
.---....,.
--"0
E"
,
.". \
U U
i-
·u
i-
·u
0 0
-......:: "Q)o
~~ >0
"0 "0
·S ~ ·S
~.
0" 0"
:.:J :.:J
~o
x . ]10
x .
\
- --- Modell
<t:~ --- Modell <t:1 - - - Model lIA
- - - Model IIA
_._.- Model lID -._.- Model lIB
0
0
--------
. Model III
Expcrimclltal Data. 0
0
":'
--------
•
Model III
Experimental Data
'f
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Radial Position Radial Position
Figure 11. Model Calculated Liquid Velocity and Data of Hills (1974) [a) lIo= 1.9 em/s;
b) ua = 16.9 em/s].
0
~
'"
(a) (b)
C! 0
$? 0
",,,
..!!? '-
E E
UC! U
.10
>-
+-' :t:: a
>-0
·u UN
0 0
"Q)o "Q)
>0 >
"0 "0
·s .- 0
:::J .
0"0
0"
:.:Jo :.:J
-'?
co ro
·x 'x
<t: <t:o
0 0 -
';'
~
-
0
0
0
~ 'f
0.0 0.2 0.4 0.6
0.0 0.2 0.4 0.6 0.8 1.0 0.8 1.0
Radial Position Radial Position
Figure 12. Model Calculated Liquid Velocity and CARPT Data [Ua= 1.99 em/s;
b) U a = 14.08 em/s).
372
o
d ,----------------------------------------,
UG Values. em/s
14.1
.
9.9
6.0
on
2.0
ci
n =5.0
c:
o
..."
U o
Cll",
U: d -
-0
n_7.4
~
n-19.7
o
o
ci L -_ _ _ _ _ _~_ _ _ _ _ _~_ _ _ _ _ __ L_ _ _ _ _ _~_ _ _ _ _ _~
0.0 0.2 04 0.6 0.8 1.0
Dimensionless Radial Position
Figure 13. Model III predicted gas holdup profiles for CARPT data.
5. Concluding Remarks
CARPT experiments in bubble columns demonstrate that while liquid circulation is
always present in the column, stationary multiple recirculation cells with height equal to
column diameter are not. Secondary cells may exist in the entry region at lower gas
velocities (bubble flow regime). The entry length is then limited to 1 to 1.5 column
diameter. Similar recirculation profiles were reported for solids in fluidized beds
(Moslemian et aI., 1989).
Turbulence intensity is an order of magnitude greater than in single phase flow.
Normal shear stresses in axial direction are much higher than Reynolds stresses.
Turbulence tends to become homogeneous in larger diameter columns at high gas
velocities (chum turbulent flow). The axial eddy diffusivities are two to five times higher
than radial diffusivities and increase with column diameter and gas velocity.
CARPT offers possibilities for mapping velocities and turbulence parameters for liquid
and solids in bubble columns, ebulated beds, fluidized beds, slurry mixed systems, etc. It
allows detection of stagnancies and assessment of distributor designs and column
internals on flow pattern and mixing. The usc of the technique in high pressure systems
is feasible.
CARPT accuracy can be further improved for measurement of liquid (or solids)
velocity. However, testing of multiphase flow models, which predict velocity and holdup
profiles, also demands experimentally measured holdup profiles. This requires
application of computer tomography (CT) which is currently planned. A combined
CARPT-CT facility would provide the necessary and sufficient velocities and holdup
information for verification of multi phase flow models based on first principles. It is
noteworthy that the liquid recirculation profiles and eddy diffusivities show remarkable
similarity to those for solids in gas fluidized beds. This gives additional support to the
373
notion that the same fundamental two phase flow models could be used to describe the
motion and turbulence of the recirculating phase in bubble columns and fluidized beds.
Significant additional research on two-phase hydrodynamics in bubble columns is
required before scale-up and design based on first principle becomes feasible.
6. Acknowledgement
The support by industrial sponsors (Amoco, BP Research, DuPont, Eastman-Kodak,

Ethyl, Exxon, Mobil, Monsanto, Phillips, Shell, Texaco and Union Carbide) of the
Chemical Reaction Engineering Laboratory at Washington University made the bubble
column research and CARPI installation possible. Partial NSF support (Grant No. CBT
8820555) and the involvement and help of D. Moslemian of Rorida Atlantic University
in exposing us to the CARPI hardware is gratefully acknowledged.
7. Notation
c - concentration
£ - concentration vector
Cb - bulk concentration
D - eddy dispersion coefficient
H - expanded column height (also recirculation height)
I - intensity of turbulence
KE - kinetic energy of turbulence
n - holdup exponent
Nvel - number of occurrences of tracer in each compartment
Nexp - number of statistically independent experiments
Q - volumetric flow rate
r - radial coordinate
p - pressure
R - column radi us
R - reaction rate of species j
RL - Lagrangian autocorrelation coefficient
t - time
TL - integral time scale of turbulence
T - temperature
u - local instantaneous velocity
u' - Eulerian local fluctuating velocity
Uj - i-th component of local instantaneous velocity
u - local time averaged velocity
U - superficial velocity
Vi - Lagrangian fluctuating velocity
v - radial velocity component
Greek Symbols
f3 - constant
E - gas holdup
Vt - eddy viscosity
p - density
374
o - Reynolds shear stress, also variance of the spreading of particles

L - operator (differential or other)
Subscripts
b - bulk conditions
o - superficial gas velocity, also feed conditions
G -gas
L -liquid
- average
8. References
Anderson, K G. and Rice, R G (1989), 'Local Turbulence for Predicting Circulation

in Bubble Columns', AIChE 1. 35, 514-518.
Baird, M. H. I. and Rice, R G. (1975) 'Axial Dispersion in Large Unbaffled
Columns', Chern. Eng. J. 9 (2), 171-174.
Beaton, W. I., McDaniel, N. K, McWhriter, W. E., Petersen, R D. and Van Driesen,
R P. (1986), 'Resid Hydrocracker Expands Crude Processing Rexibility', Oil and
Gas 1. 7,47-53.
Bendat, J. S. and Piersol, A. G. (1986) Random Data Measurement and Analysis
Procedures, John Wiley and Sons, New York. pp 1-90.
Brodkey, R S. (1967) The Phenomena of Fluid Motions, Addison Wesley,
Reading, MA . pp227-364.
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STRATEGIES FOR LOW EMISSIONS FROM
CIRCULATING FLUIDIZED BED BOILERS
F. BERRUTI and R. WONG

Department of Chemical and Petroleum Engineering
The University of Calgary,
Calgary, Alberta 12N lN4
Canada
ABSTRACT. The objective of the work presented in this paper is to review and discuss
important issues related to the combustion process carried out in Circulating Fluidized Bed
Combustors (CFBC), with emphasis on the relevant aspects relative to the emission control
strategies aimed to meet the progressively stricter environmental regulations being implemented
around the world. The treatment deals with the present knowledge of the coal combustion in
CFBCs and the relationship between pollutants emissions, combustion process and reactor
performance, on the basis of experimental evidence gained by both academicians, using
laboratory scale units, and industrial researchers, utilizing larger scale demonstration and
commercial units.
1. Introduction
Until 20 years ago coal-fired utility plants were considered a triumph of modern
technology for generating heat and electricity at reasonable costs. As of 1989, 2,777
billion kilowatt-hours of electrical power were generated in the United States, of which
56% was produced by burning coal, 19% from nuclear plants, 9.5% from hydroelectric
sources, 9.5% from burning natural gas and the remaining 6% from petroleum,
geothermal and other sources.
Recently, environmental concerns have highlighted the hidden costs of energy
generation by coal combustion. Coal burning plants emit large quantities of gases to the
atmosphere that may fall back to earth as acid rain or contribute to the global warming.
Among these gases are sulfur dioxide, oxides of nitrogen and carbon dioxide. Of the
various sources of air pollution in the U.S., coal-fired power plants contribute about 70%
of the sulfur dioxide, 30% of the nitrogen oxides and about 35% of the carbon dioxide.
However, coal accounts for more than 85% of the potential U.S. fossil-fuel reserves and,
as such, an increased exploitation of this domestic fossil fuel would drastically decrease
the risk of a possible dependence on foreign fuel supply. Even though natural gas is a
379
H.I. de Lasa et al. (eds.), Chemical Reactor Technology for Environmentally Safe Reactors and Products. 379--408.
380
much cleaner energy source, generating negligible sulfur dioxide emissions and about half
as much carbon dioxide, it accounts only for about lO% of the potential U.S. fossil fuel
reserves. Despite the great incentive in utilizing coal as an energy source, the U.S.
government has approved new amendments to the Clean Air Act aimed at tackling a
range of air pollutants, including the two major precursors to acid rain (sulfur dioxide and
nitrogen oxides). The law calls for utilities to reduce their annual sulfur dioxide
emissions from some 17.5 million tons to 8.9 million tons by the year 2000. Also it calls
for cuts in nitrogen oxides emissions, from 13 to 11 million tons per year. Although not
considered yet, limits on carbon dioxide emissions seem not too far down the road.
2. Coal Combustion Technologies
Over the last 20 years, because of the progressively tougher environmental legislations,
means of reducing emissions from coal-fired power plants have been implemented, based
on scrubbing processes applied to the flue gases produced. Scrubbers (flue gas
desulfurization units) employ alkaline solutions (limestone and water) which react with
sulfur oxides, present in the sulfur-laden flue gases, to form calcium sulfite or sulfate
(gypsum) which precipitates out as wet sludge. This type of cleaning devices have been
proven relatively efficient (up to 90% sulfur removal) but expensive, because of energy
requirements (2 - 3% of the boiler output) and especially of corrosion problems. Also,
enormous amounts of solid wastes (calcium sulfite and gypsum) are produced and
additional carbon dioxide is generated during the scrubbing process, which may negatively
affect the move towards environmentally acceptable plants (Balzhiser and Yeager, 1987).
Over the same time period of 20 years, a tremendous progress has been made to the
development of Fluidized Bed Combustion (FBC) technology, as an improved alternative
to the conventional coal-fired boiler technology. By 1985 more than 160 industrial
fluidized bed boilers were in operation in the Western nations with about 50 firms selling
fluid bed boilers all over the world (Yerushalmi, 1986).
The main design feature that distinguishes fluidized bed boilers from conventional
coal-fired boilers is that the fuel is burned in a bed of solid particles suspended in an
upward flow of air. As a result, the bed can contain pollution-controlling chemicals and
thus capture polluting gases before exiting the boiler. Also, higher heat transfer rates are
achieved because of the conductive heat transfer contribution from the solid bed particles
to the boiler tubes in the bed and on the walls, thus reducing the total surface areas
required and consequently the capital cost. A comparison of conventional and fluidized
bed boilers is provided in Table 1 (Ehrlich, 1987).
Atmospheric Fluidized Bed Combustors (AFBC), operating at nearly atmospheric
pressure, are fluidized with superficial air velocities from I to 4 mls. During operation,
the bed consists of sorbent particles (limestone or dolomite), ash particles and coal. Coal
particles bum at about 900°C, which is roughly half of the combustion temperature in
pulverized coal-fired boilers. Although the coal particles constitute only about 1% of the
total bed material, the bed temperature is uniform and about lOO°C lower than the coal
particle temperature, due to the excellent heat transfer characteristics generated by the
381
vigorous solids mixing. Coal and sorbent particles are fed into the boiler from hoppers
and are either thrown onto the top of the bed or injected into the bottom. Due to the
combustion process and the abrasive action in the bed, fines are constantly formed and
Table 1. Comparison of coal-fired and fluidized bed boilers
Item Conventional boiler Fluidized-bed boiler
Emission control Coal cleaning before Sorbent material in bed

firing or ftue gas reduces SO) emissions
desulfurization
Fuels Limited to high-quality Can bum any coal. lignite.
coals or wood waste
Heat transfer nlte 50-100 kW/m: >315 kW/m)
Waste materials Sludge of sulfur-con- Primarily gypsum (CaSO.1
taining compounds
Ash Fouls superheater Not a problem
boiler tubes
elutriated from the bed by the gas stream. Boiler tubes can be either introduced into the
bed or form the walls surrounding the bed itself. The gas leaving the bed passes through
a convective section, which can contain any combination of steam reheater, steam
superheater and economizer tube banks. The thermal efficiency of the bed can be
increased by recirculating entrained coal and sorbent particles until they are completely
reacted by an appropriate cyclone system. Figure 1 illustrates a typical atmospheric
fluidized bed boiler design (Bonn and Richter, 1990).
If a sufficient superficial gas velocity increase or particle size decrease is achieved,
the transport of solid particles through the bed increases to the point at which the entire
combustor volume is filled with a solid-gas mixture. The solid material exiting from the
top of the reactor must then be captured by a cyclone and recycled to the bed, thereby
creating a Circulating Fluidized Bed Combustor (CFBC). Most of the beneficial
features of AFBCs are found in CFBCs. The most noticeable difference is a much larger
recycling cyclone used in the CFBC. Circulating fluidized beds can achieve improved
performance over conventional fluidized bed boilers for two main reasons: (1) the
residence time of the solid particles is longer, and (2) the particle mixing is much more
efficient due to the specific regime of fluidization. There is an inherent slip velocity
between the particles and the gases, resulting in a more reactive, back-mixed
environment. Also, as smaller solid particles are typically used, the total surface area
for reaction is greater, especially for that of sulfur capture. The combustion and
pollution abatement reactions occur throughout the reaction chamber and also small
particles can participate to these reactions. Typically, combustion efficiencies greater
than 98% are achieved, and over 90% sulfur dioxide capture is attained with a Ca/S ratio
around 2. The major trade-off associated with CFBCs is the increased height of the boiler
and the increased pressure drop, requiring greater horsepower to drive the forced draft
fans. Figure 2 illustrates a typical circulating fluidized bed boiler design (Bonn and
Richter, 1990).
382
Fluidized bed boilers can also accommodate operating pressures well above
atmospheric (10 to 20 atm). Pressurized Fluidized Bed Combustors (PFBC), having
similar design features as atmospheric ones, can be either conventional fluid beds or
circulating fluidized beds. The high operating pressure allows the flue gases to be used
in expansion turbines, which drive the air compressors in addition to generating
electricity. The waste heat from the gas turbines is used subsequently for steam
generation. The resulting thermal efficiency is therefore higher than that of atmospheric
units: the PFBC has typically a net plant thermal efficiency 1 - 4% higher than that of an
equivalent AFBC. Also, the operation at high pressure leads to a drastically reduced size
Air
Figure 1. Atmospheric Fluidized Figure 2. Circulating Fluidized

Bed Boiler Bed Boiler
of boilers, with relatively lower investment costs. Reduced emissions can be obtained
using PFBCs, which adds to the attractivity of this technology. However, major
technical challenges associated with pressurized plants include gas cleanup strategies for
removal of particulate matter which can damage the turbines by erosion, without cooling
the gas (Ehrlich, 1987). Figure 3 is a schematic diagram of the PFBC concept
(Grimethorpe unit, UK) (Yates, 1983).
WA1CR-WAlL INUIT
WArn>
COAL coAL
ASH
Figure 3. Pressurized Fluidized Bed Boiler

383
3. Fundamentals of CFBC Combustion
Over the last decade, a great deal of operating experience has been gained by industry
by utilizing circulating fluidized bed boilers. However, most of the fundamental studies
on combustion have been performed using bubbling bed combustors. The combustion
characteristics in a circulating bed are substantially different than those in the bubbling
bed, due to the inherent difference in the hydrodynamics and operating conditions of the
two systems. In conventional fluidized beds, the combustion process splits between the
dense bed and the freeboard region, where in circulating fluidized bed operation, the
combustion process is more uniformly distributed. The basic phenomena involved in
coal combustion are similar in various processes and technologies:
1. heating of the coal particles to ignition temperature and vaporization
. of any trapped moisture,
2. pyrolysis of volatile matter (devolatilization) and subsequent
combustion of the volatiles outside the particle surface,
3. combustion of the remaining char material.
Figure 4 illustrates these three steps, showing the relative time
to complete each (Keairns et aI., 1984). .
Due to the differences in the time-temperature history of the coal particles in different
technologies, there can be significant quantitative differences in the burning rate and
release of pollutants.
F,,,.
partlclei
f1eaIUP 1<. 100 ~ml
Co,rse
p,t1lClfS
I> IOCuml
10 l 10 ' 10' 10' ,0' 10' ,0' 10'

Tim. (Mel
Figure 4. Combustion mechanism (Keairns et aI., 1984)
3.1. DEVOLATILIZA nON
The devolatilization process is common to all thermal coal conversion processes and
several papers have reported the results of many years of research (Anthony and Howard,
1975; Juntgen and van Heek, 1979). Coal consists of many organic molecules bound
together through relatively weak carbon-carbon bonds. Many of these bonds tend to
break at low temperatures (about 350°C), releasing aromatic hydrocarbons and gases.
384
Some of the heavier hydrocarbons may further react with the char and crack to yield
lighter compounds and carbon. The products of devolatilization eventually diffuse to the
particle surface through the internal pores and, through a boundary layer, to areas of
higher oxygen concentration where combustion occurs (Ehrlich, 1987).
Volatile combustion has been studied for bubbling fluidized beds, where the volatile
flame has been assumed, in the proposed models, to be surrounding the particle (Borgi
et aI., 1985). Stubington and Chan (1988) have concluded that the mixing of volatiles
with oxygen is the rate limiting step for combustion to occur in the dense phase of
fluidized beds. Lee and Hyppanen (1989) developed a three dimensional coal combustion
model for circulating fluidized beds, to simulate the performance of a 85 MWth CFB
boiler. Based on the model predictions, the volatile combustion is incomplete if
secondary air injection is not introduced, resulting in a small portion of volatiles escaping
from the combustor near the wall region.
In circulating fluidized bed combustors, the volatile release and combustion are
important with regard to pollutants emissions, heat release patterns and the subsequent
reactivity of the char particles. For coals with high volatiles content, the release of
volatiles is important in the selection of the feed point location, since the time constant
for volatiles release and combustion is much shorter than the char burnout time. Tn
addition, solid mixing and rate of devolatilization determine the region of volatile release.
3.2. CHAR COMBUSTION
Once devolatilization has occurred, what remains is a porous char particle with a large
C/H ratio (almost pure carbon). The rate of combustion of char is influenced by the type
of coal, particle size, temperature, oxygen concentration and fluidization characteristics.
Heat and mass transfer, coupled with the chemical reaction kinetics, are the basic
processes occurring during char combustion. The key factors influencing the combustion
rate of a coal particle are illustrated in Figure 5 (Engstrom and Lee, 1991). The mass
transfer aspects and reaction kinetics have been extensively studied (A vedesian and
Davidson, 1973; Chakraborty and Howard, 1978; Andrei et aI., 1979; La Nauze and Jung,
Figure 5. Factors affecting coal particle combustion rate (Engstrom and Lee, 1991)
385
1982; Basu, 1985; Agarwal, 1987). In general, it has been found that oxygen diffuses to
the surface of the carbon particle and reacts to form both carbon monoxide and carbon
dioxide, with CO as a major product (Basu et aI., 1975). The CO diffuses out of the
boundary layer and reacts with oxygen in both the boundary layer and in the bulk gas.
Chemical kinetics and mass transfer are the two competing rate controlling
mechanisms. The relative influence of mass transfer to reaction rate control is usually
studied by examining the exponent of the diameter in the burnout time expression
obtained from batch or single particle combustion experiments. La N auze (1985) has
concluded that time resolved changes of mass and diameter experiments are preferred in
deciding the control mechanism (Engstrom and Lee, 1991).
Conditions are such in fluidized bed systems that particles greater than 1 mm in
diameter usually bum under diffusion control and particles smaller than 300 11m bum
under kinetic control. Basu and Halder (1989), based on studies of combustion of single
carbon particles in a CFBC, observed that the burning rate of coarse particles (from 5 to
9 mm) in fast fluid beds is faster than in bubbling fluidized beds and concluded that this
is due to the high rate of mass transfer of oxygen, due to the high slip velocity. Both
Nusselt and Sherwood numbers of burning carbon particles in a CFBC are higher than
in a AFBC.
Two stoichiometries can occur:
C + O2 ~ CO 2 (1)
and 2C + O2 ~ 2CO (2)
In reality, CO is always formed in the initial reaction stages. The CO subsequently

diffuses outward and reacts with oxygen. However, if CO bums within the boundary
layer, the effective surface product is carbon dioxide, and the first stoichiometry is used.
On the other hand, if CO bums outside the boundary layer, the effective surface product
is CO and the second stoichiometry is utilized. Carbon dioxide can diffuse back to the
char particle and react:
CO2 + C ~ 2CO (3)
Based on the above observations, carbon dioxide can be expected as the surface product
from combustion of larger particles (> 1 mm), whereas, CO as that from smaller particles
« 300 11m).
A model for CFBCs, proposed by Lee and Hyppanen (1989), predicts char combustion
rate as a function of particle size, oxygen concentration and temperature.
3.3. FRAGMENTATION AND ATTRITION
Coal particle fragmentation and attrition during combustion has been extensively studied.
For bubbling fluidized bed combustion, the attrition rate has been typically assumed
proportional to the excess gas velocity above minimum fluidizing conditions, carbon
386
loading and particle size. Chirone and Massimilla (1988) studied primary
fragmentation, related to the pressure build-up in the pore network during devolatilization.
Sundback et al. (1984) have studied the secondary fragmentation, related to the burning
of bridges connecting different regions of a char particle. For small particles, Kerstein and
Niksa (1984) have proposed a percolation mechanism, where fragmentation is due to
internal combustion under chemical kinetic control. The effect of the type of coal on the
attrition rate has been experimental investigated by Chandran and Duqum (1989). Basu
and Halder (1989) showed that the attrition rate of coarse particles by fine solids in a
CFBC is proportional to the exposed surface of the coarse particle and the difference
between the average upward velocity of bed solids and that of the coarse particles.
Studies of attrition conducted by Engstrom and Lee (1991) by comparing results obtained
by burning coal in an oven and in a CFBC, concluded that attrition in the CFBC is
significant, compared to fragmentation due to devolatilization and combustion.
3.4. ASH AGGLOMERATION
Ash agglomeration has been observed in AFBCs, due to hot spots in the combustor
resulting from poor mixing, and to the sodium and potassium content (alkali) of the coal
forming sticky compounds on the particle surface. The problems caused by a high alkali
content can be corrected by adding additives such as kaolinite (Engstrom and Lee, 1991).
The hot spots are not expected to occur in CFBCs due to the extremely good solids
mixing.
3.5. COMBUSTION EFFICIENCY
The combustion efficiency is lowered by the presence of fine particles, still containing
a significant carbon content, in the gas stream leaving the cyclone as fly ash. Based on
the results obtained from commercial units, Engstrom and Lee (1991) reported the
presence of 8.5% of unburned carbon in the fly ash, with the majority of the carbon loss
due to particles smaller than 15 }Im. The carbon loss from the bottom ash is negligible
compared to that from the fly ash. Therefore, the combustion efficiency can be increased
by (1) increasing the temperature, (2) using multicylones to collect the fines and recycling
the fines back in the combustor and (3) recycling fly ash from the baghouse. In CFBCs
typical combustion efficiencies of 99% have been typically reported.
3.6. SULFUR EMISSIONS
Combustible sulfur exists in coal in the inorganic form of pyrite (FeS2) or is part of the
organic molecules of the coal. The sulfur content varies from less than I % (low sulfur
coals) to about 5%, for some eastern Canada and U.S. coals. During combustion, sulfur
dioxide is formed. In fluidized bed combustion, high calcium limestone (CaC03) or
dolomite (CaC03 MgC03) are used for sulfur capture. At high temperature (> 750°C),
calcium oxide is formed from limestone via calcination reactions:
387
(4)
For dolomite, the calcination process involves the thermal decomposition

to calcium carbonate and magnesium carbonate, followed by two half
calcination steps, the first forming magnesia (MgO) and the second CaO:
(5)
CaC03 + MgCO ---t CaC03 + MgO + CO2 (6)
(7)
The half calcination of dolomite produces a very porous stone that is capable of absorbing
sulfur in a PFBC, where the partial pressure of carbon dioxide is high enough to inhibit
the lime formation reaction.
The reactivity of dolomite is greater than that of limestone. However, dolomite tends
to suffer from the process of decrepitation, a surface cracking process resulting from the
evolution of water and carbon dioxide during calcination. At atmospheric pressure, the
calcination process is fast and a large portion of dolomite is reduced to fines. At high
pressures (PFBCs), dolomite can be efficiently used for sulfur capture, showing higher
yields than limestone.
The reaction of interest, between sorbent and S02' is as follows:
(8)
Many factors affect the sulfur capture; the most important are Ca/S ratio, recycle
ratio, temperature, sorbent type and sorbent particle size. The effects of these
parameters will be discussed later in the paper.
3.7. NITROGEN OXIDE EMISSIONS
Two sources of nitrogen oxides (NOx) are associated with the combustion of coal. The
first, called thermal nitric oxide, results when air is heated to elevated temperatures and
causes the dissociation of oxygen and nitrogen to their atomic form, which then
recombine to form nitric oxide. The second source, more significant, is due to the
reaction of oxygen with organic nitrogen. Coal contains generally from 1 to 2% nitrogen
and both common oxides of nitrogen (NO and N02) are formed during the combustion.
N02 concentration is generally less than one-tenth that of NO but, when the flue gas is
cooled, NO oxidizes to N02 . Therefore, the emission standards are based either on N0 2
or NO x limitations. Five generally accepted mechanisms for NO formation can occur
during the coal combustion in a fluidized bed system (Ehrlich, 1987):
1. reactions of atmospheric nitrogen and oxygen to form thermal NO,
2. reaction of atmospheric nitrogen and oxygen via a solid
intermediate, (e.g. calcium cyanimide CaNCN).,
388
3. reaction of organic nitrogen with air via a solid intermediate,

4. reaction of organic nitrogen directly with air,
5. reaction of volatiles with air via a gaseous intermediate (e.g. HCN).
There are also four mechanisms for the destruction of NO:
1. reaction with char to form CO, carbon dioxide and nitrogen,
2. reaction with gaseous intermediates (e.g. N~),
3. reaction with hydrocarbon volatiles,
4. heterogeneous catalytic reaction.
The most likely formation mechanism is the direct reaction with air, whereas the
reaction with char to form carbon dioxide appears to be the most favourable destruction
route. Figure 6 shows the relationship between NO formation and destruction pathways
(Gibbs and Hampartsoumian, 1984).
3.8. PARTICULATE EMISSIONS
Fly ash and elutriated bed material contribute to the typical particulate emissions from
fluidized bed combustors. Dust collectors must be particularly effective to limit solids
loadings out of the stack and to minimize erosion problems in the turbines of PFBCs.
The typical method implemented is the installation of fabric filters, Teflon coated
fiberglass or Nomex (nylon), in a gas cleaning equipment, commonly referred to as a
baghouse. These devices are located downstream with respect to the cyclone and
generally the gas is cooled before being treated.
Electrostatic precipitators can also be used for dust collection from flue gases.
Thermal 1 ComtWS\IQn NO). Formation

decompOSItIon : 1"e' 1'\ ~\lol\JllOn NO.. Reduction Products
HeterogeneoU$
Homogeneous
Figure 6. Mechanisms of NOx formation and destruction (Gibbs and Hampartsoumian,

1984)
3.9 TRACE EMISSIONS
Trace elements which can be detected in the emissions from fluidized bed combustors
include halides (chlorine, fluorine and bromine), and metals. They are typically part of
389
the incoming coal or limestone and it is desirable to capture them rather than let them
escape into the environment in the gas or in the particulate phase.
Metals have the tendency to collect in the ash and this retention is particularly
effective at the temperatures typically encountered in FBCs.
Halides are much more difficult to capture, although they can be collected, at least in
part, in the ash or, when present, in the dolomite.
4. Emission Control Strategies
Many strategies are available for controlling emISSIOns in CFB combustors. The
efficiency of each emission control strategy is linked to the operating conditions of the
combustor. Consequently, proper implementation of emission control strategies requires
an understanding of how combustor operating conditions affect emissions. The following
provides a brief overview of the sorbent injection, ammonia injection and staged
combustion types of emission control.
4.1. SORBENT INJECTION
Of all the schemes proposed for controlling S02 emissions, the simplest and most direct
method is the addition of a sorbent to react chemically with S02. As the limestone is
introduced into the combustor, it undergoes calcination (eq. 4), which gives it a porous
structure. Sulfur dioxide and oxygen diffuse into the porous structure and reacts with the
calcium oxide (eq. 8). Since the reaction product calcium sulfate (CaS04) has a larger
molar volume than the original limestone, a product layer forms around the grains and
pores of the sorbent and reaction eventually stops before all the limestone has reacted.
Usually, only 50% of the limestone reacts and it must, therefore, be fed at a rate greater
than the stoichiometric amount. Figure 7 shows the effect of calcium-to-sulfur ratio on
sulfur retention (Kullendorf et aI., 1988). Figure 7 also shows the difference sulfur
retention behaviour in CFB units as compared to bubbling bed units. Nykoping and
Karlskoga are CFB units while Chalmers is representative of a bubbling bed combustor.
The effect of temperature on sulfur retention and the different sulfur retention behaviour
observed in CFB units and bubbling beds will be discussed in detail later in the paper.
4.2. AMMONIA INJECTION
One of the methods which may be used to reduce NOx is the injection of ammonia in the
combustor. A series of homogeneous gas-phase reactions to form nitrogen and water
occur (Hoke et aI., 1980):
6 NO + 4 NH3 ~ 5 N2 + 6 HzO (9)
02 + 4 NO + 4 NH3 ~ 4 N2 + 6 HzO (10)

390
Generally, the amount of NH3 required is comparable to the amount of NO reduced

(Hoke et al., 1980). In conventional combustion processes the optimum temperature for
NOx reduction in the presence of ammonia is about 950°C. At temperatures above or
below the optimum, ammonia loses its effectiveness very quickly. However,
investigations in CFB combustors by Hiltunen and Tang (1988) have shown that
ammonia injection can also work well at temperatures as low as 870°C and satisfactorily
at temperatures around 800°C and figure 8 shows this relation between ammonia
requirements and NOx reduction. The figure also illustrates the relationship between bed
temperature and reducing properties of ammonia. The experimental data is from an
Ahlstrom Pyroflow CFB combustor. Depending on ammonia injection location, operating
bed temperature and concentration of char, sand and limestone in the combustor, the
oxidation of ammonia to NOx can also occur. The reaction is given by
(11)
100...-----..=;;-
.
z
o
E
:;:; 50
'"
..
'"~
=> • NYt(O~HG Tb- 8$0 C
7 o
4)
HYt(OPING
J( ARlSK OGA
Tb'"'900 C
Tb- ea 0 C
• CHALMERS Tb-eoo c
II< CHALMERS It.-no c
o 2 345
UMESTONE AOOU &./$
Figure 7. Sulfur retention for different plants at various bed
temperatures as a function of Ca/S ratio
100
870 "c
90
.. _ .. 870 DC
~ 80 .....c 102 P!"1
800°C
~.. ~ "" 70
• 110 Pt:m
60
Petchora coal
Corrected to 7 % oxygen (dry)
50
(NOxl ppn 110 102 150
TG 0c 800 870 870
40
Urea solutlon
(40 %wtj
• o o
J\rrm::)nla
30
Figure 8. Thermal NOx reduction in Ahlstrom Pyroflow with ammonia

or urea. Base NOx level and temperature at injection
location as parameters. Pilot plant test results
(Hiltunen and Tang, 1988).
391
Ammonia injection near the bottom of bubbling bed combustors can lead to increases in
NOx emissions (Minchener and Kelsall, 1990; Hoke et al., 1980). The effect is attributed
to the high oxygen concentration due to the close proximity of the primary air distribution
which can lead to oxidation of ammonia. Studies have revealed that the optimum
ammonia injection location is either in the upper furnace area or in the cyclone (Hoke et
al., 1980; Minchener and Kelsall, 1990; Hiltunen and Tang, 1988; Shimizu et al., 1990).
Injection locations anywhere else either increases NOx emissions or creates unacceptable
ammonia slip into the atmosphere. Experimental studies indicated that under high
concentrations of char and limestone, NOx emissions can increase with ammonia injection
(Shimizu et al., 1990). The effect is attributed to the catalytic effect of char and
limestone on ammonia oxidation. Using a kinetic model for NOx formation, 10hnsson
(1989) has shown the importance of the ammonia oxidation in the presence of limestone
and char catalyst.
4.3. STAGED COMBUSTION
Air-staging aims at reducing NO x emISSIOns by capitalizing on the enhanced NO x

destruction that occurs under sub-stoichiometric conditions. In air-staging or staged
combustion, the combustion air is separated into a primary air stream which constitutes
the fluidizing air supply to the bed and a secondary air stream that is injected higher up
in the bed. All the coal is injected into the primary stage so that the bed is maintained
at or near sub-stoichiometric conditions creating NOx reduction. Partial combustion of
coal in the reducing environment produces carbon monoxide and char, which tends to
reduce NO x by the following reactions:
(12)
NO + C ~ 0.5 N2 + CO (13)
The higher the location of the secondary air the greater the reduction in NOx
emissions. Figure 9 shows the effect of air-staging on NOx emissions in the Studvik 2.5
MW CFB prototype (Berge, 1988).
200
175 /
150
/0
.'" CI
~
0 125
0
:I
100
75
0
z 50
25
0
0.5 0.7 0.9 1.1
STOICmOMETRIC RATIO
Figure 9. NO emissions as a function of primary zone stoichiometry. (Berge, 1988)
392
A consequence of staged combustion in bubbling beds is a reduction in combustion

efficiency. Studies by Khan and Gibbs (1991) shows that the lower the quantity of
primary air, the lower the combustion efficiency. The main reason for the
decrease in combustion efficiency is due to the short residence time of the secondary air
stream and loss of unburned solids from the system. However, in CFB combustors, solids
usually have long residence time, because of high recirculation and thus, as shown by
Tsuboi and Iwasaki (1988) and Ishizuka et al. (1988), there is no apparent relationship
between combustion efficiency and staged combustion.
5. Effect of Operating Conditions on Emission Control Strategies
A review is presented on how operating conditions like temperature, excess air ratio,
sorbent type, solids recirculation rate, structure and composition of feed coal, and pressure
affect the quantity of emissions from CFB combustors.
5.1. EFFECTS OF SORBENT TYPE
Limestone is usually the sorbent used for sulfur capture. Although lime has better sulfur
capture capabilities than both limestone and dolomite, increased cost and difficulties in
solids handling acts as deterrents (Reid, 1970). The sulfur capture capabilities of
limestone and dolomite depend primarily on the different physical properties of their
calcined products, which are related to the crystal structure of the original rock.
Borgwardt and Harvey (1972) showed that the size of pores developed by calcination has
a critical effect on the rate and ultimate capacity for S02 sorption. Small pores result in
high reaction rates but if the particles are large, their sulfur retention capacity is low.
Conversely, large pores result in lower reaction rates but increased sulfur retention
capacities. Kullendorf et al. (1988) using two different limestones and one dolomite
determined the amount of sorbent required to achieve a specific S02 concentration.
Figure 10 shows the experimental results from the 40 MW CFB unit in Nykoping. The
results indicate that soft and porous limestone (Ignaberga) has larger sulfur capturing
capabilities than both crystalline limestone (Gasagruvan) and dolomite. The large
amount of dolomite required to achieve a certain degree of sulfur capture is due to its
lack of calcium oxide. As shown above it is the calcium oxide which is responsible for
reaction with sulfur dioxide. The large amount of magnesium oxide in dolomite is not as
efficient as CaO for capturing sulfur. Crystalline limestones upon calcination develops
a structure with very small pores and as a result, have lower sulfur retention capabilities
(Borgwardt and Harvey, 1972). The effectiveness of the soft limestone is not only due
to the porous structure but also due to the fact that it is structurally weak or 'soft'.
Because of the excellent gas-solid mixing in CFBCs, attrition of the soft limestone may
be considerable. A continuous break-down of the product layer surrounding the
unreacted core of the particle results in better limestone utilization. The effect of the
particle size has been investigated by Mjornell et al. (1991), Pickles et al. (1989), Basu
et al. (1989) and Kullendorf et al. (1988). Mjornell et al. (1991) found that fine limestone
393
ZOO T " - - - - - - - - - - - - ,
20 mgS/MJ
SO mgS/MJ 10.09IbSOZ/
II
10.221bSOZ/
MM8tv cl l'
Figure 10. Amount of different limestones or dolomites require to

desulfurize to various S02 concentrations in Karlskoga
boiler (Kullendorf et aI., 1988).
gave better sulfur retention than coarse particles, which contradicts the observations of
Pickles et al. (1989) and Kullendorf et al. (1988). One possible explanation for the
difference could be the type of limestone investigated. In the case of Mjomell et al.
(1991) the fine limestone had a crystalline pore structure, which enables it to withstand
a greater degree of abrasion and erosion before attrition occurs. In the case of the other
workers, the pore structure of the limestones investigated was not mentioned. However,
if the limestones were initially small and soft, attrition effects would further reduce the
size and cause the particles to escape the cyclone. Basu et al. (1989) noted that for
certain limestones there is a minimum size for achieving any sulfur retention. The effect
can be explained by the fact that the smaller the particle, the more surface area is exposed
for reaction. However, once all the surface area is exposed, further reduction in particle
size does not enhance sulfur capture.
Many studies have indicated the interaction between the use of sorbents and changes
in NOx emissions. For example, Valk et al. (1989) and Brown and Muzio (1991) have
shown that the higher the amount of limestone used, the greater the NO x emissions.
Figure 11 shows the effect of sorbent feed rate on NO x emissions for Colorado-Ute
Electric Association's 11O-MW CFB combustion unit at Nucla (Brown and Muzio, 1991).
The phenomena can be explained by the effect of limestone in catalyzing the fonnation
of NO x (Johnsson, 1989; Shimizu, 1990). Figure 12 shows the effect of sorbent feed rate
on N20 emissions in the same plant. As the figure shows, N20 emissions appear to be
independent of sorbent flow rate. An interesting observation has been noted by Senary
(1991). The use of dolomite sorbents in an atmospheric bubbling bed combustor resulted
394
in prolonged N02 emissions in the combustor than with various limestones. Since the
studies were performed with the same type of coal and CaO content, the effect can not
be attributed to the catalytic effect of CaO. Impurities such as iron and silicates in the
dolomite could explain the observed effect.
Clearly, further work is necessary to determine whether impurities are responsible for
the prolonged NOx emissions. The addition of limestone to a fluidized bed has no direct
measurable influence on the combustion of coal so that carbon loss is independent of
Ca/S ratio (Bonn and Richter, 1990). Because CO and CO2 are mostly dependent on
combustion, it is expected that sorbent addition will not cause any change in the quantity
of CO or CO2 emitted into the atmosphere. Further investigations are required to validate
the point.
260
Hue .. • ·50
III _
8U ..
..
Qo III .. _dCIIa
load: 110 MIN iii
250 .a
<i
.
02:3% ~
Bed Te".,.: 9210C 0
~ D ~
M
Nucla
• 30
2~0
@o @o
!!;
Cl.
. « .. II
::E
Q.
load: 110 MIN
~
"
0
230
D
~ .. • ~
0
20 02:3%
Bed T~~ 1121 oC
z
220 ~ II!D
OJ
C' !I!
10
210 +-~~-r--~-r-""--""-_---. a
o 2000 ~ooo 6000 8000 0 2000 ~ooo 6000 8000
Somen! Feed Rale (KglI,,) Soment Feed Rate (kglhr)
Figure 11. NOx versus sorbent Figure 12. N20 versus sorbent
feed rate. feed rate.
5.2. EFFECTS OF SOLIDS RECYCLE RATIO
The solids recycle ratio is defined as the ratio of solids circulated through the solids
recirculation leg to the amount of fresh solids entering the combustor. Hydrodynamic
studies of CFB units have revealed that the riser voidage varies both radially and axially.
The voidage profile describes the flow pattern of gas and solids, the degree of gas and
solid mixing, the heat and mass transfer rates and hence, conversion of any reactions in
the riser. Moreover, the hydrodynamic studies have shown that the voidage profile is
strongly dependent on the circulation rate. Consequently, it is expected that the solids
recirculation rate, or equivalently expressed in terms of the solids recycle ratio, can play
an important role in determining emissions from CFB combustors.
Various studies have been performed to evaluate the effect of solids recycle on the
quantity of emissions from the coal combustion process. Basu et al. (1989) and Saroff
et aI. (1989) showed that sulfur capture increases with recycle ratio. Figure 13 shows the
general relationship between sulfur retention and recycle ratio (Saroff et aI., 1989). For
a given CatS ratio the amount of sulfur retention increases dramatically at recycle ratios
between 0 and 1 and levels off at higher values. The observation can be attributed to the
395
residence time of the limestone particles in the combustor. At low recycle ratios (less
than 1.0), the amount of fresh unreacted limestone is greater than at higher recycle ratios.
At recycle ratios larger than 2, the majority of limestone has circulated around the
combustor many times and only a small fraction of limestone can still react with S02'
Basu et al. (1989) explained the increase in sulfur capture in terms of the bed density.
Initially, increases in bed density lead to increases in sulfur capture but after a certain bed
density the degree of sulfur retention levelled off. The argument presented above can also
be used to explain Basu et al.' s (1989) results. In order to increase the bed density the
recirculation rate must be increased, which leads to a corresponding increase in solids
residence time. After a certain increase in recirculation rate, the amount of limestone
available for reaction is very small if not negligible. As expected, greater Ca/S ratios,
indicating greater amounts of limestone resulted in a greater degree of sulfur retention.
The effect of recycle ratio on NOx emissions have been investigated
by Bramer and Valk (1991), Poersch et al. (1989) and Hiltunen and Tang (1988). Figure
14 shows the effect of CaO recirculation on NOx emission (Poersch et aI., 1989).
Although the experimental results are obtained from a bubbling bed combustor, similar
trends can be expected for CFB combustors. As previously mentioned, limestone is a
very important catalyst in NOx formation. The effect of recycle ratio on N20 and NO x
emissions, as determined by Bramer and Valk (1991) in a 1 MW bubbling bed combustor
is shown in Figure 15. The recycle ratio in this case is defined as the recycled cyclone
ash mass flow to the coal mass flow. The figure shows that fly ash recycling has
opposite effects on NOx and N20 emissions. NOx decreases with increases in fly ash
recirculation while N20 emissions increase with increases in fly ash recirculation.
,
.
NO
.• •
/
';3 /-
".
/
.? 92
/
~ 91 T'Y
;t 90 o CIIIS.5.4 /~
100
a c...s.3..2 T
.
89
.. c...s.2..7
88 T Anttvoc.il. 8
87 Anfhroot. A
88~O--~~L--L--~2---L--~3--~--~~
0 I
Il 15 % 20
Recycle Rale (Recycle/Coal Flow) CoO~oling
Figure 13. Sulfur retention versus Figure 14. NOx emissions versus
recycle rate for PFBC free CaO in recycle
with limestone ash
Increases in fly ash recirculation means that more char is available for reducing NOx' The
increases in N20 emissions can be attributed to the increased availability of char for
reaction. de Soete (1990) found that during char burning a small amount of the char-
small amount of the char-nitrogen is oxidized to N20. The rate of NzO formation is
396
roughly proportional to the rate of char combustion. Further evidence is provided

by Amand et al. (1991). They found that stopping fly ash-recirculation leads to
reduced N20 emissions but to an increased NO emission which suggests that N20 could
be formed from NO in the presence of fly ash. Instead of recycling solids, Hiltunen
- .. - EI-Cer - . - ilia war --6-- EI-Cer -- 0-- lIIawsr
N,O N,O NO, NO,
800
............
---
c
600 .............. -'. -'- '"
............
..
o -tr •• -.- ••• _••• -o
'iii
(I)
400 ····- •••6
'E ~.
Q)
.....
o· 200
zI
o 0
z" 0.0 0.5 1.0 1.5 2.0
recycle ratio [- J
Figure 15. NOx and N20 emissions versus recycle ratio for EI-Cerrejon
and Illawara coal; Primary air ratio = 1.2; Tbed = 825°C;
Ca/S = 1.5 (Bramer and Valk, 1991).
and Tang (1988) conducted experiments recycling flue gas. Figure 16 shows the effect
of recycled flue gas on NOx emissions in an Ahlstrom Pyroflow CFB combustor
while Figure 17 shows the effect of recycle ratio on combustion efficiency (Valk et aI.,
1989). As figure 17 indicates, increases in recycled flue gas leads to reductions in NO x
emissions. Recycling flue gas contributes to increased turbulence in the combustor
300
270
• British coal. 6S HW
o Petchora coal, 65 ,",W

2.0
""- o Ruhr Coali 30 !ofW
"""
210
,ao 30 MW
150
'20
90
60
~d3
rjJ ...
30
OOx concentraticn (dry basis) as lreaSured
8 12 16 20 24 28 32 36 40 44 48 \
Recycled flue gas/ccnbJsticn air
Figure 16. Effect of flue gas recycling on NOx emission

(15-25% excess air) (Hiltunen and Tang, 1988)
397
100
~
f
'0
95
5:~
90
fi
10
85
80
0.0 0.5 1.0 1.5 2.0 2.5
recycle ratio (-J
Figure 17. Effect of recyle ratio on combustion efficiency (Tbed = 825°C;
Ca/S = 4.5) (Valk et al. 1989)
and better gas-solid contact. The recycling of gas also tends to create an oxygen deficient
zone where the flue gas is reinjected in the combustor which promotes NOx reduction.
However, according to Hiltunen and Tang (1988), disadvantages of flue gas recycling
include a decrease in combustion efficiency and sulfur retention, and an increase in
combustor size, power consumption and costs. Combustion efficiency increases with
recycle ratio due to increased residence time of fuel particles in the bed. Consequently,
it is expected that CO emissions will be lower and CO2 emissions higher with higher
recycle ratios.
5.3. EFFECTS OF COAL COMPOSITION
The combustion behaviour of coal is determined by its structure and/or chemical

composition. The effect of coal structure has been found by Tsuboi and Iwasaki (1988)
and by Ishizuka et aI. (1988) to affect combustion efficiency. Figure 18 shows
combustion efficiency as a function of fuel ratio in an experimental CFB unit (Tsuboi and
Iwasaki, 1988). Fuel ratio is defined as the ratio of fixed carbon in weight percent to
volatile matter in weight percent. As fuel ratio increases, the combustion efficiency
decreases. Anthracite coal is an example of a coal with a high fuel ratio. Studies by
Poersch et aI. (1989) have shown that anthracite has a relatively dense structure similar
to that of graphite. The dense structure implies a high stability of bonds, which require
high temperatures (>900°C) for complete combustion. Moreover, Mulcahy and Smith
(1969) have indicated that small bituminous coal particles, which has a low fuel ratio
combust three to six times more rapidly than anthracite particles of a similar size. Figure
19 shows the difference in combustion efficiency between bituminous (low fuel ratio) and
anthracite (high fuel ratio) coal in an experimental CFB unit (Ishizuka et aI., 1988).
Coal structure and composition also affects the quantity of pollutants emitted from the
combustor. Without sorbent injection, the greater the sulfur content of a coal, the greater
the sulfur dioxide emissions. Carbon monoxide is a primary product of combustion
whose amount depends on the combustion efficiency.
398
• I'
100 100
~ • • COAL B
*
BITUMINOUS
80
>. ~
.,c
0
>.
"c
'u 60
•
.!!
:E..
;;: 'COALA
W I
••
Temper.ture 850·C 95 ANTI IRACITE
c
.~
OIl
40 .NO RECYCLE
C
.Q
~
•
"
.0
o RECYCLE FROM PRIMARY
CYCLONE "
.0
E
E 20 0
0 0
U 4RECYCLE FROM PRIMARY
& SECONDARY CYCLONES
0 90
0 2 3 0.4 0.6 0.8 1.0 1.2
Fuel Ratio (-) Primary air ratio
Figure 18. Relation between fuel Figure 19. Effect of primary air
ratio and combustion ratio on combustion
efficiency efficiency
The main impact of coal composition is on NOx emission. Generally, increases in fuel
ratio leads to a reduction in NOx emissions (Tsuboi and Iwasaki, 1988; Suzuki et aI.,
1990; Shimizu et al., 1990; Moritomi et aI., 1991). Figure 20 graphically shows the
relationship between NOx emissions as a function of fuel ratio for Ahlstrom pyroflow
boilers (Hyvarinen et aI., 1990). Coals with a low volatile content and hence a high fuel
ratio have a slow particle combustion rate. As a result, the amount of unbumt char in the
bed material is increased and accelerates NOx reduction, as discussed by 10hnsson (1989)
and Ishizuka et ai. (1988).
150,-------------,
~ 100
led T_row ... : 870 1:
so
o 10
f~el lotto (-)
Figure 20. Relation between NOx and fuel ratio (Hyvarinen et ai. 1990)
399
5.4. EFFECTS OF STAGED COMBUSTION
The main motivation behind staged combustion is the desire to decrease NOx emissions
by creating substoichiometric conditions in the lower regions of the combustor. Figures
21 and 22 illustrate the importance of staged combustion in reducing NOx emissions at
the CFBC Nucla plant (Brown and Muzio, 1991). As the figures indicate, without air
staging, the greater the excess air ratio the greater the emissions. Using a bubbling bed
combustor, Minchener and Kelsall (1990) studied the effect of secondary air injection
location and the percentage of the total combustion air added as secondary air. Their
studies indicated that higher secondary air injection locations and increases in the degree
of staging lead to larger NOx reduction. Using CFB combustors similar results were
obtained (Tsuboi and Iwasaki, 1988; Hiltunen and Tang, 1988).
70 3SO
~ ~
0 60 0
...11-
@
...11- 300
::E @
Co 50 ::IE
!':>
e:.
Q.
~ ~o
S
z:
250
30 200
2 3 ~ 5 6 2 3 ~ 5 6
Oxyv.n ("-enl, Oxygen (Pen>enl,
Figure 2l. N20 versus percentage Figure 22. NO x versus percentage

oxygen oxygen
Figure 23 shows the effect of staged combustion on NOx emissions in an Ahlstrom CFB
pilot plant (Hiltunen and Tang, 1988), with NOx emissions increasing with increases in
the % primary air. The data in Figure 23 is also plotted as a function of excess air levels
showing that at higher excess air levels, the reducing conditions created by staged
combustion is much more pronounced. Figure 24 shows the effect of secondary air
injection location on NOx emissions in the same Ahlstrom CFB pilot plant (Hiltunen and
Tang, 1988). The figure indicates that the higher the secondary injection location, the
greater is the reducing zone, where contact occurs between NO x and reducing char and
CO, and therefore the lower are the NO x emissions.
According to Hiltunen and Tang (1988), staged combustion is very effective for
medium-to-high volatile fuels, but less effective for low volatile fuels. When introduced
in the combustor the high volatile fuels quickly release the organically bound nitrogen in
the volatile matter. In these instances, the secondary injection point can be placed at
much lower locations.
400
200
150
100
Tbed ·861 - 874°C
Corrected to 7 , 0X)'geJl in dry flue gas
50 55 ~ 65 7075
'PriJauy air
Figure 23. Effects of air staging Figure 24. NO x emissions versus

on NOx emission location of secondary
air nozzles
Although staged combustion is good for reducing NO x emissions, recent studies have
shown reductions in sulfur retention efficiency, because of the oxygen deficient conditions
created by staged combustion (Beacon and Lundqvist, 1991; Khan and Gibbs, 1991). The
effect is attributed to a combination of lower oxygen concentration in the bed available
for the sulfation reaction and increased sulfur regeneration from CaS04 in the reducing
region of the bed. CO emissions do not appear to be affected by staged combustion.
Most of the CO formed in the reducing zone of the combustor combines with NOx in
reduction reactions. Any CO leftover is oxidized by the secondary air.
5.5. EFFECTS OF TEMPERATURE
Bed temperature plays a very important role in determining the amount and type of
emissions released from CFB combustors. Figure 25 shows how sulfur retention is
influenced by bed temperature, in the 40 MW CFB combustor unit in Nykoping, Sweden
(Lyngfelt and Leckner, 1989). For a constant inlet molar calcium-to-sulfur (Ca/S) ratio
the degree of sulfur retention increases up to 850°C but then decreases beyond that point.
It can also be seen that the higher the calcium-to-sulfur ratio, the greater the degree of
sulfur retention.
401
..
Z
100
.....6It1NC
00
:; ~ ~
~~t~
0 0"
.... ... ' 0 0
Z
.- .-
, 0
IIJ
....
W
a:
.~
50
a:
::>
:r
Q.
..J c./S04 ..
::>
Ul
X---~ c./S04
0
700 750 800 850 900
8EO TEMPERATURE C
Figure 25. Sulfur retention as a function of temperature at various

Ca/S molar ratios (Lyngfelt and Leckner, 1989)
Many theories have been proposed to explain the temperature dependence of sulfur
capture. They range from structure impairment theories, where the pore structure of the
limestone is altered by temperature, to theories involving oxygen depletion, which inhibits
sulfur capture. A review of the theories postulated for the temperature dependence of
sulfur capture is given by Lyngfelt and Leckner (1989). Because of the effect of sulfur
retention versus temperature, in order to maintain a certain S02 emission standard a
higher Ca/S ratio is required at higher bed temperatures. Figure 26 shows this effect
(Basak et aI., 1991). The existence of an optimum sulfur retention temperature is not
unique to CFB combustors but has also been reported by many investigators in bubbling
bed combustors (Bonn and Richter, 1990; Basu et aI., 1989, Lyngfelt and Leckner, 1989).
Typical sulfur retention results for a bubbling bed combustor are shown in Figure 27
(Lyngfelt and Leckner, 1989). In this case, the experimental data is from the 16 MW unit
at Chalmers University of Technology. It should be pointed out that the experimental
results shown in Figures 26 and 27 have been determined using the same type of coal and
limestone. A comparison of the figures indicates that the temperature behaviour of sulfur
capture in a bubbling bed combustor and a CFB combustor is very different. In bubbling
beds, sulfur retention drops off much faster than in CFB units. By extrapolating the
curves in Figure 27, it is evident sulfur retention decreases toward zero at temperatures
around 900°C, whereas with CFB units sulfur retention can still occur at much higher
temperatures. As mentioned by Lyngfelt and Leckner (1989), because of the differences
in observed temperature behaviour using the same limestone and coal type, the
temperature dependence can be attributed to the type of fluidized bed used. Possible
explanations for the observed behaviour include greater limestone retention time due to
solids recirculation, and a better distribution of oxygen in the reaction zone of CFB units.
The longer limestone stays in the combustor the greater the degree of sulfur capture
(Jonke et aI., 1972; Pickles et aI., 1989). Particles which have a short residence time are
usually not sulfated. Oxygen is required before the sulfation reaction can occur.
402
Investigations by Jonke et aI. (1972), Lyngfelt and Leckner (1989) and Khan and Gibbs
(1991) have shown that low oxygen levels in bubbling beds create reducing conditions
(e)
10. 126 1.1 871 8113 815 831
7
5 h ../ /
Cal5 •
// L
"V
3
2
. .
-I---- •
.~
/
•
1410 1520 1 seo 11100 ,..0 16eo 1720
_ Tempenot..,. (1')
50% !s FEED .,)'FEED LS 1:mo BdCED FEED
Figure 26. Ca}S requirements for different coal feed configurations

(S02 retention of 70±3% and 02 in flue gas at 3% vol.)
(Basak et aI., 1991)
.. 100
--- ~
-....... ~~_,I
z
0
~"~ ~.I
z
.......
a: SO
a:
~-'
j
r
o-i.........
CI.
oJ
j CtJ'S-t..
UI
ob
can-.
0
700 750 BOO 850 900
SED TEMPERATURE C
Figure 27. Sulfur retention as a function of temperature at various

Ca}S ratios in a AFBC (Lyngfelt and Leckner, 1989)
and act as inhibitor to sulfur retention. As previously mentioned, the greater degree of
mixing in CFBs cause considerable limestone attrition. This exposes unreacted limestone
and hence prolongs the possible sulfur retention.
Nitrogen oxides are also affected by temperature. The effect of temperature is
403
different for each type of nitrogen oxide. Figure 28 shows the effect of temperature on
nitrous oxide, while Figure 29 shows that on nitric oxide. The experimental data comes
from an experimental 8 MW unit built by Gotaverken Energy and involve three types of
coal (Amand and Andersson, 1989). As the figures indicate, for the three types of coal
tested an increase in bed temperature leads to a reduction in nitrous oxide emissions while
the opposite is true for nitric oxide. The effect can be attributed to the mechanisms
involved in forming the NOx species. Using a kinetic model based on 88 radical
reactions which occur in a homogeneous gas phase system, Amand and Andersson (1989)
showed that the relationship between N20 and bed temperature is due to the strong
influence of temperature on the rate of destruction of nitrous oxide by radicals in the gas
phase. The same reasoning can also be used to explain the difference in N20 emissions
with coal type. Coals with a high volatile content emit proportionally more gaseous
components in the devolatilization process. Consequently, the effect of the nitrous oxide
reduction reactions would be more pronounced compared to low volatile coals. The
relationship between nitric oxide and temperature for the low volatile coals can be
attributed to the char combustion rate. Unlike high volatile coals, nitrogen emission rate,
which is a function of char combustion rate, is much slower. Consequently, most of the
nitrogen compounds are released above the secondary air injection level where the greater
oxygen content contributes to increased oxidation of the nitrogen species. The higher
the bed temperature the greater the effect. In the case of brown coal the effect of
temperature on NO can be explained by examining the composition of the coal. lohnsson
(1989) and Moritomi et al. (1991) showed the importance of char in reducing NO. Brown
coal has a lower char content than either bituminous coal and petroleum coke.
"')
120 60
CITY 88
::E
"-
CITY 88
..,
~
0 100 ::E 50
N
Z "-
N
C>
e 0
80 Z 40
UJ
0 e'"
H
X
60 UJ 30
0 0
H
en 40
X
0
::> 20
0
cr u
~
H
I-
H 20 cr 10
Z I-
H
Z
0
780 820 860 900 820 860 900
BED TEMPERATURE C BED TEMPERATURE C
x BROWN COAL
x
o IIZTUN%NQU8 COAL.
o
BROWN COAL
e%TUM%NOUa COAL
• PeTROL.EUM COKE
.... PI!TROL.I!UN COKI!
Figure 28. Effect of bed temperature Figure 29. Effect of bed

on N20 emissions temperature on NO emissions
(Am and and Andersson, 1989) (Amand and Andersson, 1989)
The effect of temperature on CO at the Nucla CFB unit is shown in Figure 30 (Basak
404
et aI., 1991) with high temperatures leading to more efficient combustion which, in turn,
decreases the amount of CO fonned. The higher combustion efficiencies also lead to
increases in CO 2 emissions.
(C)
760 788 816 843 8tt
.
871 127 .55
200
180
160
140
. .
~
.
COppmv ~.
.: L'--- ... ..
(0 3'JI, 02) 120
..
.~
.
100
80
60
. .\:' .--_.....--
..
40
1400 1450 1500 1550 1800 1850 1700 1750
M•• n Bad Temperatura, F
I·~ ..... c-_-,,-,- •
Figure 30. Effect of bed temperature on CO emissions
(Basak et aI., 1991)
5.6. EFFECTS OF PRESSURE
Pressurized fluid bed combustors (PFBCs) have higher thennal efficiency and lower
investment costs than atmospheric units. Moreover, pressurized combustors can lead to
lower air pollutant emissions. Using a bubbling bed combustor, Boersma and Hein (1989)
showed that increases in operating pressure result in decreasing NOx emissions and Figure
31 is an example of their findings. As Figure 31 indicates, the lower the oxygen content
in the combustor, the greater the NO x reduction. The observation can be attributed to
enhanced reaction rates at higher pressures. The volatiles in the coal are released quicker
and have a greater chance to come into contact with reducing agents like char and
CaO. Studies by Wallman et aI. (1991) confirmed the increased importance of
heterogeneous reactions in NOx reduction at higher pressures. Figure 32 compares
the NOx and CO emissions at various levels of pressure and oxygen (Boersma and
Hein, 1989). Within a particular 02 range, increases in pressure lead to reductions
of both NO x and CO emissions. The results seem to suggest that the reduction of NOx
by CO becomes more important at higher pressures. However, as shown by Bonn and
Richter (1990), the reduction in CO at higher pressures only occurs with certain types of
coal. The effect of increased pressure on sulfur capture is not clear. Some investigators
have observed no sulfur capture at high pressures while others have noticed increased
sulfur retention. The different point of views may be due to the type of limestone
used in the experiments. As mentioned by Verweyen et al. (1991), impurities in the
limestone can either enhance or inhibit sulfur retention at high levels. Further studies are
required to establish the effect of operating pressure on sulfur retention.
405
2,5 bar 5 7,5
Figure 31. Influence of pressure Figure 32. Effect of pressure

on NOx emissions and oxygen levels on
NOx and CO.
6. Conclusions
A review and discussion of the strategies used to curtail environmentally damaging air
pollutants from the combustion of coal in circulating fluidized bed boilers has been
conducted. The analysis deals with the present knowledge of the coal combustion process
in CFBCs and the relationships between the combustion process, pollutant emissions and
reactor performance. In the face of progressively stricter environmental regulations being
implemented around the world, successful understanding and control of CFBC emissions
will require continued exchange of experimental data and technical information between
academic and industrial researchers.
7. References
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406
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Bonn, E. and E. Richter (1990), "Aspects of Coal Combustion in Atmospheric and
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Ehrlich, S. (1987), "Fluidized-Bed Combustion", in RA. Meyers (ed.), Encyclopedia of
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407
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KINETIC MODELING OF COMPLEX PROCESSES. THERMAL CRACKING AND
CATALYTIC HYDROCRACKING
G.F. FROMENT
Laboratorium voor Petrochemische Techniek
Rijksuniversiteit Gent
Krijgslaan 281, S5
B9000 Gent, Belgium.
ABSTRACT. A fundamental approach is outlined for the kinetic modeling of complex processes like
thermal cracking or catalytic hydrocracking of mixtures of hydrocarbons. The reaction networks are
written in terms of radical mechanisms in the first case and of carbenium ion mechanisms in the second
case. Since the elementary steps of the networks pertain to a relatively small number of classes, the
number of rate coefficients is kept within tractable limits. The reaction networks are generated by
computer through Boolean relation matrices. The number of continuity equations is limited by the
elimination of radicals or carbenium ions through the pseudo-steady-state approximation.
1. Introduction
One of the main problems the refining and petrochemical industry are facing is the accurate
simulation of processes involving complex reactions and complex feedstocks. In thermal
processes like naphtha cracking for olefins production or visbreaking, or in catalytic processes
like naphtha reforming, catalytic cracking of gas oil or hydrocracking of vacuum gas oil the same
questions arise. How to predict the conversion of the feedstock? What is the product
distribution in the effluent? Will it satisfy the quality specifications? In today's models the
actual reaction network is still often reduced either to a single overall reaction or to a simple
scheme involving a limited number of lumps only. The kinetic parameters of these models
inevitably depend upon the feed composition and even upon the type of reactor in which they
were determined. Product specifications cannot be predicted by such models and have to be
generated by empirical correlations linked to one or more of the lumps. Also, for each new
feedstock extensive experimentation is required.
The approach taken in this paper is completely opposite. It retains the full detail of the reaction
network of the individual components of the feedstock. The kinetics relate to the elementary
steps of the network and therefore the parameters are invariant, i.e. independent of the feedstock
composition. Since the elementary steps pertain to a limited number of types only, the number
of parameters is kept within tractable limits, even for the most complex mixture. The approach
will be illustrated by means of two examples: thermal cracking of naphtha for olefins production
and hydrocracking on zeolites.
409
410
2. Kinetic Modeling of Naphtha Cracking
2.1. LUMPED AND MOLECULAR MODELS
The thermal cracking of naphtha for olefins and aromatics production is carried out in long coils
in which the residence time is of the order of 0.4 seconds and in a temperature range 650-840"C.
The modeling of the cracking of a complex mixture like naphtha, containing more than 100
components, has gone over the years through increasing levels of complexity. Van Damme et
al (1981) provided an experimental data base that permitted an evaluation of various levels of
kinetic modeling. In the first level, naphtha was considered as one big lump, disappearing
through a first order reaction. Three naphthas were investigated. The rate coefficient varied
significantly with the feedstock composition. The next level of modeling considered three lumps
based upon the PIONA-analysis of the naphtha: normal and iso-paraffins and naphthenes. Olefins
are usually not present in the feedstock, while aromatics not only disappear but are also formed.
Each lump was converted through 1st order kinetics, but again, the rate parameters for the lumps
were found to be different for each of the three naphthas investigated, simply because the
composition of the lump was not the same for a light or a heavy naphtha.
A complete analysis of the naphtha using gas chromatography has become possible in recent
years. A number of typical components for normal and iso-paraffins and naphthenes were
selected and their disappearance was described through first order kinetics. Even with this
detailed breakdown some variation in the rate coefficient for a given component was observed
between the three naphthas" The variation can be traced back to the interaction between reacting
species, which cannot be accounted for through simple molecular disappearance kinetics. The
chemical environment in which a given component is cracked evidently depends upon the naphtha
composition.
None of the above models can predict the effluent composition. This requires sets of kinetic
equations describing the production of at least the main products, like methane, ethylene,
propylene, benzene etc. In the seventies this was attempted through molecular equivalents of the
real radical schemes, partly to limit the number of kinetic equations, partly to circumvent the
mathematical problems arising in the solution of sets of stiff differential equations associated with
rigorous radical models.
Today only kinetic models based upon individual components and the full reaction scheme can
satisfy the accuracy required by olefin producers and address questions related to the cracking
of feedstocks going from ethane to naphtha and even gas oil. These models account in detail for
the radical nature of thermal cracking (Ranzi et al (1983), Willems and Froment (1988». In the
following, these radical mechanisms will be briefly presented. The necessity for a reduction in
the number of parameters will be discussed. It will also be shown how to reduce the number of
differential equations and how to generate the complex reaction network by computer.
2.2. RADICAL MECHANISMS
The cracking process is decomposed into elementary steps reflecting its radical chemistry.
Radicals are produced by initiation. Taking propane cracking as an example, possible initiations
are:
(1)
C3HS - CH; + C2 H;
C3HS - H" + l-C3 H; (2)
411
The radicals then isomerize, interact with the molecules or decompose, depending upon their size
and nature.
When they interact with the molecules to abstract hydrogen they are said to behave as
(J-radicals, Rp:
(3)
The radical thus produced may isomerize, or it may decompose by C-C scission in (J-position
with respect to the free electron carrying C-atom:
(4)
(5)
A radical can also interact with an olefin or a diolefin produced in the process or present in the
feed by addition to a double bond:
(6)
Termination consumes the radicals, e.g. as follows:
CH; + CH; - CZ H6 (7)
CH; + CzH; - C3 Ha (8)
Paraffinic feed components or products disappear according to two parallel operating networks
consisting of:
- Initiation, radical isomerization and decomposition
- Hydrogen abstraction, radical isomerization and decomposition
The first network accounts for 5 to 10% only of the paraffin consumption.
Olefins and diolefins in the feed or produced by the reactions also disappear along the two
networks given above, including also mesomerization and cyclization. A third parallel route of
disappearance for the olefins consists of:
- Addition of radicals, isomerization and decomposition of the resulting radical.
Initiation of naphthenes is possible by scission in the ring, yielding a diradical with rearranges
into an olefin. Hydrogen abstraction in the ring and decomposition are also possible. Long side
chains evidently behave like paraffins or olefins.
Aromatics are not initiated below 900"C, but H-abstraction is possible. Phenyl radicals, thus
produced, are active chain carriers which lead to substituted and polycondensed aromatics.
Figure 1 shows the network for n-decane disappearance by initiation, radical isomerization and
decomposition. It contains 32 elementary steps. The isomerizations 19 -I 12 are identical to 15 - 18
and the decompositions Du - D l5 are identical to D6 - D IO • Therefore, only 23 rate coefficients
are required.
The reaction network of Figure 1 is not terminated yet, because some of the products might
still undergo further reactions. The other networks mentioned above for the n-decane
disappearance contain roughly the same number of parameters. It is clear that as such the use
of a radical model would lead to a number af rate coefficients too large to be determined
412
significantly from experimental results. The approach would not be realistic, unless the number
of pa:ameters were drastically reduced. This is feasible, without sacrificing the detailed
description of the reaction pathways, by a systematic scrutiny of the elementary steps and their
rate coefficients.
k2 /.~
Figure 1. n-Decane disappearance through initiation, radical isomerization and decomposition.
2.2.1. Reduction of the Number of Parameters. An initiation of the type represented by reaction
(1) can occur twice, that represented by reaction (2) six times. In other words an elementary step
like (1) consists of what may be called two single events, one like (2) of six single events. When
the rate coefficients are expressed in terms of these single events, values are derived from the
experimental data which are determined only by the nature of the C-atoms on the bond ruptured
in the initiation and this is reflected in the type of radicals produced. Consequently, the following
set of rate coefficients suffices to account for initiations in paraffins, regardless of their chain
length:
413
where the first rate coefficient e.g. refers to initiation by C-C-bond scission producing a primary
and a methyl radical. Figure 2 shows, by way of example, the types of C-C-scissions which may
occur simultaneously in the initiation of 2-methylpentane. The first type of initiation can happen
twice. The rate coefficients defined here relate to single events. Similarly, hydrogen abstraction
by a given radical from a C IO or from a C20-paraffin should not affect the single event rate
coefficient. What matters is the nature of the abstracting radical and that of the abstracted
hydrogen, Le. the strength of the C-H-bond. The strength of the C-H-bond decreases from
primary to tertiary.
The reduction of the number of parameters can be systematically pursued for the other types
of reactions encountered with paraffins and, of course, also for naphthenes and aromatics.
2:<r n (C-C) s,·,e

.,
,.. CH 3
IV\
kr n (C-C) ~ 5
~
./\ 1\
A.
kr n (C-C) pp
,.. \
k r n ( C- C) p :'; e
~ Jj + C:..:·
., ~
..J
Figure 2. Initiation of 2-methylpentane.
Further reduction of the number of independent kinetic parameters results from thermodynamic
constraints. Initiation and termination or decomposition and addition can be considered as
reversible reactions and their rate parameters are related through thermodynamics. Accounting
for these constraints allowed Willems and Froment (1988) to reduce the number of rate
parameters in their rigorous naphtha-cracking model from 140 to 68. This is a number that can
be significantly determined from a broad data base covering the cracking of various naphthas and
a number of specific components.
2.2.2. A Systematic Reduction of the Number of Species and Continuity Equations. If the kinetic
equations are to be tested against experimental data or used for predictive purposes they have to
be inserted into the continuity equations for the various species. It is clear from the preceding
that the set of continuity equations, which for all practical purposes are differential equations, is
very large. In addition, these differential equations contain large right hand sides and are not
414
linear, except for radicals with carbon number exceeding 5, which isomerize and decompose
faster than they abstract hydrogen and add to olefins. They behave as Wradicals only, subject
to monomolecular reactions, so that their continuity equations are linear. The concentration of
radicals in the reaction mixture is very low and does not change drastically along a tubular
reactor, once beyond the inlet zone. Therefore, the pseudo-steady-state approximation may be
applied, at least over increments of the reactor. The differential equations for the JL-radicals are
then further reduced to linear algebraic equations, from which the concentration of the Wradicals
can be calculated.
From Figure 1 it follows that the rate of disappearance of n-decane (M) can be written:
r (M) (9)
The net rate of formation of the 1-nonylradical CJLI) and that of the 5-nonylradical ~) can be
written:
(10)
(11)
If pseudo-stead y-state is satisfied:
o (12)
Equations (10) and (11) can then be solved to yield:
(k r , + k D,) k]
C
--;-;---:;-7-;.:;----';----,---;--:.. -
(k r , + k D,) (k r , + kD) - kr,kr, M (13)
CII, = (14)
(k r 1 + k D1 ) (k r 2 +kD)
2
- kr 1kr
;.1
CM
The concentrations of the other JL-radicals are derived in the same way. They can be written:
(15)
where F; is a ratio of sums and products of rate coefficients. F; is temperature-dependent.

The 1-nonylradical decomposes into ethylene and the 1-heptyl radical CJL'I). The rate of
decomposition of JLI can be written:
415
kDl (k I2 + k D2 ) kl (16)
(k r+ kD ) (k I + k D ) -
1 1 2 2
= kD,F1C M
where kDlF) is called a pseudo-rate coefficient (PRC) for the formation of ethylene out of
n-decane. But ethylene is also formed from other intermediate radicals, so that the PRC for its
formation is a sum of terms. The rates of formation of the olefins and the Cs'radicals are of the
form:
(17)
(18)
The disappearance of n-decane according to the scheme of Figure 1 can now be represented by
the single reaction:
(19)
The produced 1-olefins react further. Those with II.: ~ 6 are dealt with in separate networks of
the type of Figure 1. The oletins with II.: :s; 5 are also dealt with in a special subnetwork.
Similar derivations can be performed for the other networks of paraffins.
The PRC's are not strongly temperature-dependent. They can be calculated off-line for every
20'C in the interval encountered in the reactor and stored. This saves considerable computer time
in the integration of the continuity and energy equations.
The scheme for the cracking of naphtha, containing some 200 components, consists of some
120000 elementary steps:
873 initiations, 105000 H-abstractions, 34 H- and 34 CH3-additions, 10000 decompositions, 3000
isomerizations, 250 mesomerizations and 250 C-H-scissions.
Evidently, these reaction schemes cannot be generated manually. Clymans and Froment
(1984), Hillewaert et al (1988) devised a method for the computer generation of reaction
networks based upon Boolean relation matrices.
2.2.3. Computer-Generation of Reaction Schemes. The structure of hydrocarbons can be

represented in a Boolean matrix.
Row 1 indicates connections between the atoms numbered 1 and 2, 1 and 6, 1 and 7. The
vector A expresses which C-atoms are part of the aromatic ring. The number of l's on a row
reveals whether a C-atom is primary, secondary, tertiary or quaternary. The description of an
416
olefin requires, in addition, a vector Q indicating which C-atoms are part of the double bond.
Figure 3 represents the Boolean relation matrix for n-butylbenzene.
679
5~1
810
4~2
3
lie 1 2 3 4 5 6 7 8 9 10
r
10100011000 lr 1
2 1010000000
3 0101000000
4 0010100000
.\1 = 5 0001010000 /\ 5:
6 1000100000
7 1000000100 7/ 0
S' 0
S 0000001010
Jo
90000000101
10 LOOOOOOOO 1 0
Id 0 L
Figure 3. The Boolean relation matrix for n-butylbenzene.
Initiation is derived from the non-zero elements of the matrix above the diagonal. Initiation by
scission of the bond between the carbon atoms 6 and 7 in n-decane, e.g. leads to:
6 8 2 4 06 9 07
~+~
3 1 3 5 I) 8
The matrix M is reduced to M' by setting the elements ~7
101000000001 0 ] 00000000
II0IOOOOO[)[)1 1010000000
10101000000 [ 0]01000000
1001010000°1 00]0]00000
H =IOOOJOJOOOOI 'H' = 0001010000
'--- 10000]01000 ,'--- i 0000] 000,00 I
100000]0100 10000000100j
,000000]010 10000001010
10000000]OJ
LoOOOOOOO]oJ l
o 0 0 0 000 ] 0 1
00000000] 0
and m76 zero and leads to 2 matrices representing the radicals produced by the initiation. The
location of the free electron is given by a number:
417
1 [010000
~ = if'HHj,
2101000
~l = 3 0 I 0 100
4001010 , KRADPl = 6, 2 KRADP2 = 7
5 1 000101 10 0010
6 L000010
Decomposition of a radical by is-scission is given by the matrix Mq e.g. for the I-hexylradical:
2 4 6 2 4 6
o~
1 3 5 1
-::/ +o~
3 5
01 0000 rOOlOOO
101000 000100
[
o 1 0 100 2 100010
!j = 0 0 1 0 1 0 ' KRADP= I, M - I 010001'
000 I 0 1 001000
l000010 000100
The elements m23 and m32 in M are set zero and M is split into 2 submatrices
1-5-isomerizations are identified from
The cracking simulation model developed by the Laboratorium voor Petrochemische Techniek
contains 1680 reaction networks for some 550 hydrocarbons. The components involved in the
model are normal and iso-paraffins and olefins up to Czs , 5- and 6-ring naphthenes up to C:n and
aromatics up to Cw. The computation of the reaction networks for the heavy components
requires many hours.
3. Kinetic Modeling of Catalytic Hydrocracking
3.1. LUMPED SCHEMES
The second example deals with the hydro isomerization and hydrocracking of hydrocarbons on
418
aPt-loaded ultrastable Y-zeolite, encountered in the second stage of a vacuum gas oil
hydro cracking process.
Various relatively crude lumped reaction schemes were presented in the literature. Vazquez
et aI (1988) described the hydrocracking of n-heptane in terms of a set of parallel reactions.
Steijns and Froment (1981) and Baltanas et aI (1983) described the hydroisomerization and
hydrocracking of Cg, C IO and C 12-paraffins in terms of the following scheme:
(20)
A "'MB "'MTB - CR
where A represents a normal paraffin, MB the lumped monobranched isoparaffins, MTB the
multibranched isoparaffins and CR the lumped cracked products. The rate equations were based
upon the bifunctional character of the catalyst, with (de)hydrogenation taking place on the metal
and the rate determining isomerization and cracking on the acid sites. Physisorption inside the
zeolite cages was also accounted for. The rate coefficients for the various steps of the reaction
scheme (20) were found to increase with the number of carbon atoms in the paraffins. The
physisorption coefficient of the feed paraffin reached an asymptotic value from n-decane onwards.
3.2. A FUNDAMENTAL APPROACH
3.2.1. Carbenium Ion Mechanisms. Although the above kinetic modeling goes quite a way
beyond what is usually done, it is clear that extrapolation of the rate parameters to higher
paraffins is still hazardous, so that further experimentation is required, in particular for mixtures.
Also, the kinetic modeling of complex mixtures would require an overwhelming number of
parameters if the effluent composition were to be predicted with some degree of accuracy.
Again, as for thermal cracking, the reaction network was developed in far greater detail, down
to the elementary steps (Baltanas et aI (1989); Froment (1991)). After physisorption in the zeolite
cage paraffins are dehydrogenated on the Pt. The resulting olefin is protonated on the Bmnsted
acid sites into a carbenium ion, e.g.
/VVV
The latter then isomerizes, through hydride- and alkyl shifts along the chain, e.g.
or through a protonated cyclopropane PCP-intermediate, into a branched carbenium ion

419
Cracking occurs through the scission of a C-C-bond in is-position with respect to the carbon atom
bearing the positive charge, yielding a shorter carbenium ion and an olefin which can be
hydrogenated on the Pt and desorb as a paraffin.
Similar steps occur with naphthenes, but in addition ring expansion and contraction are
possible, also through PCP-mechanisms.
Hydrocracking of aromatics starts with hydrogenation into naphthenes.
Written in terms of the above elementary steps, hydro isomerization and hydro cracking lead to
extremely large networks. For mixtures the task of developing such networks manually becomes
overwhelming. Again, as for thermal cracking, computer generation of the networks is a
necessity for the elementary step approach (Baltanas and Froment (1985)).
It is clear that here too the rate coefficients have to be related to some elementary steps,
encountered over and again in the multitude of reactions making up the reaction networks. These
elementary steps are the protonation and deprotonation, the hydride- and alkyl shifts and PCP-
isomerization, the ring contraction and expansion, and the is-scission illustrated above.
Since the rate determining steps take place on the acid sites the dehydrogenation and
hydrogenation on Pt are in quasi-equilibrium, so that the olefins can be related to the paraffins
(normal and iso) through thermodynamic equilibria, without requiring any additional kinetic
parameter.
The n-octane reaction network consists of 383 elementary chemical steps (52 hydride shifts of
the 1.2- and 36 of the 1.3-type, 24 methyl shifts, 96 PCP branching isomerizations, 15
is-scissions, 75 protonations and 85 deprotonations) involving 14 octanes, 5 paraffinic and 9
olefinic cracking products, 49 octenes, 42 octyl carbenium ions and 6 carbenium ions with a
smaller carbon number, disregarding the methyl- and primary carbenium ions, which are known
to be less stable. There is, however, no need to consider 383 rate coefficients, since the
elementary chemical steps belong to only 6 types when no distinction is made between 1.2 and
1.3 hydride shifts. Yet, since the values of rate coefficients depend upon the structure of the
reactant and the product, the true number of parameters depends upon the detail of the structure
accounted for in the modeling.
An illustration of the need for introducing structural aspects of the species involved in the
reactions and not just the type of reaction, is encountered, e.g. in the methyl-shift from the
2-methyl-3-heptyl carbenium ion to the 3-methyl-2-heptyl carbenium ion, two secondary
420
carbenium ions. In the forward direction two methyl groups can shift, in the reverse direction
only one. Different values would be derived for the elementary rate coefficient of a methyl shift
between two secondary carbenium ions, depending upon the structure of the reacting carbenium.
To avoid this, a further refinement of the rate coefficients is necessary. For this purpose Baltanas
et al (1989) introduced the concept of single event rate coefficients. Elementary chemical steps
may consist of a number of identical single events. The number of these, n., is related to the
symmetry changes associated with the formation of the activated complex out of the reactant:
in which Ur and u. are the global symmetry numbers of the reactant and activated complex. The
rate coefficient of the elementary step is a multiple of the single event rate coefficient. It is the
latter which is used in the following.
3.2.2. The Number of Single Event Rate Coefficients. Assuming that the rates of hydride shift
and methyl shift do not depend upon the number of C-atoms in a chain, but only on the type of
carbenium ions involved (secondary or tertiary), the following single event rate coefficients are
retained for the isomerizations,
by hydride shift:
kHS(S;s);kHS(t;s);kHS(S;t);kHS(t;t)
by methyl shift:
kMS(S;s);kMS(t;s);kMS(S;t);kMS(t;t)
by PCP-isomerization:
kpcp(s;s );kpcp(t;s) ;kpcp(s ;t) ;kpcp(t;t)
Assuming a planar structure for the activated complex, very similar to that of the olefin, leads
to single event rate coefficients for protonation independent of the olefin, so that only two values
have to be retained: kp.(s) and kPr(t).
Such a simplification is not justified in deprotonation. To reduce the number of rate
coefficients of deprotonation, thermodynamic constraints have to be accounted for. In the
sequence consisting of protonation of an olefin, 01> isomerization of the resulting carbenium ion
by elementary steps involving one type of carbenium ion, and deprotonation of the isomer
carbenium ion into an olefin, O2 the isomerization equilibrium relation
k De (Si0 2 )
kpr (02i s) (21)
has to be satisfied. Since the protonation rate coefficients were assumed to depend only on the
nature of the carbenium ion, equation (21) reduces to:
421
(22)
where m stands for s or t and 0, for a reference olefin isomer with the double bond in such a
position that both a secondary and a tertiary carbenium ion can be formed by protonation.
It follows from (22) that there are only two independent deprotonation rate coefficients per
carbon number. This reduces their total number in the hydro isomerization and hydrocracking
of n-octane, e.g. from 85 to 7.
Thermodynamic relations also reduce the number of rate coefficients for cracking by iJ-scission,
so that the total number of rate coefficients for n-octane hydro isomerization and hydrocracking
is reduced to 17 only. This is a number that allows meaningful parameter values to be
determined from experimental data. It is clear also from the preceding that the set of single event
rate coefficients determined in this way, is valid for the hydroisomerization and hydrocracking
of any paraffin, whatever its chain length, provided, of course, there are no diffusional limitations
or configurational constraints.
Deriving the single event rate coefficients from experimental data requires the rates to be
expressed in terms of observables. Baltanas et al (1989) and Froment (1991) derived the
following equation for the rate of formation of a paraffin:
(23)
The index R + U is an abbreviation of either R + kl.ml or R + kl.m2, i~. carbenium ions with a longer
chain than those appearing inside the first summation. In (23) k = o.k.
The concentrations of R +ij.ml and R +ij.m2 are eliminated through the pseudo-steady-state
approximation for the carbenium ions and CH + through a balance on the total number of active
sites.
The approach outlined here is easily extended to aromatics and naphthenes, without significant
increase in the number of parameters.
3.2.3. Complex Feedstocks. Rate Coefficients/or Lumped Schemes. Feedstocks for hydrocrackers
are complex mixtures of hydrocarbons with a wide range of molecular weights and carbon
numbers extending, e.g., from 15 to 33. A combination of high pressure liquid chromatography,
HPLC, and GC-MS permits an individual identification and quantification of all the normal
paraffins, but for the iso-paraffins an identification beyond the carbon number is not or only
partly possible. Mono-, di-, tri-naphthenes and -aromatics can be separated per C-number.
Further insight may be obtained from High Resolution Mass Spectrometry and 13C NMR
spectrometry. Nevertheless, pending further progress in analytical or separation techniques, a
certain amount of lumping cannot be avoided in the kinetic modeling. The rate of disappearance
of feedstock lumps can be constructed from that of its components using the single event
approach outlined here, but this evidently requires the composition of the lump. Liguras and
Allen (1989) were confronted with this vicious circle in their kinetic modeling on the catalytic
cracking of vacuum gas oil. It was practically impossible to define unique compositions for the
422
lumps, but, fortunately, no significant differences in the predicted product distributions were
observed when the lumps were sufficiently detailed and did not span more than one C-number.
Conclusion
The present paper has outlined an approach for the detailed kinetic modeling of both thermal
cracking and catalytic hydrocracking. The parallelism between the two cases is remarkable.
Expressing the rate equations in terms of elementary steps and single events of either radical -
or carbenium ion chemistry keeps the number of rate parameters within practical limits. The
approach should stimulate the commitment of oil and petrochemical companies to the
improvement and refinement of their analytical means.
Nomenclature
11 vector indicating aromatic carbons

Cr cracking
Ci concentration of species i (kmollm3 or kmol/kg",J
Q vector indicating carbons bearing double bond
De deprotonation
H- hydrogen radical
HS hydride shift
k single event rate coefficient (lis)
k elementary step rate coefficient (lis)
K equilibrium constant
kcr(m;n) single event rate coefficient for l1-scission of a carbenium ion of type m to a
carbenium ion of type n and an olefin (lis)
single event rate coefficient for deprotonation of a carbenium ion of type m to
olefin Oij (lis)
single event rate coefficient for initiation of a carbon carbon bond, forming type
m and n radical (m,n = Me, p, s, t) (lis)
ku.o(m;n) single event rate coefficient for isomerization (iso = HS, MS or PCP) of a
carbenium ion of type m to a carbenium ion of type n (m,n = s,t) (lis)
kp,(m) single event rate coefficient for protonation of an olefin to a carbenium ion of type
m (k~/(kmol.s))
m type of carbenium ion, either s or t
M molecular species
M Boolean relation matrix
Me methyl radical
MS methyl shift
n. number of single events
Q Boolean relation matrix of olefin
Oij olefin related to Pi
OJ olefin
P primary radical
PCP PCP branching
Pi paraffin
423
Pr protonation
PRC pseudo-rate coefficient (1/s)
r reaction rate (kmolJ(m3. s»
.R Boolean relation matrix of radical
Rij,ml + carbenium ion related to Pi and Oij
Rl p>-radical
RPi rate of formation of paraffin Pi (kmolJkgcat,S)
S secondary radical or carbenium ion
t tertiary radical or carbenium ion
(J global symmetry number
;r. activated complex
LIST OF REFERENCES
Baltanas M.A" Vans ina H, and Froment G,F, (1983) 'Hydroisoimerization and
Hydrocracking', 5, 'Kinetic Analysis of Rate Data for n-Octane', Ind, Eng, Chern, Prod, Res,
Dev, 22, 531-539,
Baltanas M,A, and Froment G.F. (1985) 'Computer Generation of Reaction Networks and
Calculation of Product Distribution in the Hydroisomerization and Hydrocracking of Paraffins
on Pt-Containing Bi-functional Catalysts', Comp, Chern, Eng, 9, 1, 71-81.
Baltanas M.A., Van Raemdonck KK, Froment G.F. and Mohedas S.R. (1989) 'Fundamental
Kinetic Modeling of Hydroisomerization and Hydrocracking on Noble-Metal-Loaded Faujasites,
1. Rate Parameters for Hydroisomerization', Ind. Eng. Chern. Res. 28, 899-910.
Clymans P.J. and Froment G.F. (1984) 'Computer Generation of Reaction Paths and Rate
Equations in the Thermal Cracking of Normal and Branched Paraffins', Compo Chern. Eng.
8,2, 137-142.
Froment G.F. (1991) 'Kinetic Modeling of Complex Catalytic Reactions', Revue de 1'l.F.P., 46,
491.
Hillewaert L.P., Dierickx J.L. and Froment G.F. (1988) 'Computer Generation of Reaction
Schemes and Rate Equations for Thermal Cracking', A,LCh.E. J. 34, 1, 17-24,
Liguras D.K and Allen D.l. (1989) 'Structural Models for Catalytic Cracking, 2. Reactions of
Simulated Oil Mixtures' Ind. Eng. Chern, Res. 28, 674-683.
Ranzi S., Dente M., Pierucci S. and Biardi G. (1983) 'Initial Product Distribution from Pyrolysis
of Normal and Branched Paraffins', Ind. Eng. Chern. Fundam. 22, 132-139.
Steijns M. and Froment G.F. (1981) 'Hydro isomerization and Hydrocracking. 3. Kinetic Analysis
of Rate Data for n-Decane and n-Dodecane', Ind. Eng. Chern. Prod. Res. Dev, 20, 660-668.
Van Damme P.S., Froment G.F. and Balthasar W.B. (1981) 'Scaling Up of Naphtha Cracking
Coils', Ind. Eng. Chern. Process Des. Dev. 20, 366-376.
Vazquez M.L, Escardino A. and Ancejo A. (1988) 'Hydrocracking of n-Heptane with a
NiO-MoOiHY Ultrastable Zeolite as Catalyst. The Network of the Reaction', Ind. Eng.
Chern. Res. 27, 2039-2043.
Vynckier E. and Froment G.F. (1991) 'Modeling of the Kinetics of Complex Processes based
upon Elementary Steps' in 'Kinetic and Thermodynamic Lumping of Multicomponent
Mixtures', Eds. S.l. Sandler & G. Astarita, Elsevier.
Willems P.A. and Froment G.F. (1988) 'Kinetic Modeling of the Thermal Cracking of
Hydrocarbons. 1. Calculation of Frequency Factors', Ind. Eng. Chern, Res. 27, 1959-1966,
424
Willems P.A. and Froment G.F. (1988) 'Kinetic Modeling of the Thermal Cracking of
Hydrocarbons. 2. Calculation of Activation Energies', Ind. Eng. Chern. Res. 27,1966-1971.
ENGINEERING OF HYDROTREATING PROCESSES
P. TRAMBOUZE
Institut Fram;ais du Petrole
69390-So1aize
France
ABSTRACT. A general ovetview of hydrotreating and hydrocracking processes is given, considering

chemistry, catalysts and technologies. The environmental qualities of the fuels produced are especially
taken into consideration when comparing these processes.
1. Introduction
The terms hydrotreating and hydroprocessing are used rather loosely for designating processes
in which various operations such as hydrodesulfurization, hydrocracking and hydrogenation occur
more or less simultaneously. The common characteristics of these various processes is that a
hydrocarbon cut is contacted with hydrogen under pressure in the presence of a heterogeneous
catalyst. However, the following distinction is generally made between hydrotreating and
hydrocracking:
Hydrotreating refers to a relatively mild operation whose primary purpose is to saturate
olefins and/or reduce sulfur and nitrogen content without changing too much the boiling range
of the feed. Hydrotreating is applied to a wide range of feedstocks from naphtha to reduced
crude oil. If the process is used specifically for sulfur removal, it is usually called
hydrodesulfurization or HDS.
Hydrocracking refers to processes whose primary purpose is to modify the boiling range
of the feed and convert it to lighter products (with boiling ranges lower than that of the feed).
In addition to these two broad classes of processes, there also exist some applications of
hydrotreatment more specifically oriented toward a given goal, such as the manufacture of lube-
oils or waxes, the reduction of aromatic compounds in middle distillates or the selective
hydrogenation of pyrolysis products. In this presentation we shall focus our attention on
Hydrotreating and Hydrocracking.
These processes have been developed for a long time, but their industrial applications have been
growing rapidly during the last ten years due to the great evolution of the markets for oil
products:
reduction of the demand for heavy products such as heating oils,
large increase in the share of the demand for light products, especially middle distillates
(diesel oil and jet fuel).
To cope with this fundamental evolution of the markets, the world refining industry has had
to implement, within their processing schemes, heavy oil and residues conversion. In this
respect, hydrotreating and hydrocracking processes are certainly the best suited for the situation.
425
H.I. de Lasa et al. (eds.), Chemical Reactor Technology for Environmentally Safe Reactors alld Products, 425-442.
426
Additionally, more constraints will be put on the refinery by more stringent environmental
regulations on the products and the processes. The removal of sulfur is already an absolute
necessity. Again, hydrotreating processes are certainly the only ones able to lead to products
meeting the existing as well as future specifications.
2. Chemical Reactions [Gary et al, 1984; Dufresne, 1989; Le Page et al, 1987]
2.1. HYDROTREATING
The main hydrotreating reaction is that of desulfurization, but many others take place
simultaneously to various degrees, such as denitrogenation, various hydrogenations and
hydrocracking (in some cases deoxidation and dehalogenation) (see Table 1).
Table 1. Main chemical reactions involved in the hydrotreating process.
1. Desulfurization
a. Mercaptans RSH + H2 ----> RH + H2S
b. Sulfides RI-S-R2 + 2 H2 ----> RIH +R2H + H2S
c. Disulfides RI-S-S-R2 + 3 H2 ----> RIH + R2H + 2 H2S
d. Thiophenes C4I-4S + 4 H2 ----> C~lO + H2S
2. Denitrogenation
a. Pyrrole C4I-4 NH + 4 H2 ----> C~lO + NH3
b. Pyridine CsHsN + 5 H2 ----> CSH12 + NH3
3. Hydrogenation CnH2n+2 + H2 ----> CnH2n+2
4. Hydrocracking
(n=m+p)
Many kinetic models have been proposed for the description of hydrodesulfurization reactions
[Le Page et al, 1987]. A first-order kinetic law is generally accepted for hydrogen as well as for
a single sulfur compound. For actual feedstocks, since the number of the different existing sulfur
compounds is quite large, a lumping of all these molecules into a single one leads to an
approximate second order (between l.5 and 2). Furthermore, it has been observed that H2S
inhibits the reaction and that the overall activation energy is of the order of 100 kJ/mol.
Nitrogen removal requires more severe operating conditions than does desulfurization. Lower-
boiling compounds are desulfurized more easily than higher-boiling ones. The difficulty of sulfur
removal increases in the following order: paraffins, naphthenes and aromatics.
All these reactions are exothermic, the heat of reaction being roughly proportional to the
chemical hydrogen consumption.
In the case of residue treatment, metals (nickel, vanadium and iron) removal occurs
simultaneously with the depositing of solid material on the catalytic surface. The consequence
of this metal deposit is the irreversible deactivation of the catalyst.
427
2.2. HYDROCRACKING
Hundreds of simultaneous chemical reactions occur in hydrocracking. Roughly speaking, the

mechanism of hydrocracking may be considered as catalytic cracking with hydrogenation
superimposed. Catalytic cracking is the scission of a carbon-carbon single bond and
hydrogenation is the addition of hydrogen to a carbon-carbon double bond (see Table 2).
Table 2. Hydrocracking Reactions [Gary et ai, 1984; Dufresne, 1989; Le Page et

ai, 1987]
Bifunctional mechanism of hydrocracking
H A A
nP ~nO ~nC+ • iC+
~VUA
(P+O) iO
P:Paraffin
O:Olefin
n:Normal
Cracked i:lsomerised
Products C+:Carbenium Ion
iP
Hydrocracking of Aromatics
R'
~A
~ t +2H2
R'
IOCJOl R
+ +4 H 2
These reactions proceed essentially through a bifunctional mechanism involving two types of
catalytic sites: hydro-dehydrogenating sites and acidic sites. A saturated hydrocarbon (paraffin
428
or naphthene) is first converted to an olefin on a hydro-dehydrogenating site and moves to an

acidic site. There it is chemisorbed as a carbocation. This cation can undergo various reactions,
such as rearrangement and cleavage, and finally desorbs from the acidic site as an olefin. In the
case of cracking, two fragments are desorbed, one being paraffinic, the other olefinic. The olefin
then moves to a hydrogenation site to take up hydrogen. Cracking and hydrogenation are
therefore complementary. The overall reaction actually provides an excess of heat.
Another reaction that occurs and illustrates the complementary operation of the hydrogenation
and cracking reactions is the initial hydrogenation of a condensed aromatic compound to a
cycloparaffin. This allows subsequent cracking to proceed to a greater extent and thus converts
a low-value component of catalytic cycle oils to a more valuable product.
It is important to keep in mind that the hydrogenation of aromatics is thermodynamically
limited; it is favoured by high hydrogen pressure and low temperature. Moreover, the heavier
the molecule, the more unfavourable is the thermodynamic equilibrium constant. The kinetics
of hydrogenation depends on the type of molecule. Polyaromatic structures are more easily
hydrogenated than light ones, if the thermodynamic conditions are satisfied.
The effect of hydrogen partial pressure on the various hydrotreating reactions (HDS, HDN,
HDA) is quite different from one reaction to another. HDS is much less sensitive to hydrogen
pressure than the two other reactions. Due to thermodynamic constraints, HDN and HDA
require a minimum hydrogen pressure. The two reactions are nevertheless essential in the overall
process and the operating pressure is often chosen by considering the performance of
denitrogenation.
The kinetics of paraffin and naphthene isomerization or cracking can be described by a
mathematical equation in which the hydrogen pressure is in the denominator. This would mean
that the rate decreases when hydrogen pressure increases. However, the reverse effect is
observed for heavy feedstocks. This can be explained by considering all the reactions taking
place simultaneously, especially the HDN and HDA reactions, and by knowing that the acidic
sites of the catalyst are very sensitive to nitrogen and heavy aromatic compounds.
Hydroisomerization reactions are generally intimately associated with hydrocracking reactions.
The overall scheme is rather complex. It involves the independent action of both types of
catalytic sites and the existence of a transport mechanism for olefins between these sites.
Therefore, the catalyst must be designed according to this bifunctional mechanism. The relative
strength of the hydro-dehydrogenation and acidic components must be adjusted for the desired
operation.
3. Catalysts [Dufresne, 1989; Trimm et ai, 1989; Le Page et al, 1987]
3.1. HYDROTREATING
The catalysts developed for hydrotreating include cobalt, molybdenum, nickel, vanadium and
tungsten oxides on alumina. Cobalt and molybdenum oxides on alumina catalysts are in greater
use today, being highly selective, easy to regenerate and relatively resistant to poisons.
If the removal of nitrogen is also important, catalysts composed of nickel-cobalt-molybdenum
or nickel-molybdenum compounds on alumina are generally used. Nickel-molybdenum catalysts
have a higher hydrogenation activity than cobalt-molybdenum, leading to a greater saturation of
aromatic rings at the same operating conditions.
For heavy feedstocks internal diffusion limitations are generally observed. This is particularly
important for residue demetallization, with the final result being pore mouth plugging due to the
429
preferential deposit of metals on the external part of the catalyst peJlet. As a consequence,
catalyst pore size and particle size must be chosen accordingly for a given feedstock [Toulhoat
et al, 1990].
3.2. HYDROCRACKING
There are a number of hydrocracking catalysts available; they are generally tailored to the
process, the feed material and the products desired. Most of these catalysts consist of a mixture
of silica-alumina with a small, uniformly-distributed amount of metals. The silica-alumina
portion, amorphous or crystalline, provides the cracking activity while the metals promote
hydrogenation. The main types of hydro-dehydrogenation components are mixed metal sulfides
and noble metals. The main noble metal used is palladium (less than 1 weight %); it is used
preferably with zeolite as the acidic component.
Noble metals are strongly inhibited by sulfur compounds and unable to promote any
hydrotreatment reactions; consequently they must be associated with a hydrotreatment catalyst.
In most cases it is preferable to use an association of metals such as nickel-molybdenum or
nickel-tungsten, which are more sulfur resistant. These catalysts need to be presulfided, because
the metals are active in the sulfided state.
The acidic function of hydrocracking catalysts can be provided by various solid acids such as
amorphous silica-alumina, zeolites and doped alumina. The type of application dictates the nature
of the acidic component. Hydrocracking catalysts designed for the production of naphtha require
strong acidity, provided by zeolites (Y-zeolite). For special applications, such as dewaxing,
where shape-selective reactions must be promoted, zeolites such as ZSM-5 and mordenite are
used.
Hydrocracking catalysts designed for a maximum production of jet fuel or gas oil utilize a
moderate acidic function, made of modified zeolite or amorphous silica-alumina. Doped alumina,
essentially by fluorine, can also be used for these applications.
3.3. SIZE AND SHAPE OF CATALYST PARTICLES
Along with the increasing activity of catalysts, it has been necessary to reduce the size of the
particles in order to reduce as much as possible the negative effect of intraparticle diffusion.
Presently, commercial catalysts are offered for hydrotreating and hydrocracking processes under
various forms. There are cylindrical extrudates or more complex shapes such as cloverleaf
extrudates and sometimes spheres. The nominal size (diameter) varies from 0.8 to 1.5mm for
extrudates and from 2 to 4mm for spheres. The bulk specific gravity varies roughly from 0.5
to 0.75; dense packing loading techniques are more and more frequently used for loading the
catalyst into the reactors. Internal porosity is between 0.5 and 0.75. Crushing strength is also
an important characteristic of the catalyst, especially for moving bed or ebullated bed processes,
for which it becomes of prime importance to have values as high as possible.
Using small size catalyst particles can bring some detrimental effects such as high pressure drop
in reactors or even bed plugging. The most common instances of these are due to the presence
of particulate material in the feed stream. This problem can be avoided if particular attention is
given to crude oil desalting and feed filtering operations. The major plugging component is iron
sulfide formed by decomposition of iron soluble compounds (generally naphthenates) present in
some feedstocks. A guard reactor is especially useful in this respect.
430
3.4. REGENERATION AND DISPOSAL [Trimm et al, 1990)
Catalysts may be deactivated as a result of fouling by coke or inorganic deposits, by chemical

poisoning, sintering and phase transformation. When a fresh hydrotreating catalyst is put into
operation, there is a rapid accumulation of coke. This coking is accompanied by fairly rapid
deactivation. After a certain time of operation, the coking and catalyst deactivation rates
decrease. Accumulation of metals on the surface does not lead to complete loss of activity, since
both Ni and V are slightly active in sulfide forms.
Coke can be removed by combustion. Therefore, regeneration of catalysts have hydrotreated
feeds with low metal contents is generally performed. However, the regeneration conditions must
be carefully controlled, particularly with respect to temperature, in order to avoid phase changes
or sintering. More and more these regenerations are performed off-site, and catalysts are
presulfided before being reloaded into the reactors.
Spent catalysts, after hydrotreating of residues, contain combinations of Co, Ni, Mo and W,
supported on alumina and contaminated by coke, V, Ni and Fe. Regeneration is generally not
performed, and these spent catalysts are discarded. Some studies have shown that a partial
rejuvenation of these catalysts is possible by leaching of fouling metals [Trimm et al, 1990).
Sometimes unloading operation can be difficult due to agglomeration of the catalyst particles;
this is more often experienced with guard reactors.
The disposal of spent hydrotreating catalysts is not an insignificant problem. This may involve
recovery of metals for environmental and/or economic reasons. Solutions to this problem still
have to be imprOVed upon, especially in reducing the cost of the operation. The amounts of
catalyst involved are large and will increase rapidly in the coming years.
4. Technologies [Gary et ai, 1984; Trimm et ai, 1990; Le Page et ai, 1990; Mohanty et al, 1990)
4.1. HYDROTREATING
Although there are about thirty hydrotreating processes available for licensing, most of them have
essentially the same process flow for a given application. Figure 1 illustrates a typical
hydrotreating unit.
Off·Gas
H•• 'er Reactor
~<--l~
-I sOUl7f Wat., I
MP I-~
Steam t
Wild Naphtha
~
F,..h feed
I
i~
SourWa'..
,.....-.4-...L...'--ir~· C
oJ To Second
51...
I Recyc ..
Compre.lor
Figure 1. Typical Scheme of a Hydrotreating Unit.

431
The oil feed is mixed with hydrogen-rich gas and then preheated to the proper reactor inlet
temperature. The combined feed (oil + hydrogen) enters the top of the fixed bed reactor, called
a trickle-bed reactor. Generally the catalyst bed is divided into several beds, which are separated
by quenching zones where cold hydrogen-rich streams are injected in order to control the
temperature inside the reactor. The catalytic beds are adiabatic and therefore temperature
increases along each bed since the reactions are exothermic.
The reactor effluent is cooled before the oil is separated from the hydrogen-rich gas. The oil
is stripped to remove H2S, NH 3 , and light hydrocarbons produced by the various reactions. The
gas is treated to remove H2S and NH3 , before being recycled to the reactor as quench gas.
The main problem encountered in designing this type of reactor is the distribution of gas and
liquid phases at the top of the reactor, in order to obtain a good contact between the reactants and
the catalyst. The distributors (Figure 2) must be carefully designed and a sufficiently high linear
velocity of the phases is necessary in order to have a high interaction flow regime.
Gas + LiqUId
++
liquId
Distributor plate
50 to 60 hole.
per m2
Figure 2. Internal arrangements of a catalyst bed crossed by a two-phase flow.
Typical data concerning the hydrotreating of an FCC gas-oil cut (LCO) are given in Table 3.
A gradual increase in processing severity, first shown by an in an increase in hydrogen partial
pressure, with the other conditions remaining the same (Cases 2 and 3), and then an increase in
temperature (Case 4), brings about the almost complete hydrogenolysis of the sulfur and nitrogen
compounds, as well as a deeper hydrogenation of polyaromatics.
However, the cetane number is not greatly improved, due to the small amount of paraffinic
compounds present in the feedstock. More severe operating conditions are needed (Case 5) to
perform hydrodecyclization reactions and further mono aromatics hydrogenation.
432
Table 3. Hydrodesulfurization of a light cycle-oil. Temperature and space velocity

identical for the three cases. Taken from [Billon et al, 1987]
Feed Case I Case 2 Case 3 Case 4 Case 5

Hydrogen Pressure P 1.5 P 2.5 P 2.5 P 2.5 P
Temperature T T T T+20 T+20
LHSV V V V V V/4
Hydrogen Consumption 180 230 270 290 410
HDS% 93.0 96.4 98.3 >99 >99
HDN% 75.0 98.3 >99.5 >99.5 >99.5
Sulfur wt% 2.33 0.18 0.09 0.04 0.02 <0.003
Nitrogen ppm 53.0 10.0 1.0 3 <2 <1
Cetane Number <20 22 24 28 29 40
Aromatics wt% 87.3 80.0 75.0 65.3 54.0 26.0
Polyaromatics wt% 32.3 12.0 6.0 4.6 4.9 1.7
4.2. RESIDUE HYDROTREATING
With the first commercial residue hydrotreating plant being built in Japan in the late 70s, several
units for direct residue HDS have been planned and constructed (Kuwait, for example).
Residue hydrotreating in fixed-bed reactors is similar to heavy distillates hydrotreating, used
as a feed preparation step for conversion processes (FCC or hydrocracking). The main
application of the process is the removal of impurities such as sulfur, nitrogen and metals. In
addition to this, the process provides partial conversion of the residue feedstock of up to 35wt%
of the feed.
Recent progress in catalyst technology has made residue hydrotreating a viable route to lighter
products with sufficient flexibility to handle a wide range of feeds. Several processes are offered
by various process licensors with varying degrees of industrial achievement [Timm et al, 1990;
Le Page et al, 1987; Billon et al, 1991; Reynolds et al, 1989].
Due to the rapid deactivation of catalyst as a consequence of metal deposit, the technology
needs to be adapted. When conventional fixed beds are used, a first reactor is used as a guard
reactor to protect the catalyst in the subsequent reactors (Figure 3). Generally, the guard reactor
is operated as a swing reactor, with frequent replacement of the catalyst, which is rapidly
poisoned or even plugged by metals and suspended solid deposits. Therefore, it is of great
importance to perform extensive desalting and fine filtering of the feed before it enters the
hydrotreating unit.
Typical data concerning the hydrotreatment of a vacuum residue are given in Table 4.
Other technologies have been proposed in order to overcome the difficulties linked to metals
deposit. Moving bed processes have been developed to continuously replace the catalyst. Shell
has developed the bunker flow reactor, operating concurrently. This technique can be used for
hydrodemetallization as well as for residue hydroconversion (HCON process).
Elf, IFP and Total formed the ASVAHL association for heavy oil upgrading in early 1980 with
the objective of developing processes for residue conversion. Several schemes and processes
were experimented at a 20,000 t/year scale. Among these processes [Le Page et al, 1990; Billon
et al, 1991; Euzen, 1991], a dual fixed bed version (HYVAHL) and a countercurrent moving bed
system have been developed (see Figure 4).
433
HOS
HOM D..ullurlzallon
Demel.JUzalion. Conversion Retlnlnq
Swing
R.Klors
II
FEED
.... ldu.
To
Fracllonallon
Sec1lon
Figure 3. Hyvahl-F process. Reaction section.
Table 4. Hydrotreating of a Vacuum Residue (Iranian Heavy) HYVAHL Process-

Data taken from [Billon et ai, 1991]
Typical Material Balance

(Wt%)
H2S + NH3 3.3
CI-C4 3.0
Gasoline 3.7
Gas oil 19.5
Vacuum Gas oil 34.2
Vacuum Residue 38.0
TOTAL 101.7
Characteristics
FEED GAS OIL ATM. RESIDUE
Specific Gravity 1.025 0.86 0.960
Sulfur (wt%) 3.28 0.03 0.50
Nitrogen (ppm) 7700 800
Viscosity (1()()0C) 2460 cSt 55 cSt
Ni + V (ppm) 505 46
Cetane Index 43
434
FRESH CATALYST
U]~
aoo.I-'---<><JI>O------ G.O. LP
MAKE UP
CATALY~
G.QHP
Figure 4. Catalyst Circulation for Countercurrent Moving Bed Operation.
Chevron also developed a moving bed technology, the OCR (onstream catalyst replacement)
process, with a countercurrent movement of catalyst and feed [Reynolds et ai, 1989]. The
countercurrent mode of operation has been proven to be the most favourable for minimizing the
consumption of catalyst (see Figure 5). The oil with the highest metals content contacts the
dirtiest catalyst, and then this catalyst with the highest metals contaminants is withdrawn.
Cocurrent
6 Moving Bed ...........
Plus Fixed Bed
Relative Catalyst,
Consumptlonl
Vol of Feed 4
2
Countercurrent
"
__
Moving Bed
Plus Fixed Bed
o~--~--~--------~--~ ~
o 100 200 300 400 500 600
Feed Metals, ppm NI + V
Figure 5. Comparison of Catalyst Consumption for Various Technologies.
435
As for residue hydrocracking, and if high conversion is desired, the ebullated bed system, as
in the H-oil and LC-fining processes, is also a proven technology (see Figure 6). The process
can be utilized either for desulfurization at low conversion or for high conversion in the
hydrocracking mode. To achieve conversion above 60-65%, two reactor stages are needed; the
first stage achieves demetallization-desulfurization and the second stage provides conversion. To
achieve more than 85% conversion a third reactor is needed.
WillE -UP H1 HP SEPARArORS HP SEPARAtOR

(aWPAr o;'jOR HiGH MEO cOw
AlAe IOM5 TEMP TEMP f [ ... p
,--'--_____ r--.----,---- puRr.f
OFF GAS
CATALYST
ADDITION
~1 HE AYE"
HED
CATAl.YST
,-------------
H,
W.THO"AWAL
ri~\H
OIL HEATER
PROOUClS
Figure 6. LC-fining Expanded Bed Hydroprocessing Unit.
As shown in Figure 7, the hydrogen-rich gas and the oil are heated to the required temperatures
and then mixed in a specially designed mixer, before being fed into the bottom of the reactor
through specially designed spargers. The reactor is a back-mixed isothermal reactor. At the
bottom of the reactor, the feed and gas mixture is mixed with the ebullating fluid in a special
pump (EP). The mixture is then passed through a grid into the reactor chamber, which contains
the catalyst. One of the main advantages of this system is the possibility of adding fresh catalyst
and withdrawing spent catalyst. However, due to the intense backmixing in the reactor, the
catalyst withdrawn is a mixture of catalyst particles present in the reactor without any segregation
between fresh and used catalyst.
Ebullating reactors are generally operated at a higher temperature than fixed bed ones, in order
to compensate for the loss of conversion due to backmixing. As a consequence, the quality of
the products, especially that of diesel oil, is slightly lower [Radsdale et ai, 1991]. Data
concerning the H-oil process are given in Table 5.
436
CATALYST
AOol TION
EFFLUENT
EXPANDED
CATALYST
SED
...
FEED 'OIL
HYDROGEN
CATALYST RECYCLE Pu MP
WITHQRAWAL
Figure 7. Expanded or Ebullated Bed Reactor
Table 5. Hydrotreating of a Vacuum Residue (Arabian Light + Heavy) H-OIL

Process - Data taken from [Ragsdale et aI, 1991]

(Wt%)
H2S + NH3 4.95
CI-C4 20.27
Gas oil 24.09
Vacuum Gas oil 34.99
Vacuum Residue 9.91
TafAL 102.64
Characteristics
FEED GAS OIL ATM. RESIDUE
Specific Gravity 0.988 0.86 0.970
Sulfur (wt%) 4.25 0.42 1.90
Nitrogen (ppm) 2600 1150 3500
Ni + V (ppm) 111 60
Cetane Index 41
Aromatics (Wt%) 47
CANMET hydro cracking and VEBA Combi-Cracking processes are presently demonstrated.
Both processes use the same concept of liquid-phase hydrogenation of the feed and of gas phase
437
hydrogenation of the products. Slurry phase operation has been developed as a solution for the
requirement of a highly dispersed catalyst in which particles act as nuclei for metal deposition.
Problems encountered in this type of operation include difficult separation of the solids from the
liquids and uncertainties concerning the scale-up rules and designing of large plants.
High residue conversion levels up to 95 wt%, and an on-stream factor of around 87% with high
quality products have been reported [Trimm et al, 1990]. A special additive is used in the
CANMET process to suppress coke formation and obtain higher conversion.
4.3. HYDROCRACKING
The process is either single-stage or two-stage (Figures 8 and 9). In the latter case (Figure 9),
there is a first step with one or several reactors, followed by a fractionation section, where the
H2S and HN3 are removed together with lighter cuts. The unconverted fraction is fed to a second
stage which involves one or more reactors containing hydrocracking catalysts. This scheme is
the most efficient and flexible, but also the most expensive configuration.
The single-stage process (Figure 8) consists of one or several reactors in series without any
inter-stage product removal. Thus products such as H2S and NH3 are carried through the
hydrocracking catalyst beds and cause partial inhibition of active sites. The unconverted cut
separated by fractionation can be recycled to the reactors or used as a feed for other processes
(lube manufacture, steam-cracking, catalytic cracking). Zeolite catalysts, which are more
resistant to ammonia poisoning than amorphous silica-alumina, have made this cheaper
configuration even more attractive.
To Amine Unit
LPG
Stripper
Gasoline
Karas ne
G II
HP
Separator
,...._-.1 ------------------------------------~--"Q_"'-----'A;.::e:.:::.:.:::ld"'ue
'--__tit)
Hydrogen
Figure 8. Single Step Hydrocracking. Residue Recycle at 2nd Reactor.

438
To Amine Umt
~i
Topper
LPG
"~~."~ ,~~J---~--------------'
Figure 9. Two-step Hydrocracking
It is known that, when heavy feedstocks such as heavy vacuum gas oil are processed
simultaneously with all the hydrocracking reactions, heavy polynuclear aromatics are formed.
These compounds are concentrated in the heaviest fraction of the effluent; they have a detrimental
effect on the activity of the catalyst and on its life. For an operation with recycling for complete
conversion, these heavy polynuclear aromatics accumulate in the liquid recycle stream causing
fouling and rapid deactivation of the catalyst. A solution often practised is to accept a slight
reduction in conversion by purging part of the liquid recycle stream; catalyst activity and stability
are thereby improved.
Table 6 gives typical data concerning a two-step hydrocracking operation.
4.4. MILD HYDROCRACKING
Mild hydro cracking is quite different from conventional hydrocracking. This rather new process
is actually an intermediate between hydrotreating and hydrocracking. Due to the decreasing
demand for low-sulfur fuel oil and the shortage of middle distillates, it appears attractive to
modify already existing hydrotreating plants in order to produce more middle distillates. The
operating conditions remain the same (relatively low hydrogen pressure, between 30 and 45 bars).
The catalyst however is different, generally with Co-Mo on alumina being replaced, at least
partly, by Ni-Mo on a more acidic carrier. The more acidic support can be doped alumina or
silica-alumina.
439
Table 6. Two-step Hydrocracking of Heavy Vacuum Gas Oil. IFP Process - Case
of maximum middle distillates production.

(Wt%)
H2S + NH3 2.75
C 1 + C2 0.47
C3 + C4 3.45
Light Naphtha 6.50
Heavy Naphtha 9.10
Jet Fuel 35.20
Diesel Oil 45.13
Residue Purge o
TOTAL 102.70
Characteristics
FEED (HVGO)
Sulfur, wt% 2.38
Nitrogen, ppm 1600
LIGHT NAPHTHA
Sulfur, ppm <1
Nitrogen, ppm <1
REAVY NAPHTHA
Sulfur, ppm <1
Nitrogen, ppm <1
PIN/A, wt % 49/47/5
JET FUEL
Sulfur, ppm <5
Nitrogen, ppm <5
Smoke point, mm 29
Freezing point, °C <-60
DIESEL OIL
Sulfur, ppm <5
Nitrogen, ppm <5
Cetane number 63
Pour point, °C -12
Aromatics, vol % 12
5. Process Variables
5.1. DISTILLATE HYDROTREATING
The principal operating variables are temperature, hydrogen partial pressure and space velocity.
Increasing temperature and hydrogen partial pressure accelerate all the reactions and increases
hydrogen consumption. Increasing pressure also increases hydrogen saturation and reduces coke
formation.
440
Typical ranges of process variables in distillate hydrotreating operations are:

Temperature: 31O-440°C
Total pressure: 20-100 bar
Space velocity (LHSV): 1-8m3/m 3 .h
Hydrogen recycle: 6O-400m3/m 3
Hydrogen consumption: 20-1OOm3/m 3
5.2. RESIDUE HYDROTREATING
When dealing with residues, the operating conditions must be more severe. The temperature at
the inlet of the reactors varies along the cycle in order to compensate for the deactivation of the
catalyst, generally between 380 and 4400C. The space velocity is greatly reduced (0.3 to 1.0)
since the rates of the various reactions (HDS, HDN and HDM) are much smaller than the same
rates observed with lighter products.
The relative completion of the various reactions depends greatly on the type of catalyst used.
For example:
with a Co-Mo type catalyst, almost complete hydrodesulfurization can be achieved;
removal of metals reaches 60% and denitrogenation is between 40 and 50% [Trimm et al, 1990].
with a combination of HDM and HDS type catalysts, demetallization and desulfurization
can both be performed at around 90% [Billon et aI, 1991].
The temperature has quite a marked influence on the HDM/HDS activity ratio [Reynolds et aI,
1989]. At lower temperature, HDM is favoured compared to HDS; this behaviour might be
explained by considering the intragranular diffusion limitation of the demetallization reaction.
The total pressure must be high, generally greater than 120 bar.
For residue treatment, an important economic factor is the lifetime of the catalyst. Even with
a guard chamber to protect the main reactors, the catalyst can rarely process more than 5000 tons
of feed per ton. Of course, the lifetime of the catalyst is directly related to the type of feed
processed and inversely proportional to its metal content. For a feedstock containing more than
400 ppm of metals (Maya crude, for example), if a demetallization level of 60% is achieved, the
deposit of metals on the catalyst will be 240kg (counted as metal) per ton of catalyst after an on-
stream time corresponding to lOOOm3/ton.
For this reason, great efforts have been undertaken to tailor catalysts for demetallization and
offering large pore volume and a large proportion of macropores [Toulhoat et al, 1990]. For
example, catalysts with 30 to 40% of their total porosity as macropores greater than 100
nanometers are nearly 50% more active in HDM than catalysts having similar specific areas with
similar average micropore diameters. We have already mentioned that the demetallization
reaction is diffusion limited; the incorporation of macropores or "access channels" in the catalyst
makes for an increase in the effective diffusivity of large molecules containing metal atoms.
5.3. HYDROCRACKING
The severity of the hydrocracking reaction is measured by the degree of conversion of the feed
to lighter products. Conversion is generally defined as the weight percent of the feed which
disappears to form products boiling below the desired product end point. As for hydrotreating,
the primary reaction variables are reactor temperature and pressure, space velocity, and hydrogen
consumption; furthermore, the nitrogen content of the feed and the hydrogen sulfide content of
the gases are of some importance.
441
Temperature: reactor temperature is the primary means of conversion control. At normal

reactor conditions, a 15°C increase in temperature almost doubles the reaction rate constant. As
the run progresses, it is necessary to raise the temperature to compensate for loss of catalyst
activity.
Reactor pressure: an increase in total pressure increases the partial pressure of both
hydrogen and ammonia. Conversion is enhanced by increasing hydrogen partial pressure and is
lowered by increasing ammonia partial pressure. The hydrogen effect is greater than the
ammonia one, and the net effect of raising total pressure is to increase conversion.
Space velocity: space velocity varies directly with feed flowrate. As the feed rate
increases, conversion is lowered.
Nitrogen content: the hydrocracking catalyst is deactivated by contact with organic
nitrogen compounds. Therefore, an increase in the organic nitrogen content of the feed causes
a decrease in conversion.
Hydrogen sulfide: at low concentrations the presence of HzS acts as an inhibitor of the
hydrogenation of aromatic rings.
The selection of the catalysts is of prime importance and must be made according to the
characteristics of the feed, the process scheme and the operating conditions and product
specifications. One of the keys of catalyst design is the balance between the two association of
different hydrotreating and hydro cracking catalysts.
6. Conclusion
Market trends will continue to dictate long-term emphasis on the conversion of heavier oil
feedstocks in order to produce clean distillates. For the coming years, not only conventional
crude oil residues will be treated, but other sources of hydrocarbons will also become more and
more important, such as heavy crudes, tar sand bitumen, shale oils or coal liquids. As a
consequence, flexibility in processing schemes must be a major design consideration. In this
respect, the hydroconversion processes appear to be the most flexible tool able to produce the
good-quality fuels needed by the market and to be adapted to changes in crude supplies. Stricter
specifications to be met by diesel oils in the future (less sulfur, less nitrogen, less aromatics,
lower final boiling point, reduction of gums, etc.) imply an increase in high severity hydrotreater
and hydrocracker capacities.
Another application of the hydrocracking process could become important during the next
decade, when the transformation of natural gas into liquid fuels is considered to be economically
feasible. In a route going via the manufacture of synthesis gas and the production of heavy
paraffins by Fischer-Tropsch synthesis, a hydrocracking operation could be the final step in order
to produce a high quality diesel engine fuel.
Hydrotreating processes have been markedly improved during the last 30 years, and as the
front-end technology for heavy feed upgrading they will continue to undergo changes in order
to enlarge their technical possibilities and improve their economic profitability.
As in recent years, improvements may be expected from various sources:
Catalysts: new zeolites, improved texture, combination of different catalyst types,
regeneration or rejuvenation techniques, disposal of spent catalysts;
Reactor: the simplest technology, the fixed bed reactor, will certainly be favoured, but
improvements concerning distributor design, use of guard or swing reactors, implementation of
graded bed with several catalyst types and sizes could be looked for. Other technologies such
as moving bed, ebullating bed or slurry type system should also be considered for new and more
442
refractory feedstocks, since they certainly offer a greater potential for improvement and
adaptation.
Process schemes and auxiliary operations: as already done, the coupling of several
complementary processes or steps will remain essential, and the overall economics may thereby
be greatly improved. Preliminary treatments such as filtration and desalting should also be
improved due to their growing importance, especially if fixed bed systems are used. The
availability of cheaper hydrogen is also a key factor in the overall cost of all upgrading
technologies.
References
Books:
Dufresne,P., (1989), Distillate Hydrocracking. Seminar 'Acid Catalysis in Refining and
Petrochemistry', Lisbon, June 6-9, 1989.
Gary,J.H. and Handwerk, G.E., (1984), Petroleum Refining: Technology and Economics.
Second Edition. Marcel Dekker, Inc. New-York and Basel.
Le Page,J.F. and coworkers, (1987). Applied Heterogeneous Catalysis. Editions Technip,
Paris, 1987.
Le Page,J.F., Chatila,S.G. and Davidson,M., (1990), Raffinage et conversion des Produits
Lourds (in French). Editions Technip, Paris, 1990.
Trimm,D.L., Akashah,S., Absi-Halabi,M. and Bishara,A. (editors), (1990). Catalysts in
Petroleum Refining 1989. Proceedings of the Conference on Catalysts in Petroleum
Refining. Kuwait, March 5-8, 1989. Elsevier Amsterdam.
Journal Articles:
Bachtel,R.W., Kramer,D.C., Scheuerman,G.L., Stangeland,B.E., and Yuan,S., (1990),
'Onstream catalyst replacement: a breakthrough in residuum processing'. Paper
presented at the Japan Petroleum Institute Petroleum Refining Conference, Tokyo,
October 18-19, 1990.
Billon,A., Heinrich,G. and Quignard,A., (1987), 'Hydrotreating of Middle and Vacuum
Distillates from Coking and FCC'. Hydrocarbon Technology International, P.Harrison
ed. p67-72. Sterling Publications Ltd., London, 1987.
Billon,A., Peries,J.P., Espeillac,M. and Des Courieres,T., (1991), 'Hyvahl F versus Hyvahl
M, swing reactor or moving bed'. NPRA Meeting, USA, 1991.
Euzen,J.P., (1991), 'Moving-bed process for residue hydrotreating'. Revue de l'Institut
Fran~ais du Petroie. Vol 46, N°4, July-August 1991.
Mohanty,S., Kunzru,D. and Saraf,D.N., (1990), 'Hydrocracking: a review'. Fuel, Vol 69,
December 1990, 1467-1473.
Ragsdale,R. and Widsom,L.I., (1991), 'Sequential Operation of H-Oil and Resid FCC'.
Paper presented at the A.I. Ch.E. Meeting, Houston, April 7-11, 1991.
Reynolds,B.E., Johnson,D.R., Lasher,J.S. and Hung,C., (1989), 'Heavy Oil Upgrading for
the Future: the New Chevron Hydrotreating Process Increases Flexibility'. Paper
presented at the NPRA Meeting, San Francisco, March 19-21, 1989.
Toulhoat,H., Szymanski,R. and Plumail,J.C., (1990), 'Interrelations between Initial Pore
Structure, Morphology and Distribution of Accumulated Deposits, and Lifetimes of
Hydrodemetallisation Catalysts'. Catalysis Today, Vol. 7, 1990,531-568.
THERMAL SENSITIVITY AND RUNAWAY
IN CHEMICAL REACTING SYSTEMS
G. CAO and M. MORBIDELLI A.VARMA

Dipartimento di Ingegneria Department of Chemical
Chimica e Materiali Engineering
Universita' di Cagliari University of Notre Dame
Piazza d' Anni Notre Dame, IN 46556
09123 Cagliari, Italy USA
ABSTRACT. The sensitivity behavior of various chemical reacting systems, including homogeneous and
catalytic reactors as well as explosive systems, is analyzed. A generalized sensitivity criterion is illustrated.
It defines the boundary between sensitive and non sensitive behavior as the location, in the relevant
parameter space, where the normalized sensitivity of an appropriate output variable with respect to any
input variable of the system exhibits a maximum. This criterion can be applied to any reacting system,
regardless of the existence of temperature profiles, thus bringing together, with respect to their sensitivity
behavior, seemingly different chemically reacting systems. The reliability of the sensitivity criterion is
defined by comparison with the experimental behavior of some reacting systems.
1. Introduction
In general, a chemical reacting system is said to operate in the region of parametric sensitivity
or thermal runaway when, for a given small change of one of the input variables, the system
undergoes a large variation in the output conditions. This concept was first introduced in the
context of chemical reactors, by Bilous and Amundson (1965), with specific reference to
nonadiabatic nonisothermal tubular reactors, where one or more exothermic reactions take place.
These reactors are characterized by the occurrence of a maximum in the temperature profile,
often referred to as a "hot-spot", whose magnitude is taken as an index for reactor runaway.
Specifically, under parametric sensitivity conditions, for small changes in the inlet conditions the
temperature maximum increases dramatically, leading to unsafe operating conditions as well as
possible changes in catalyst activity (i.e. deactivation mainly through sintering) and in process
performance (i.e. occurrence of undesired side reactions). Thus, it is convenient to be able to
identify a priori the regions corresponding to safe operation and those corresponding to runaway.
Suitable criteria, mostly originated in the context of thermal explosion theory [cf. Semenov
(1928); Zeldovich et al. (1985)], have been adopted in chemical reactor theory to identify the
nature of reactor behavior. These are based on a definition of runaway in mathematical terms
which allows us to identify in the reactor parameter space the boundary separating runaway and
nonrunaway operating conditions. Most of these criteria are based on some geometrical
characteristic of the temperature profile in the system. In particular, in the context of thermal
explosion (cf. the batch system considered in the classical Semenov problem) we refer to the
temperature profile in time, while in the case of tubular reactors we refer to the temperature
profile along the reactor axis.
443
444
A more general approach has been recently developed [Lacey (1983); Boddington et al. (1983);
Morbidelli and Varma (1988)] based on the rigorous definition of sensitivity of the system
behavior to its operating conditions. Such criterion provides estimates of the runaway region
boundaries which are in close agreement with those given by earlier criteria. However, this
criterion can be applied to any reacting system, including situations where no temperature profile
can be defined (cf. the non adiabatic nonisothermal CSTR) as well as isothermal systems where
earlier criteria cannot be used.
We will analyze the sensitivity behavior of various reacting systems and identify through the
generalized criterion mentioned above a unique feature which brings together the sensitivity
behavior of all such systems. From a practical point of view, such a unifying concept can be
used to evaluate the boundary of the runaway region for each reacting system in the relevant
parameter space. In particular, the sensitivity behavior of homogeneous and catalytic tubular
reactors is first analyzed using appropriate models. Thus, in the case of catalytic reactors,
heterogeneous models are considered. The analysis of chemical reactor models is then completed
by applying the generalized sensitivity criterion to the case of a single n-th order irreversible
exothermic reaction occurring in a nonisothermal nonadiabatic CSTR.
We then proceed to analyze reacting systems involving more complex reaction schemes, such
as the homogeneous combustion reaction between hydrogen and oxygen. The sensitivity behavior
of such a system is analyzed through a detailed kinetic model by considering the sensitivity of
both the maximum temperature and the maximum concentration of the radical species responsible
for carrying out the reaction. Since the runaway of this system actually corresponds to its
explosion, it is possible to verify the reliability of the sensitivity criterion by comparing the
predicted runaway region boundaries with the ignition limits measured experimentally.
2. Parametric Sensitivity Criteria
A clear understandig of the characteristics of the various parametric sensitivity criteria reported
in the literature can be best achieved by considering the following simple model, describing the
temperature - conversion phase plane behavior of a pseudohomogeneous plug-flow reactor, where
an exothermic irreversible n-th order reaction occurs [c.f. Morbidelli and Varma (1988)]:
(1)
with ICs: v = vi at X = 0, where the wall temperature has been taken as reference temperature,
To' By simply changing the definition of some of the involved dimensionless parameters, the
same eq. (1) describes the thermal explosion process in a homogeneous batch reactor. More
complex heterogeneous models [cf. Froment and Bishoff (1979); Doraiswamy and Sharma
(1984)] should be used to simulate catalytic reactors operating close to the region of parametric
sensitivity. The response of the homogeneous model above is reliable only when slow chemical
reaction occurs, thus well outside the region of parametric sensitivity.
Apart form the pioneering works by Bilous and Amundson (1956) and Barkelew (1959), the
criteria for parametric sensitivity mostly used in practice have been developed by Thomas and
Bowes (1961) and Adler and Enig (1964) in the context of thermal explosions. Runaway was
defined to occur when the temperature profile exibits a region with positive second-order
derivative somewhere before the hot-spot, in the temperature-time or temperature-conversion
445
planes. A comparison between the two criteria [which have been applied to chemical reactors
through a suitable numerical procedure by Dente and Collina (1964), van Welsenaere and
Froment (1970) and Morbidelli and Varma (1982)] has shown that the one proposed by Adler and
Enig (1964), based on the temperature vs conversion phase plane is probably the most reliable
one, since it provides slightly less conservative boundaries for the non runaway region, while
including only conditions truly safe for the reactor [Morbidelli and Varma (1985)].
By introducing suitable approximations, simple analytical relationships have been derived to
represent critical ity in terms of the heat transfer parameter, (3, as a function of the reaction order,
n, and the heat of reaction parameter, a. Some of the expressions obtained are summarized in
Table 1.
Table 1. Approximate Analytical Expressions of the Parametric Sensitivity Region Boundaries.

Criticality equations Limitations References
1 ~ = ea[1-2.85(nla)2/3] vi = 1; )' = 00; large a Thomas (1961)

2 ~ = ea[1-2.52(n/a)2/3] vi = 1; )' = 00 Gray and Lee (1965)
3 ~ = e(a-l) vi = l', )' = 00', n = 1 Hlavacek et a1. (1969)
4 ~ =e(a-l)[1-(a-l)-0.5] vi = l', )' = ,n= 1
00' Hlavacek et a1. (1969)
5 ~ = e(a-2) vi = 1; )' = 00; n= 1 Hlavacek et a1. (1969)
6 a =)'(h- 1)(I+P+p2) # vi = 1; n=1 van Welsenaere and
Froment (1970)
The corresponding results are compared with the exact values obtained numerically through the
Adler and Enig criterion in Figure 1.
n' I, v', o. r; '"
O~, ______ ~ ______L -_ _ _ _ _ _ ~ ____ ~ _ _ _ _ _ __
o 10 20 30 40 50
- HEAT TRANSFER PARAMETE'<, !3
Figure 1. Comparison between approximate analytic (curves with numbers as in Table 1) and
exact numerical runaway criteria {-, Barke1ew (1959); ~, Dente and Collina (1964); 0,
Morbidelli and Varma (1982)} [from Morbidelli and Varma (1985)].
446
An accurate representation of the results obtained through the Adler and Enig criterion in the
entire region of model parameter values is given by the following equation [cf. Morbidelli and
Varma (1985)]:
aD 2{3
~ = ,,-ea [1_(_C)
a
]
(2)
where A = 8.7 { (7.66+nO. 6) and a~ is the critical value of a in the case of adiabatic reactor
(i.e., (3 = 0), given by:
2
0i
-? -
ag = 9 - y(vi-l) - n9(1~) -/ [(1~) - (3)

y y
where () is the solution to the fourth order equation:
-4 -3 -2
(11-1)9 +2y(n-l)(2-y)8 +r2(n-l)(3-y)-y(y-2)]y29
(4)
+ 2[2(n-l )+y]y39+(n-l )t=O
lying in the range 9 < 9 < 9+. 9± = [(y - 2)±{ y(y - 4)0.5}] y /2.
3. The Generalized Criterion for Parametric Sensitivity
In general the sensitivity behavior of a chemical reacting system can be described through the
normalized sensitivity of the generic output variable, g with respect to the generic input
parameter, rp:
S(g;<p) = ~ (og) (5)

g o<p
where the presence of the ratio (rp/g) has a clear physical meaning since it serves to normalize
the magnitudes of the parameter rp and the variable g.
In the case of the pseudohomogeneous reactor model given by eq. (1), we consider as a model
output variable, g, the maximum temperature value along the reactor, v*. In this case we talk
about a normalized objective sensitivity S(v*;rp), where the model input parameter can be
any of the five independent parameters in eq.(1), i.e. rp = vi, aD, (3, 'Y and n. The values of the
normalized sensitivity, S(v*;rp) can be computed most conveniently by following the numerical
procedure developed by Cacuci (1981), which is usually referred to as the "adjoint sensitivity
analysis" .
The obtained values of S(v*;rp) for various choices of rp are shown in Figure 2 as a function
447
of the Semenov number,1/; = a / (3, for a given set of reactor parameter values. The region of
1/; values where S(v*;cp) exhibits its maximum value is the same for all choices of the input
parameter 1/;, thus indicating that the reactor becomes simultaneously sensitive to small variations
of all its input parameters. Therefore the intrinsic nature of parametric sensitivity is apparent,
being independent of the specific nature of the disturbance entering the system. These results led
to the introduction of a new generalized criterion for parametric sensitivity [Morbidelli and
Varma (1988)] which defines as the critical value o/the model input parameter, CPc the one which
maximizes the normalized sensitivity, S(g;cp), o/the variable g with respect to any o/the model
input parameters, cpo
~ 20r-----~----~------~----_r----~
'>
Vi n s 1; vi % 1
~ 15 ~s20; r'20
;;
.;;
.,
c
I"',
10
(f)
=06!61
'"., 5
"0 5
E
z
:s 0
0.4 0.5 06 0.7 0.8 0.9
- - - Semenov Number. til
Figure 2. Normalized objective sensitivity, S(v*;~), as a function of the Semenov number,1/; for
various input parameters, cp: 1=1/;°, 2=ao, 3=vi, 4='Y, 5=n, [from Morbidelli and Varma
(1988)].
With reference to the pseudohomogeneous reactor model (1) the critical values of the Semenov
number 1/;c obtained with different choices of cp = 1/;, a, 'Y, vi and n are reported in Table 2.
Only for small values of the dimensionless heat of reaction parameter (i.e. well outside the region
where the runaway phenomenon manifests itself) the generalized criterion loses its generalized
character, i.e. its answer becomes a function of the particular input parameter considered.
Moreover, for increasing a values, the values of the critical Semenov number predicted by the
generalized criterion approach those obtained by Adler and Enig (1964). This indicates that in
the simple case where both criteria can be applied, they provide essentially the same answer
which, in the limit where 'Y, a --- > 00 and the reactant consumption can be neglected,
approaches the classical result of Semenov's analysis, i.e. 1/;c = exp(-I).
Table 2. Critical v~lues 1/;c' as a funct.ion of a, obtained by maximizing S(v*;cp) with respect to
1/; for fixed a, 'Y, v· and n; 'Y = 00, v· = 1, n = 1.
a <p=Ijf' <p=ao <p=vi 'F"t <p=n
.-~.------~.--
(I) (I) (I) (I) (I) (2)

3 1.66 44.3 4.78 2.43 2.53
4 1.54 5.88 2.63 196 1.99
5 1.36 2.58 1.80 158 158 2.38
7 lOS 1.22 1.13 110 109 109
10 0.781 0.794 0.787 0.786 078-1 0785
20 0.545 0.545 0.545 0.5-15 0.545 0.5-l5
30 0.490 0.490 0.490 0.490 0490 0.490
* No runaway for any <p.

(I) Generalized sensitivlty criterion.
(2) Adler and Enig (1.964) criterion.
448
We will now apply the above criterion to more realistic models so as to generate boundaries
between runaway and nonrunaway operation which can be used for practical purposes.
4. Parametric Sensitivity of Catalytic Tubular Reactors
4.1. THE CATALYTIC TUBULAR REACTOR MODEL
By neglecting intraparticle thermal gradients and both axial and radial dispersion phenomena, a
fixed - bed catalytic reactor can be simulated by a heterogeneous one - dimensional plug-flow
model. This provides a picture, at least from a qualitative point of view, reasonably close to the
real one [cf. Carberry, 1975; Pereira et al., 1979]. Let us introduce new dimensionless
temperatures:
and
(6)
where the reference temperature To is taken again equal to the wall temperature, and the subscript
s refers to the catalyst particle surface. In the case of a n-th order irreversible reaction the model
reduces to [Morbidelli and Varma (1986b)]:
(7)
Xs = X + As11s(1-x)n (8)
gees)
es-- e +Bs11s(1-x)n
----
(9)
gees)
where g(Os) = exp [ - r(1 - 1 / 0.)] and the IC is 0 = oi at X = O. The value of the catalyst
effectiveness factor 11. in eq. (7) can be computed through the approximate relationship developed
by Aris (1965), Bischoff (1965) and Petersen (1965), as follows:
3~coth(3~ )-1
11 s = --'------'----'-'----
(10)
3~2
where q, is the normalized Thiele modulus, defined by
(11)
449
where
(12)
4.2. APPLICATION OF THE GENERALIZED SENSITIVITY CRITERION
The sensitivity behavior of this model has been investigated [cf. Morbidelli and Varma (l986b)]
by considering the sensitivity of the particle temperature maximum value along the reactor, i.e.
S(Os* ;<,0). Such a choice is justified considering that this is the temperature value at which the
reaction occurs, and thus it controls heat production, conversion, selectivity, catalyst activity and
so on. Moreover, this choice allows us to account for both the so-called global sensitivity [cf.
Raiadhyaska et al. (1975)] - i.e. the runaway phenomenon which originates in the fluid phase and
is related to the runaway in homogeneous systems described above - and local sensitivity. The
latter refers to the runaway phenomenon which originates in the catalyst phase when one of the
catalyst particles along the reactor approaches its ignition condition [Mc Greavy and Adderley
(1973)]. The phenomenon of local sensitivity is directly connected to the possibility of the single
catalyst particle to exhibit multiple steady states.
In the following, the normalized objective sensitivity S(Os* ;<,0) of the particle temperature
maximum, Os* to the generic model input parameter, <,0
* <p Cle
*
s
S(es;<p) =-; (-) (13)
es Cl<p
is considered. Similarly, as in the case of the pseudohomogeneous reactor, the S(Os* ;<,0) curve
(shown in Figure 3 as a function of the heat of reaction parameter, a, for various input
parameter, <,0) exhibits a sharp peak at a specific value of a e , which according to the generalized
criterion above corresponds to the critical value for runaway. Thus, the generalized nature of
the adopted criterion is confirmed, since the value of a e does not depend upon the particular
choice of the parameter <,0. Moreover, in Figure 3 it can be noticed that immediately after the
maximum value has been reached (ae = 13.84), the normalized objective sensitivity, S(Os* ;<,0),
undergoes a discontinuity (a = 13.85). This indicates the occurrence of ignition somewhere
along the reactor. This result has important practical implications since it indicates that if
runaway is avoided in reactor design, ignition phenomena are also automatically excluded (while
the reverse is not true).
Without entering the details of the analysis above [for which the reader can refer to Morbidelli
and Varma (1986a)] we can justify the final conclusion on physical grounds by considering that
when ignition is present along the reactor, the catalyst particle temperature undergoes a step
discontinuity. This occurs when such temperature goes across the bifurcation point of the single
catalyst particle. Thus, in the situation where ignition is about to occur some of the catalyst
particles along the reactor are operating close to the bifurcation point, where the derivative of Os
with respect to 0 becomes infinite. For such particles the value of this derivative is then although
finite very large. Any perturbation in the reactor operating parameters, leading to an even small
450
change in the fluid temperature, would cause large changes in the particle temperature and then
the reactor runaway. This is the mechanism of the local sensitivity behavior mentioned above,
which guarantees that before entering the multiplicity region the catalyst would lead to reactor
runaway.
150 r. d, Le ~I
yl'I, Y'20
",'001; {3'30
<1>.'0
S. 100
!'
j
~
50
~
;;
z
- - Heal of Reachon PorOmell!f I a
Figure 3. Normalized objective sensitivity, S(O/;cp) as a function of the heat of reaction

parameter, a for various input parameters, cp: 1=8', 2=ao, 3=A., [from Morbidelli and Varma
(1986b)].
By applying the generalized criterion to the heterogeneous reactor model given by eqs. (7) to
(12), the values of the critical heat transfer parameter, a c ' can be computed for various values
of the other reactor parameters. These are reported in Table 3 and compared with those obtained
through the Adler and Enig criterion, applied to the particle rather than the fluid temperature
profile. It appears that the generalized character of the parametric sensitivity criterion vanishes
for a values sufficiently small, since the value of a c becomes a function of the choice of cpo
However, this is again the situation where runaway is a rather mild phenomenon since the heat
of reaction involved is small. This therefore is not an interesting issue in designing the reactor.
On the other hand, for larger a values (where runaway is a significant phenomenon) the
generalized character of the criterion is preserved and the result approaches that of the Adler and
Enig criterion.
Table 3. Critical values of the heat of reaction parameter, a c for various sensitivity criteria: n = 1,
Oi=O, ,),=20, Le= 1, A.=O.Ol, cPw=O.
f3 <p=n <p=Oi <p=y
(I) (1) (1) (2)

0.1 2.46 1.99 3.50 3.74
5 6.93 6.93 7.07 6.81
10 8.83 8.84 8.88 8.54
30 13.8 13.8 13.8 13.8
50 17.5 17.5 17.5 17.5
(1) Generalized sensitivity criterion (particle temperature).

(2) Adler and Enig (1964) criterion (particle temperature).
451
4.3. REGIONS OF REACTOR PARAMETRIC SENSITIVITY
The influence of inter and intraparticle transport resistances on the region of generalized
parametric sensitivity is shown in Figure 4. For sufficiently large values of A. and CPw the
reactor becomes transport - limited, and runaway does not occur. On the other hand, in the
region of small As values, as As increases (with Le fixed), transport limitations increase, so that
it becomes more and more difficult to remove heat from the particle. This leads sooner to
runaway, i.e. for lower values of the heat of reaction parameter a.
30
c:l
.: 25
.!!
cu
E
...00 20
a..
c
0
15
u
0
oc'" <Pw "" 0.01

.... 10
0
n=I;Le=1
0
cu 5 8 1=0; y=20
I
f3 = 20
0
10- 4 10- 3 10- 2 10- 1
- - Mass Transfer Resistance Parameter, As
Figure 4. Influence of Thiele modulus CPw on region of parametric sensitivity in the a-As plane,
[from Morbidelli and Varma (1987)].
A complete picture of the reactor runaway behavior is illustrated in Figure 5. The critical a c
values are shown as a function of the Thiele modulus, CPw, for various values of each of the other
six parameters involved in the model [cf. Morbidelli and Varma (1987)]. The region of
parametric sensitivity enlarges for lower values of the reaction order, n (Figure S.a) as well as
for larger values of the activation energy, 'Y (Figure S.c). Larger values of the heat transfer
parameter decrease the region of parametric sensitivity (Figure S.b). The dimensionless inlet
temperature, Oi (Figure 5.d) and the interparticle mass transfer resistance parameter, A. (which
being Le = const, implies also the heat transfer resistance) (Figure S.t) have an enhancing effect
on reactor runaway. In Figure S.e the effect of the Lewis number is shown. Since Le is defined
as the ratio between the interparticle rates of heat and mass transport, (the latter being constant
since As is fixed) the interparticle rate of heat transfer has a depressing effect on reactor
sensitivity.
452
50 ~·r-~~~771~~~
50
L. -1,
0 1 '0: r
f3
-20
'20
8t.I~: L;: ~O
'0
1'1. 5 .0004 A '0
As 00 004
'0 '0
fl··o
20
30
20
'0t===0;;:;5;:::.~==:::::::/ 10 10
°
°OLO-'~~~~O~,--"-~l--~~~,~ 0
001
10 001 01 10
~<l'). -<t>_
50 50
n ~ I. L e ' I n 01, Le.1

40 0 1 '0; f3 -20 r '20,fl'20 0
As·Q 004
C 40
AS'OOO4
'0 '0
20 20
10 10
15
10 ° 001 01
- 4>_
10
50 -.~.r-~~"'-~--rr-vr~ 50
n o l,O I ,O
,'20: /3'20
el·.~;L;:~O
40 40
As·aOO4
E fl·20
30 '0
Ltr 10 -
'0 20
10
01 01
0
10 001 01 10
-<t>_
Figure 5. Influence of various parameters on the region of parametric sensitivity: reaction order
n (A), heat transfer fJ (B), activation energy 'Y (C), inlet temperature Oi (E), Lewis number Le
(E), interparticle mass transfer resistance As, [from Morbidelli and Varma (1987)].
4.4. COMPARISON WITH EXPERIMENTAL DATA
The reliability of the developed generalized criterion can be verified via the comparison of two
independent sets of experimental data. In both cases the adopted kinetic expression has been
obtained from a preliminary ad-hoc experimental analysis performed in a suitable gradientless
reactor. The transport parameters have been estimated from semi-empirical literature correlations
[ef. Doraiswamy and Sharma (1984)].
The first set of data has been reported by Emig et al. (1980) and refers to the vinyl acetate
synthesis reaction catalyzed by zinc acetate supported on activated carbon. A comparison
between the boundaries predicted by the generalized criterion and the experimental findings is
shown in Figure 6. The open and closed circles refer to safe and runaway operating conditions,
453
respectively. The pseudohomogeneous model, i.e. eq.(l) or As = 0 in eqs.(7) to (12), is not able
to predict the boundary separating the non sensitive from the sensitive region of the experimental
reactor behavior. The boundary is, on the contrary, well reproduced by the heterogeneous
model, i.e. eqs. (7) to (12). This result clearly indicates the importance of mass and heat transfer
resistances in determining the reactor behavior when the sensitivity region is approached.
tI 2
"-
<Q
- - ¢. =0
- - ¢. =0 I
10 20 70 100
_a
8'=0; Le=1
3 r' 20
2
tI
"-
<Q
As ¢.
CD 0 0
® 0.0015 0
® 0.0017 0.1
10 40 70 100
--a
Figure 6. Comparison of predicted region of parametric sensitivity with experimental data; •

runaway condition, 0 nonrunaway condition: data of Emig et al. (1980), [from Morbidelli and
Varma (1987)]. (a) - Generalized criterion: cfJ w = 0; --- Generalized criterion, cfJ w = 0.1 (b)-
Generalized criterion; - - - Barkelew (1959), homogeneous model; _0_.- Emig et al. (1980),
homogeneous model.
454
The second set of experimental data has been reported by Bauman and Varma (1990). The
carbon monoxide oxidation on CuO catalyst supported on 'Y - alumina was chosen as a test
reaction. The plug - flow, non isothermal, non adiabatic heterogeneous fixed-bed reactor model
given by eqs. (7) to (12) was used to describe the experimental reactor behavior. Figure 7 shows
the ability of the generalized sensitivity criterion (applied to the particle temperature maximum)
to predict the region of sensitivity as a function of the feed flow rate. The curve, computed from
the generalized sensitivity criterion, separates sensitive from non sensitive reactor behavior. A
few exceptions are due to the uncertainty in estimating the critical transport parameters such as
interphase heat and mass transport coefficients, reactor wall heat transfer coefficient and
intrapellet mass diffusivity. Nevertheless, there is a rather good match between experiments and
theory which clearly supports the reliability of the developed sensitivity criterion.
2500 ,---------r-----------,
non·sensltive sensitive
2000
-=E
U
u
1500
•• •
"
'~" lOCO
• • •
~
u.
500
a
SO lOa 150 200 250
Inlet temperature, 'C
Figure 7. Comparison of predicted region of parametric sensitivity with experimental data: •

runaway condition, 0 nonrunaway condition, [from Bauman and Varma (1990)].
5. Parametric Sensitivity of a CSTR
The sensitivity analysis of chemical reactors can be completed by applying the generalized
sensitivity criterion to the case of a single n-th order irreversible exothermic reaction, occurring
in a nonadiabatic CSTR, whose steady-state behavior can be represented in the following compact
dimensionless form [cf. Kaushus et al. (1978)]:
F(w,Da,a,n) = Da(1 +a-w) 11 exp[c(l-l/w»)/(w-l) - a 11-1

(14)
(w-l) - a(l-u) = 0
(15)
455
As discussed by Chemburkar et al. (1986), none of the previous criteria based on the presence
of some temperature profile can be applied in this case, since there is neither a temperature
profile nor a hot spot. Therefore, only the generalized criterion for parametric sensitivity
developed above can be used.
In Figure 8, the normalized sensitivity of the outlet reactor temperature, w, is reported as a
function of the dimensionless heat of reaction parameter, C¥, with respect to each of the four
independent parameters of the model (14) to (15). The critical value C¥c is again the same for
any choice of the input model parameter, cpo
20~----.-----r----'r----'----~-----'
15
10
6-
i p' €
U1
ii
5
Do
a c • 0248 n
0
0.24 025 026
-a
Figure 8. Behavior of the sensitivity S(w;cp) as a function of the dimentionless heat of reaction, a
for the following set of parameter values: Da=O.l1, e=20, n=l, [from Chemburkar et al.
(1986)].
The regions of parametric sensitivity for the CSTR are obtained by examining the behavior
of S(w;Da) as a function of C¥, for various values of the parameter e and the reaction order n.
These results are shown in Figure 9, where the region of parametric sensitivity lies above the
curve and that of safe operation below. As the dimensionless activation energy (e) increases, and
the reaction order (n) decreases, parametric sensitivity becomes more and more likely.
0.5 0.5 r - - T n - ' - - ' - - - ' - - - ' - - b "
0
n• I
0.4
ItJ 0.3
ItJ
I 0.2 0.2
0.1 0.1
o 0.5
0 0.1 0.2 0.3 0.4 0.5 0 0.1 0.2 0.3 04 0.5

- Do - Do
Figure 9. Effect of (a) dimensionless activation energy, e and (b) reaction order n on the
parametric sensitivity region of a CSTR in the c¥ - Da plane, [from Chemburkar et al. (1986)].
456
Moreover, for very large values of the heat of reaction parameter, the so-called Semenov
number (1/1 = Daae) representing the ratio between the rate of heat production and of cooling,
approaches the same asymptotic value obtained in the context of both thermal explosion theory
and pseudohomogeneous plug - flow reactors. In the particular case where also e -+ 00, the
classical Semenov's result, 1/Ic = exp(-I), is again obtained. This clearly supports the intrinsic
nature of the generalized criterion, which brings together seemingly different chemically reacting
systems.
Finally, also for this kind of reactor model, it can be shown that once the region of parametric
sensitivity is avoided, steady - state multiplicity is also automatically avoided. This conclusion
is illustrated in Figure 10, where it is seen that the multiplicity region is entirely contained in the
runaway region.
010
n' I
I 8. 100
I
008 I
\
\
\
\
\
Itl 006 \
\
""'- ,
004
002
0 01 02
Do
03
-------
04 05
Figure 10. Regions of multiplicity and parametric sensitivity in the a - Da plane. The region
of parametric sensitivity lies above the solid line. The region of multiplicity is enclosed by the
dashed and the solid line, [from Chemburkar et al. (1986)].
6. Explosion Limits For a Hydrogen - Oxygen Mixture
It is common practice, when considering an explosive system such as a stoichiometric mixture

of hydrogen and oxygen, to use the concept of explosion limits. These limits are generally
referred to in the literature [cf. Glassman (1987)] as the boundary in the pressure - temperature
plane which separates the regions of "slow" and "fast" reaction. For example, when a fixed
pressure value is considered, the ignition or explosion temperature is defined as the minimum
initial temperature at which the reacting mixture undergoes an explosion. In the case of the
hydrogen - oxygen mixture mentioned above, such explosion limits have been measured
experimentally and are shown in Figure 11.
According to the analysis reported above in the context of thermal explosion theory, we can
use the generalized sensitivity criterion to identify the explosion limits of the hydrogen - oxygen
mixture. By this we imply that the runaway of such a system actually coincides with its
explosion (Le. a very rapid reaction).
457
ro'
.'
i'(\()
Figure 11. Comparison of predicted explosion limits with experimental data; • experimental
explosion limits [from Lewis and von Elbe (1961)]; - model prediction, [from Wu et al. (1990)].
In order to describe the rate of the reaction between hydrogen and oxygen, we adopt a rather
complex kinetic scheme, which accounts for all the relevant elementary reactions which occur
among various radical species in the system. Such reactions have been studied quite extensively
in the literature [ef. Dougherty and Rabitz (1980); Maas and Warnatz (1988)], so that it is
possible to describe the explosion behavior of the hydrogen - oxygen mixture using only kinetic
parameters estimated from independent measurements reported in the literature, (i.e. without any
fitting procedure of the experimental explosion limits reported above). We adopted the kinetic
scheme shown in Table 4 together with the values of the kinetic parameters reported by
Dougherty and Rabitz (1980), except for the wall termination steps involving the H, 0, OH
radicals, whose kinetics have been taken from Semenov (1959).
Considering a homogeneous non - adiabatic vessel with spherical geometry CRv = 3.7 cm),
which corresponds to the reactor where the experimental data shown in Figure 11 were obtained,
the relevant mass and energy balances describing the system behavior are as follows:
dy
CIt = f(t,y,<p) (16)
(17)
with ICs:
(18)
yet = 0) = yi , T(t = 0) = Ti
where t is the time, y is the concentration vector of the species involved, !p is the vector of
458
independent parameters (e.g. kinetic constants, initial temperature and pressure) and f is the
vector of functions representing the reaction rate of each elementary step reported in Table 4.
All the other parameters are defined in the Notation.
Table 4. Reaction mechanism and kinetic parameters for the H2 - 02 system.

No. Reaction Af Bf EflR g -\ Br ErlRg
H0 2 + H = H2 + 02 2.50d13 0 0.35d3 3.lOd13 0 28.7d3

2 H+ 02 =OH+O 2.30d14 0 8.4Od3 3.00dI2 0.28 0.00
3 0+H2 =OH+H 1. 80d 10 1 4.48d3 8.30d09 1 5.5Od3
4 OH + H2 = H2 0+ H 2.50d13 0 2.6Od3 1.40d14 -.03 1O.2Od3
5 ° + H20 = OH + OH 5.80d13 0 9.07d3 6.30d12 0 0.55d3
6 H+H+M=H2 +M 2.57dl8 -1 0.00 6.29d14 0 4S.3Od3
7 H + OH + M = H 20 + M 2.40d22 -2 0.00 1.14d24 -2.2 59.0Od3
S 0+0+ M=02 + M 5.43d13 0 -0.9Od3 5.14dl8 -1 59.4Od3
9 H + 02 + M = H0 2 + M 6.00dl8 -1 0.00 6.00dI5 0 23.0Od3
10 H+02 =OH+ OH 2.50d14 0 0.95 1.20d13 0 20.2Od3
11 H + H02 = H20 + ° 5.00dI3 0 0.5Od3 4.S0d14 0.45 28.7Od3
12
13
° + H0 2 = OH + 02 5.00dI3
5.00d13
0
0
0.50
0.50
l.30d13
5.60d13
O.IS
0.17
28.2Od3
OH + H0 2 = H20 + 02 36.6Od3
14 H0 2 + H02 = H 20 2 + 02 1. SOd 13 0 0.50 3.00d13 0 21.6Od3
15 H 20 2 + M = 20H + M l.71d17 0 22.90d37.71d14 0 -2.65d3
16 H + H20 2 = H2 + H02 1.70d12 0 1.9Od3 6.00d11 0 9.3Od3
17 H+H 202 =H2O+OH 5.00dI4 0 S.OOd3 2.40d14 0 40.5Od3
18 0+ H20 2 = OH + H02 2.00dI3 0 2.95d3 5.20dlO 0 1O.6Od3
19 OH + H20 2 = H20 + H0 2 l.OOd13 0 0.91d3 1. 80d 13 0 IS.lOd3
20 ° + OH + M = H02 + M 2.29d17 0 0.00 1.94d20 -.43 32.2Od3
21 H2 +02 =OH+OH l.70d15 0 24.20d3 1.70d13 0 24.1Od3
22 H+O+ M=OH+M 2.26d16 0 0.00 l.74d16 0 51.lOd3
23 H2 + H02 = H20 + OH 6.50dll 0 9.3Od3 7.2d09 0.43 36.1Od3
24 0+H20 2 =H2O+02 8.40dll 0 2.13d3 3.40dlO 0.52 44.8Od3
°
25 H+WALL 1.20d01 0 0.00
26 + WALL 9.20dOl 0 0.00
27 OH+WALL 9.20dOl 0 0.00
28 H0 2 +WALL l.OOd-l 0 0.00
29 H 20 2 + WALL l.OOd-2 0 0.00
M=H2 +0.402 +6.5 H20; kf=AfTBf exp(-Ef!RgT);~=~ TBr exp(-ErIRgT).
The sensitivities of both the maximum temperature, T* and the maximum concentration of
radicals H, y~, are considered [cf. Hua et al. (1990)], since near the boundary between explosive
and non-explosive behavior of the system both the temperature and the concentration of the
species responsible for carrying on the reaction become sensitive to small changes in the initial
conditions. These quantities are defined in terms of objective normalized sensitivities with
respect to the initial temperature (Le. at fixed initial pressure) as follows:
459
(19a)
(l9b)
and to the initial pressure (Le. at fixed initial temperature) as follows:
S(YH;pi) = ~ (dYH)
YH dPI (20a)
(20b)
For a fixed pressure (P = 6.31 Torr), the critical condition for ignition can be obtained by
plotting the normalized objective sensitivity, S(y~ ;Ti) of the maximum concentration of the
radical H with respect to the initial temperature, T as a function of Ti as shown in Fig. 12.
'(
5
";'
0
f.- 4
*" i
.c.
en
I
31-
"
O~.~O==~~~~--TL'~6~LO----------~670
Figure 12. Normalized objective sensitivity, S(y~ ;Ti) as a function of the initial temperature,
Ti at pi = 6.31 Torr, [from Wu et al. (1990)].
460
It appears that the sensitivity S(y~;T i) exhibits a sharp maximum at the value T = 658.3 K
which, according to the generalized sensitivity criterion, can be regarded as the critical value
separating the non sensitive (i.e. non explosive) from the sensitive (i.e. explosive) behavior of
the system. The reliability of the criterion for defining the explosion limits of the H2 - 02 system
can be verified by examining the temperature and concentration profiles of all species shown in
Fig. 13 as a function of time for two of the initial temperature values considered in Fig. 12.
Th~se two cases, i.e. an initial temperature (Ti = 657 K) near but lower than the explosion limit
(T~ = 658.3 K), and an initial temperature (T = 659 K) near but higher than the explosion
limit, are illustrated in Fig. 13a and Fig. 13b, respectively. Although the difference between the
initial temperature in Fig. 13a and 13b is only 2 K, the system behavior is very different, thus
indicating that the explosion limit, obtained by applying the generalized criterion, indeed
represents the boundary between non - explosive and explosive behavior.
- 6 ;,0 -6
(a)
H, (b)
",
0,
lv-
0,
-6 -8 -:;.
-r ",0 1.0 ~
~
!:'
';1°1 _(0
I-
,0,
i.o _(1
,,0
T T
H
-( 7 o
50 rOo ~ 4
;t (5) t (Sl
Figure 13. Temperature and concentration profiles of all species as a function of time at
Ti=657K (a) and T=659K (b), [from Wu et aI. (1990)].
From Fig. 14, where the normalized objective sensitivity S(T*;pi) of the maximum temperature
with respect to the initial pressure, pi is shown as a function of pi for the model (15) to (17),
further support to the reliability of the generalized sensitivity criterion can be obtained. From
the experimental explosion limits shown in Figure 11, it can be seen that the explosion boundaries
are crossed three times when increasing the initial pressure for a given initial temperature value.
Accordingly, by applying the generalized sensitivity criterion to the results shown in Figure 14,
it is seen that three explosion ljmits are predicted. These .are determined by the positive
sensitivity maxi":la at P~l and. P~3 and the ~egative one at P~2' which indicate that explosion
oc.curs when I;'~1 < pi < P;2 and pi> P ;3' while no explosion occurs in the region where
P~2 < pi < P;3'
The isothermal model, constituted by eqs. (16) and (18) alone, does not predict the occurrence
of the third explosion limit. In particular, when applying the generalized criterion to this model,
it is found that the predicted values of the second explosion limit increase continuously as the
initial pressure increases. For values larger than about 100 Torr the curves representing the
normalized objective sensitivities become flatter and the maximum tends to vanish. Using the
non-isothermal model, given by eqs. (15) to (17), the explosion limits predicted by the
461
generalized criterion compare with the experimental values as shown in Figure 11. No
adjustment of the kinetic parameters of the model has been performed in order to fit the
experimental data in Figure 11.
'"' 1
50 -
a.
*'f- -
r~l
(f) 0 I I
/0'
r;, la' 10'
~~------- P' (T,,,)
-50 b-
'''~ l
Figure 14. Normalized objective sensitivity, S(T*;Ti) as a function of the initial pressure, pi at
Ti = 750K, [from Wu et al. (1990)].
Again with reference to Figure 11, it should be noted that the curve representing the ignition
limits has been obtained by applying the generalized criterion both to the sensitivity of the
maximum temperature, i.e. S(T*;Ti), and to the sensitivity of the maximum concentration of
radicals H, i.e. S(y~ ;T i ). The results are identical for most of the initial pressure values
considered, except for the lower ones, pi < 6 Torr, where the explosion is a very mild
phenomenon and actually quite difficult to be detected experimentally.
In particular, for pi < 6 Torr, the criterion based on S(y~ ;Ti) provides two explosion limits:
a lower (curve a) and a higher (curve b), while the criterion based on S(T*;Ti) predicts only the
second one (i.e., curve b). This behavior can be explained [cf. Hua et al. (1990)] by noting that,
in the case of a fixe<! initial.pressure value pi = 2.5 Torr, the S(y~ ;Ti) curve exhib~ts two
positive maxima at T~ and T~, while the S(T*;Ti) curve exhibits only one maximum at T~. The
first maximum shown by the S(y~ ;Ti) curve occurs at very low system temperature and
hydrogen conversion and thus it is purely due to radical branching. The second involves larger
hydrogen conversion, and can then be related to thermal explosion. Therefor~ the criterion based
on S(T*;Tl) . provides the same answer of that based on S(YH* ;T 1)
. only at T b'1
7. Concluding Remarks
We have shown that the generalized sensitivity criterion illustrated above can be used to identify
the location of the critical transition between sensitive and nonsensitive behavior in the parameter
space for a variety of chemical reacting systems. In particular, when dealing with explosive
462
systems the criterion can be used to identify the explosion limits.

The sensitivity analysis reported above has also evidenced that in the neighborhood of criticality
all the reacting systems exhibit a similar sensitivity behavior. This is characterized by a peak in
the normalized sensitivity, whose location does not depend upon the specific input parameter
considered in the definition of the sensitivity.
One aspect that has not been considered in the analysis reported above relates to the effect of
the external cooling capacity, which has always been considered sufficient to assume a constant
coolant temperature. This assumption has been removed in the context of homogeneous tubular
reactors with co-current cooling, in various studies reported in the literature [Soria Lopez et al.
(1981), Henning and Perez (1986) and Rosten and Froment (1986)]. Bauman et al. (1990) have
studied the sensitivity behavior of such reactors using the generalized sensitivity criterion
illustrated above. The most important result of this analysis is that the Adler and Enig criterion,
which was found to give consistent results with the generalized criterion in all cases examined
before, fails to predict the reactor runaway in the pseudo - adiabatic region leading to
inconsistent results. The failure of the Adler - Enig criterion is a consequence of the increased
complexity of the shape of the temperature profile in that region, which demonstrates the intrinsic
weakness of the criteria based on some geometric features of the temperature profile. This point
allows to stress the reliability of the generalized criterion, which is based on the observation of
the quantity of direct interest for establishing reactor parametric sensitivity, rather than of some
geometric feature of the temperature profile which is only indirectly related to the sensitivity of
the maximum temperature value.
Finally, it should be mentioned that the generalized sensitivity criterion can be conveniently
used to identify the region in the parameter space where a certain characteristic of the reactor
behavior, not necessarily the temperature, becomes sensitive to small changes in the operating
conditions. This is tipically the case where more than one reaction occur in the system. Along
these lines, a study of the sensitivity behavior of the outlet selectivity in a pseudohomogeneous
tubular reactor, where either two parallel or two consecutive reactions occur, has been reported
by Morbidelli and Varma (1989). Another example is given by the sensitivity behavior of a
polymerization reactor, where the problem is to control the quality of the product, for example
in terms of molecular weight distribution [cf. Tjahjadi et al. (1987)].
In all these cases, as in those related to reactor safety discussed above, the generalized
criterion provides a useful tool to determine a priori those operating conditions leading to reactor
runaway, which can be avoided in the early stage of reactor design.
Acknowledgements
We gratefully acknowledge the Consiglio Nazionale delle Ricerche (CNR), Rome, Italy, for the
fellowships awarded to two of us (G. C.) and (M. M.), which permitted to complete the writing
of this manuscript.
Notation
Lk(To)C on·1 / Vs
mass transfer resistance parameter, k(To)C on • 1 / kg lly
area of heat transfer
463
lly particle surface per unit reactor

Bs (-~H)k(fo)Con')'/hlly To
C rectant concentration
cp heat capacity of the fluid
cvm mean value of the heat capacity at constant volume
Dep effective diffusivity within the particle
Da Damkohler number, VCon-1k(fm) I q
e exp(l)
E activation energy
F 2LU I vsPcp~
g output system variable
g«(Js) exp[-')'(l-l!(J.)]
G k(fo)(-m)ConL')'1 pCpTovs
h interphase heat transfer coefficient
k interphase mass transfer coefficient
kfro) reaction rate constant at the reference temperature
k(fm) reaction rate constant at the mean temperature
k(fs) reaction rate constant at the catalyst particle surface temperature
L reactor length
Le external transport Lewis number, AsCI. I Bs = h I kgpcp
n reaction order
NR number of reactions
p pressure
q volumetric flow rate
rk,net net reaction rate of the k-th reactive step
~ reactor tube radius
Rg gas constant
particle radius
~
Sp
radius of the explosion vessel
particle external surface
S(g;cp) normalized sensitivity of g with respect to cp
T temperature
Tm mean temperature, (f0 + oTco) I (1 + 0)
Teo coolant temperature
t time
u dimensionless concentration, C I Co
U overall heat transfer coefficient
V volume of the CSTR
Vp particle volume
V dimensionless temperature, T I To
Vs superficial velocity
X conversion, (Co - C) I Co
Y vector of concentration species
YH concentration of radicals H
464
Greek letters
a dimenionless heat of reaction parameter, GIA = (-AH)C o-yIT,pcp

a dimenionless heat of reaction parameter, (-AH)C o /T,pcpCl +15)
aO a I -y
{3 dimensionless heat transfer parameter, F I A =2U I ~k(To)pcpCon-l
-y dimensionless activation energy, E I RgTo
15 Ua I qpcP
e dimensionless activation energy, E I RgT m
AH heat of reaction
.:lHk heat of reaction of the k-th reactive step
1/s effectiveness factor
(J dimensionless temtRerature, (T-To) I -yTo
A 8.7 I (7.66 + nO. )
cp normalized Thiele modulus defined by eq. (11)
cpw normalized Thiele modulus defined by eq. (12)
<p input parameter of the model
p fluid density
I/; Semenov number, a I (3
1/;0 I/; I a
w dimensionless temperature, T/Tm
Superscript
initial conditions
* maximum value
Subscript
e explosive conditions
c critical conditions
o reference conditions
s particle surface
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Semenov, N.N. (1928) 'Zur theorie des verbrennungsprozesses', Z. Phys. 48, 571-581.
Soria Lopez, A., de Lasa, H.I. and Porras, J.A. (1981) 'Parametric Sensitivity of a Fixed Bed
Catalytic Reactor', Chern. Engng. Sci. 36, 285-291.
Tjahjadi, M., Gupta, S., Morbidelli, M. and Varma, A. (1987) , Parametric Sensitivity
in Tubular Polymerization Reactors', Chern. Engng. Sci. 42, 2385-2394.
Thomas, P.H. (1961) 'Effect of Reactant Consumption on the Induction Period and Critical
Condition for a Thermal Explosion', Proc. R. Soc. A262, 192-206.
van Welsenaere, R.J. and Froment, G.F. (1970) 'Parametric Sensitivity and Runaway
in Fixed-Bed Catalytic Reactors', Chern. Engng. Sci. 25, 1503-1516.
Wu, H., Cao, G. and Morbidelli, M. (1990) 'Sensitivity of the Hydrogen - Oxygen Explosion
Limits', Proc. Combust. Inst., 6.19.
Zeldovich, Y.B., Barenblatt, G.I., Librovich, V.B. and Makhviladze, G.M. (1985) The
Mathematical Theory of Combustion and Explosions, Plenum Press, New York.
KINETICS OF CAYfURE OF SULFUR DIOXIDE AND APPLICATIONS TO FLUE
GAS DESULFURIZATION
Giilsen DOGU
Chemical Engineering Department
Gazi University
Maltepe - Ankara - mRKlYE
Timur DOOU
Chemical Engineering Department
Ankara - mRKlYE
ABSTRACT. Among all the processes for the desulfurization of flue gases, the use of carbonates of
calcium and sodium is the simplest and the most direct method. The conversion of calcium oxide to
calcium sulfate is limited by the plugging of pores with the solid product during reaction. Pore diffusion
limitation becomes significant at the initial stages of the reaction unless the particle size is in the order of
magnitude of a few microns. On the other hand, diffusion of SOz through the product layer becomes the
most important resistence at later stages of the reaction. Activated soda shows a much higher activity and
reacts with S02 at much lower temperatures. In this manuscript, the significance of structural variations
on the reaction and diffusion parameters, the models proposed in the literature, and the experimental
techniques used are reviewed and illustrated. It is shown that detailed information can be obtained about
desulfurization reactions using the single pellet dynamic technique. Comparison of calcium and sodium
based desulfurization processes has indicated that activated soda is an attractive alternative to limestone if
natural soda is available.
1. Introduction
The emission of sulfur dioxide into the atmosphere by the combustion of high sulfur fossil fuels
has been recognized as a serious environmental and health hazard. Sulfur, leaving smokestacks
in the form of sulfur dioxide is generally returned to the earth as sulfuric acid and sulfate ions.
Consequently, the control of SOz emissions has become an increasing concern allover the world.
Over two hundred dry or wet processes have been proposed for the removal of SOz from flue
gases. Limestone and dolomite find extensive use in many of the desulfurization processes.
Activated soda is considered as an attractive and more reactive alternate to limestone. In addition
to calcium and sodium based processes, ammonia based, magnesia based, organic based
scrubbing systems and catalytic processes have also been proposed for SOz removal. Calcium
based dry processes have found wide application especially in fluidized bed combustors and in
467
© 1993 KiLMer Academic Publishers.
468
dry injection systems.

In recent years, considerable attention has been devoted to the understanding of SOz-limestone
reaction mechanism. Kinetics of this reaction is complicated by the changes in the pore structure,
in surface area and by the variations of diffusional effects during the reaction. In this manuscript,
emphasis is given to the mechanism of SOz-limestone reaction in a dry system and a detailed
review of literature is presented. In the second part, kinetics of SOz-activated soda reaction is
discussed and applications to flue gas desulfurization are summarized.
2. Sulfur Dioxide - Limestone Reaction Kinetics
Limestone-sulfur dioxide reaction is generally considered to take place in two steps, namely, the
calcination of limestone and the reaction of calcine with S02'
CaC03(s) ----> CaO(s) + CO2 (g)
CaO(s) + SOlg) + 1I20lg) ----> CaS04 (s)
The capture of S02 by limestone in a dry system is a high temperature process. Calcination step
requires a temperature level over 750°C. It was reported by Ferguson and Rissman (1970) that,
the major reaction product of SOz-calcined limestone reaction was CaS0 3 below 500°C. On the
other hand, CaSO. was the major product over 500°C.
In the reaction of S02 with CaO the pore plugging effect of CaS04 complicates the kinetics
of this reaction. The ratio of molecular volumes of CaSO. to CaO is 3.09 below 473 OK while
at higher temperatures this ratio is expected to be 2.72 (Milne et aI, 1990; Dam-Johansen et aI,
1991a). As a result, formation of CaS04 causes pore mouth closure and increases the pore
diffusion resistence. In this reaction, gas phase mass transfer, pore diffusion and surface reaction
rates might have significant effects on the overall rate especially at low conversions. Formation
of CaS04 creates an additional resistence for S02 to reach active CaO surface. The product
CaS04 is essentially nonporous and diffusion through this layer is very slow. Variations in pore
structure during the reaction cause changes in active surface area. The major limitation of S02
capture by CaO is the low conversions to CaS04 which is caused by the pore plugging effects
of the product. The overall conversion level of CaO to CaS04 is generally less than 0.4 unless
the starting material is very porous and particle size is very small (a few microns).
It was shown by Dogu (1981) that the initial pore size distribution of the solid reactant (CaO)
was very important for its activity towards S02' It was also reported that pore size distribution
and surface area of CaO samples were strong functions of calcination temperature. Over about
900°C, considerable reduction in porosity was observed due to sintering. Sintering temperature
depends upon the origin, chemical composition and crystal structure of the limestone. Decrease
of porosity with calcination temperature is illustrated in Figure 1 for two different limestones.
Some typical pore size distribution curves of CaO samples obtained at different calcination
temperatures are given in Figure 2. It was illustrated by Dogu (1981) that as temperature was
increased pore size distribution curves shifted to the larger pores upto about 950°C and then
average pore radius decreased.
469
B.S ~--------...,.Dcc'c-_-n----ccllc---,-to-ne-----.
......
61<llrucaslle ltnestone
B.5
B.4
Calcination TBftperature • UC
Figure 1. Effect of calcination temperature on the porosity of CaO (Dogu, 1981; Koyuncu,
1985).
0-0 75B "C &-& 8SO "C u - u 959 0,..

0-0 IIBB "C &-& !lOB "C . - . 1000 DC
1.4
1.3
1.2
1.1
~'"u
loB
f\
B.9
..
B.8
~
jf~
B.7
oS B.6
B.S
~ B.4
~
0.3
0.2
0.1
.////
B.B
1.B£-2 B.1 1.0 10.0
Pore rad ius, a. ,,'ero "eter
Figure 2. Pore size distibutions of CaO obtained at different calcination temperatures (after Dogu,
1981).
2.1. MODELS FOR S02 - CaO REACTION
Pore and product layer diffusion resistences, changes in pore structure and variation in surface
area during the reaction are some important factors to be considered in the modelling of S02-CaO
reaction. There are over thirty models proposed in the literature. A summary of these models are
given in Table 2.1.
These models are classified into two groups. The models listed in the first group do not
consider pore diffusion resistence. First group models are extensions of the unreacted core model
and they are limited to small particle sizes in the order of magnitude of a few microns. Pore
diffusion resistence becomes important especially at high temperatures and at the initial stages
470
of the reaction for larger particles. In the second group of models, pore diffusion resistence is
considered together with product layer diffusion.
These models are also grouped from a different point of view as grain models, pore models,
volume reaction models and deactivation models. In number of these models, changes in pore
structure during the reaction and variations in diffusion and reaction parameters are considered.
TABLE 2.1. Models Proposed for S02 - CaO Reaction
Models which do not Models which consider pore diffusion

consider pore diffusion
Grain Models Snowet al (1988) Pigford,Sliger (1973)
Borgwardt,Bruce (1986) Szekelly,Evans (1970)
Marsh, Ulrichson (1985) Wen,Ishida (1973)
Grain Models with Weinstein (1989) Hartman,Coughlin(1976)
pore structure Ramachandran, Smith (1977 a)
variations Georgakis et al (1979)
Hartman et al (1978)
Hartman, Tranka (1980)
Dam-Johansen et al (1991b)
Overlapping Sotirchos,Yu (1988)
Grain Models Milne et al (1990)
Single Pore Model Ramachandran, Smith (1977 b)
Chrostowski, Georgakis(1978)
Pore Structure Bhatia,Perimutter Sotirchos, Yu (1985)
Models (1980) Christman,Edgar (1983)
(distributed, Bhatia,Perimutter (1981,83)
random,pore tree) Simons et al (1985,86,87)
Bhatia (1985)
Volume Reaction Fan et al (1984)
Models
Deactivation Zheng et al (1982) Dogu et al (1981, 1986)
Models Lee,Georgakis (1981, 1980) Orbey,Dogu,Dogu (1982)
Chang,Thodos (1984)
Uddin,Orbey,Dogu (1991)
2.1.1. Grain Models Neglecting Pore Diffusion. For very small CaO particles, SOz partial
pressure within the pore structure becomes uniform. In this case, either a homogeneous first
order reaction can be considered within the grains or an unreacted core model can be used. For
a first order pseudohomogeneous reaction within the grain the following expression for the
conversion time relation can be written.
- In (1 - X) = kh t (2.1)
471
This model does not generally give a good fit with the experimental kinetic data for the CaO-SOz
reaction.
The controlling differential equation for the unreacted core model with diffusion of SOz
through the product layer can be expressed as:
d 2
_(rD_)=O
dC, (2.2)
dr ' dr
at r=r&t (2.3)
D dC'=kC (2.4)
'dr "
The solution of this equation together with the boundary conditions gives the concentration profile
within the product layer.
C..
r r (2.5)
1+(k -=-)(1-(-=-))
'D, r&t
If the increase in grain size during the reaction is neglected rgt can be taken as equal to rg • This
is an oversimplifying assumption and is corrected in structural models. Using this equation
together with
(2.6)
and
(2.7)
the following conversion time relation was obtained:
(2.8)
For the chemical reaction and product layer diffusion controlling regimes conversion-time
relations for the unreacted core model simplifies
Kinetics controlling:
t M. C.o k.
(1-(1-x)113) = __"_'_' (2.9)
472
Diffusion controlling :
1-3(1-x)2/3+2(1-x) = 6 t Me Ds Cso (2.10)
pe r2 g
In CaO-S02 reaction, diffusion resistance through the solid product layer is a major rate limiting
step. Limitations of chemical reaction rate is important only at the initial stages of the reaction.
It is reported that after the formation of about 5 A CaS04 layer, reaction is controlled by the
diffusion of S02 through the product layer. The values of diffusion coefficients reported in the
literature are summarized in Section 2.3.
Reaction Order
In the majority of the kinetic studies, the reaction of sulfur dioxide with calcium oxide was
considered as first order with respect to S02 concentration. On the other hand, in a recent study
of Borgwardt and Bruce (1986) an equilibrium relation between the partial pressure of sulfur
dioxide in the gas phase and concentration of sulfur dioxide on the product layer surface was
proposed.
(2.11)
Basing on their experimental studies, Borgwardt and Bruce recommended the value of m as 0.62.
This approach gives a reaction order of less than 1. Experimental results of Yang et al (1978)
indicated a reaction order of 0.59. This approach was extended by Milne et al (1990) considering
the finite vapor pressure of S02 above the solid CaS04 • Instead of Eq.2.11 they advise the use
of following equilibrium relation:
Cso = Klo ( Co - cy (2.12)
where
(2.13)
Borgwardt and Bruce (1986) used the unreacted core model with product layer diffusion
control and showed good aggrement with the experimental data obtained with 1 /lm particles.
Combining Eq.2.11 with Eq.2.1O, and expressing the diffusion coefficient (D,) in the product
layer in Arrhenius form (see Section 2.3) and writing the grain radius in terms of surface area
as
(2.14)
they expressed the conversion time relation in the following form:
1-3(I-x)2/3 + 2(1-x) = 2.65(S)2 (PSQ )O.62 exp(_36600)t. (2.15)

8, RT
473
2.1.2 Models Considering Pore Diffusion. Pseudo steady state transport equation for SOz in a
spherical porous solid reactant (CaO) can be written as follows:
~ ~ (R2 D dC) + R =0 (2.16)

R2 dR ' dR S
The effective diffusion coefficient of S02 which appear in the first term ofEq.2.16, is a function
of pore size distribution. Changes in porosity and average pore radius of the solid during the
reaction causes variations of D, with local reaction extent. In general, D, changes both with
respect to time and also with respect to radial position. In grain models, which do not consider
the variations in pore structure during the reaction, D, values were assumed as constant. On the
other hand, in some models radial variations of D, were not considered but variations with
respect to time were taken into account (Hartman and Coughlin,1976; Hartman et al,1978;
Dogu,1981). Position and time variations of D, were considered in number of structural models.
Prediction of D, and its dependence on porosity and conversion are discussed in Section 2.2.
The reaction term R. can be expressed as
(2.17)
The reaction order m is generally taken as 1 (see Section 2.1.1 for details of reaction order). The
active surface area per unit volume of the solid reactant (ppSg) changes during the reaction. The
local effectiveness factor (11s) is included into the equation to take into account the local product
layer diffusion resistance in the porous solid. It is the ratio of actual local reaction rate to local
reaction rate without product layer diffusion resistance.
In the literature, number of models were proposed to predict 11s and the variations of qpSg
(Table 2.1). A review of these models is given in the following section.
Grain Models
There are number of publications in the technical literature which utilize the spherical grain
theory to model the sulfation reaction of CaO with SOz. In these models it is assumed that the
solid reactant pellet is an aggregation of spherical grains and each grain is modelled by the
shrinking core with a sharp reacting interface (Figure 3). In these models, Rs can be expressed
as
(2.18)
where F is the specific reaction interfacial area per unit volume of the pellet. In the model
proposed by Hartman and Coughlin (1976). F is expressed by the following equation;
F =3 ( 1 _ E) (ry (2.19)
(rgY
Substituting Cslr~rc from Eq. 2.5 into Eq. 2.18 and solving Eq.2.16 together with Eq.2.6 gives
the concentration profile within the pellet. In many models Cso which appear in Eq.2.5 was taken
to be equal to gas concentration in the pores. A better approach would be to use Eq.2.12 in
474
expressing C.ro' Numerical solution of these equations gives the variation of fractional conversion
with position and time. The local and overall conversion in terms of position of the reaction
interface (rJ can be found from
(2.20)
(2.21)
Grain models were further developed to include changes in the grain size (rJ during the
reaction. This causes reductions in porosity of the pellet with reaction extent. Ramachandran and
Smith (1977a), Hartman et al (1976,1980,1978) Georgakis et al(1979) proposed modified grain
models which included grain expansion and porosity changes. It was shown by Dogu (1981),
Ramachandran and Smith (1977a) and Hartman et al (1980) that grain radius at any conversion
(rst> can be expressed in terms of the densities of the reactant and product solids and in terms of
rc by a mass balance for the product layer.
(2.22)
where
(2.23)
Hartman and Tranka (1980) extended this approach and reported the following expression for the
grain radius in terms of the fractional conversion of CaO to CaS04 as follows:
r = r(l-x(l-P e(l+ w(Mg-M) )_1_»113 (2.24)

gl g P, Mee -w(Mee -M) I-f,
Using this equation and the following relationship,
(2.25)
the change of porosity can be expressed in terms of conversion. In Eq.2.24, f. corresponds to

the porosity of product layer CaS04 and its value is very close to zero. If the reactant is pure
CaO, the relation between porosity and conversion becomes (Ulkiltan, 1982)
(2.26)
In recent years, Sotirchos and Yu (1985) and Milne et al (1990), extended the grain model
concept and developed overlapping grain models. They formulated model equations for randomly
overlapping grains and showed that the overall reactivity of porous solid is a strong function of
475
grain overlapping and grain size distribution.
Pore Models
A second approach in modelling S02-CaO reaction is the represention of the porous network
by a collection of capillaries which are usually assumed as cylindrical. One of the simplest pore
models is the single pore model proposed by Ramachandran and Smith (1977b). This model
accounted for the influence of pore diffusion, diffusion through the product layer which builded
upon pore walls and surface reaction. Changes in pore geometry during the reaction was also
accounted for. In their work, the complex nature of the CaO-S02 reaction was simplified by
focusing attention on a single pore. Schematic represantation is given in Figure 4.
1
S02
Gt-ain
~ .:'!
Co.)
:··:",,11:::
;:.;0
·.:iU
\Ii
v
::::.
:;:::
.;",.
",
(.. . &
-',if
Unreact@d core
Pl"oducl (CaS04) ·i}
la.yer
Figure 3. Schematic representation of grain Figure 4. Schematic representation of single

model. pore model.
The pseudosteady state diffusion equation through the solid product layer of a cylindrical pore
is
d dC
_ (r D_') =0 (2.27)
drp P 'drp
where rp is the radial coordinate in the pore model. Solving this equation together with the
boundary conditions
C, = C at rp = ap (2.28)
dC
(2.29)
r 'I,.a
-D, -d II
l
P
= k, C,I,=a
P
1
P
P
gives the concentration of S02 at the reaction interface (at rp = a 'p) (Christman and Edgar, 1983).
The point reaction rate at any position in the pore can then be written as
476
Pc da'p
- R's
a' k a' Mc dt (2.30)
1 + _p_s ln~
Ds ap
Solution of these equations together with the diffusion equation through the pore requires
numerical techniques. Similar to the grain model approach pore size reduction due to product
layer formation was considered in these pore models.
One of the major limitations of the single pore model is the assumption of taking a uniform
pore size. Generally, an average pore may not be a good representation of a porous solid with
a wide distribution of pore sizes. Christman and Edgar (1983) extended the pore model and
presented a distributed pore size model. A probabilistic approach was used for the pore size
distribution and a population balance approach was followed. This model was further improved
by Sotirchos and Yu (1985) to include pore overlap which becomes significant especially at high
conversions. Their results indicated that conversion time relations are strongly influenced by the
type of pore size distribution. Various pore structures characterized by the same values of internal
surface areas and porosities gave quite different conversion time predictions. The effect of pore
structure changes were also investigated by Bhatia and Perlmutter (1980,1981) using the random
pore model. They showed that three parameters namely pore volume, surface area and pore
length were needed to adequately characterize the pore structure. Their results indicated that a
solid with a wide pore size distribution would be more reactive than a solid with uniform pores.
In the recent work of Simon et al (1987,1986) model equations were derived assuming a pore
tree model. Their work indicated that the plugging of small pores by the formation of CaS04 ,
resulted in significant decrease in internal surface area and caused the deactivation of the solid.
Deactivation Models
As it was discussed in the previous sections, predictions of random pore models indicated very
strong dependence of reactivity on the pore size distribution. Similar conclusions can be
expressed for the grain size distribution in grain models. In the absence of such detailed
information about the pore structure, the success of the predictions of these models would depend
upon the correct selection of the adjustable parameters.
In the deactivation model proposed by Dogu (1981), instead of assuming a model for the pore
structure and writing the diffusion equation through the product layer over the grains or in the
distributed pores, an activity factor was included into the reaction term of Eq.2.16.
-
Rs -- p° So k a C -
_ pop dX
-- (2.31 )
p gs Mdt
c
Activity of the solid decreases with time due to the changes in surface area and the formation of
product layer over the reactive surfaces. The rate of change of local activity can be expressed
as
477
da '" fJ a" em (2.32)

dt
In the original development, Dogu (1981) assumed n is equal to one and m is equal to zero and
obtained analytical solutions of the model. The concentration profile of S02 within the porous
CaO was then obtained as
R sinh«3.!) exp( -fJ~»

oRo 2
e=e 0 (2.33)
• R sinh(3 <1>. exp(-fJ~»
where 1/>. is the initial value of the Thiele Modulus and it is given by Eq.2.34 .
• S· k R
 '" (p p g S)1/2"'::' (2.34)
• D. 3
Combining Eq.2.33 with Eq.2.31 and carrying out the integration, local conversion can be
obtained. Average fractional conversion of the solid was then obtained for the pellet from
!
R t sinh(3.! exp( -fJ~»
3 S· k M e ' R 2
= f
0
X g s c • R· exp( -fJt) dt dR
R2. ! sinh(3<1>. exp( -fJ~»
(2.35)
Analytical expressions were reported for the average conversion-time relations for the pore
diffusion and kinetics controlling regimes.
Pore diffusion controlling:

6 M(S· k D)1/2 C
X = c g s. ·(1 - exp(-fJ~» (2.36)
R. fJ(p· ;l12 2
Reaction controlling:
M S· k C
X = c g s • (1 - exp( -fJt» (2.37)
fJ
Deactivation model was later applied by Orbey et al (1982) for the sorption of S02 with calcined
limestone in a packed bed. Values of the deactivation constant fJ was reported both by Dogu and
Orbey et aI (1981,1982). In a more recent work this approach was extended by Uddin, Orbey
and Dogu (1990) by taking both nand m being equal to one in Eq.2.32 and numerical solutions
were compared with experimental data. A similar approach was also used by Fan et aI (1984)
and it was shown that the results are in good agreement with the data in the literature.
478
Deactivation model is simpler than the random pore and grain models and it involves only the
surface reaction and deactivation rate parameters. An expression was also proposed by Dogu
(1981) for the prediction of {3 from the known values of surface area and porosity. Lee and
Georgakis (1981) proposed a similar deactivation model for the overall reaction rate. In the work
of Lee et al (1980) and Zeng et al (1982), deactivation model was applied for desulfurization with
limestone in a fluidized bed cumbustor. In these studies, pore diffusion was neglected and the
decrease of overall rate with respect to time was expressed in exponential form.
Chang and Thodos (1984) proposed another model for the overall rate which was represented
by the exponentially combinational decaying with respect to reaction extent.
(2.38)
This model contains three adjustable parameters (u, b, n) to represent the deactivation process.
2.2. EFFECTIVE PORE DIFFUSION COEFFICIENT OF S02
One of the parameters which determine the reactivity of CaO towards S02 and the overall
conversion to CaS04 is the effective diffusion coefficient in the pores. The value of the effective
diffusion coefficient in the general transport equation (Eq.2.16) can be predicted from the pore
structure information.
(2.39)
D = ( _1_ +_I_tl (2.40)

T DSA. D KS
Here, the Knudsen diffusion coefficient D KS can be predicted from
D
KS
= 9700 aP (~)1I2
AI (2.41)
so,
Using
2 E
a = (2.42)
p PpSg
Eq.2.41 can be written for S02 as
(2.43)
The molecular diffusion coefficient of sulfur dioxide can be predicted from Chapman-Enskog
theory and its value is 1.13 cm2/s at 840 ·C and 1 atm and for the temperature range of interest,
it can be approximated from
479
(2.44)
In the absence of experimental data, the tortuosity factor can be estimated from random pore
model as
1 (2.45)
7=-
f
Recently an overlapping grain model was proposed by Dogu and Dogu (1991) for the tortuosity
f
for f:2:0.476 7 = ------=-- (2.46)
1 - 11"«1 - f) ~)2J3
411"
f
for f~0.476 T = -------------------
r r (2.47)
- 11"(.2.)2 + 2(2)2 (a - sina)
ac ac
(2.48)
(2.49)
Combining Equations 2.39-2.46, the following expression was obtained for the effective diffusion
coefficient of SOz in the pores of CaO for f :2: 0.476
(2.50)
Eq.2.50 can be used for the prediction of initial value of De as well as its variation during the
reaction. To predict its variation with reaction extent, either porosity and surface area data
should be available at different conversions or variation of porosity can be predicted from
Eq.2.26. Structural variations with reaction extent are discussed in Section 2.6.
The value of effective diffusion coefficient depends upon the pore structure. Some numerical
values reported in the literature are given in Table 2.2.
480
TABLE 2.2 Some Effective Diffusion Coefficient Values Reported (e=0.56),

(Orbey et al, 1982)
roc 720 800 860 900 950
D,xlO", m2/s 0.097 0.17 0.15 0.19 0.20
2.3. DIFFUSION THROUGH THE PRODUCT LAYER
Calcium sulfate product layer is essentially nonporous and the diffusion process through this layer
is generally considered as a solid state migration of ions. The effective diffusivity values reported
in the literature for the diffusion coefficient of S~ in the calcium sulfate layer ranged between
10-13 m2 /s - 10-10 m2/s and it is defined in Arrhenius form as follows:
E
D
,
= D exp(----..:..)
0 RT
(2.51)
The activation energy values reported in the literature are summarized in Table 2.3. Temperature
dependence of solid diffusion coefficient is given in Figure 5. The activation energy estimated
from this figure is also given in Table 2.3. The differences of diffusion coefficients reported in
the literature are majorly due to differences in chemical and physical properties of the limestones,
differences in experimental techniques and differences in proposed models from which D, values
were evaluated by fitting the experimental data .
• Marsh-Ulrichson .1985 v ChristMdn-Edgar.19B3

6 Calcula.ted frOM data. of ~ Bhatia-PerIMutter.1901
Borgwardt-Bruce.1986 o Bhatia-PerIMutter.1901
o HartMan-Tranka.19BO ... RaMachandran-SMith.1977
lE-9 r--------------------------------------------,
IE-to A
til
6 0
•
'!" lE-11
l>
0
(0
""
lE-12 L;
L>.
lE-13
7 B 9 HI
U)4; T ( "K -1)
Figure 5. Temperature dependence of D,

481
TABLE 2.3. Activation Energy of Diffusion Coefficient (D,) of S02 in CaS04 layer
Activation Model Fitted Reference Source of Data

Energy
MJ/kmole
153 Grain Borgwardt,Bruce(1986)

120 Random Pore Bhatia, PerImutter(1981) Borgwardt (1970)
103 Distributed Pore Christman, Edgar (1983)
149 Slab Marsh, U1richson(1985)
129 All Data This work Figure 5
In most of the data reported in the literature, no differentation is made between the gas and
solid state concentrations of S02 within the product layer. On the other hand, as it is discussed
in Section 2.1.1 an equilibrium relation should be used between the gas and the solid phase
concentrations (Eqs.2.11, 2.12). There is no independent data reported in the literature for the
equilibrium constant Ko. The relation between the true solid state diffusivity D's and the
diffusivity calculated without considering any equilibrium relation (DJ is
Ds = D'
s
K' 0
Cl.38
= D' K
sop
~0.38
(2.52)
SO,
Milne et aI (1990 a,b) reported D: Ko as an effective diffusion coefficient. D', Ko is a

function of temperature. On the other hand, Ds also depends upon the concentration of S02. This
indicates that fluctuations of Ds values shown in Figure 5 might also be partially due to
differences in S02 concentrations in different work. D's Ko values corresponding to all data points
in Figure 5 were calculated and plotted as a function of liT in Figure 6.
2.4. SURFACE REACTION RATE
Surface reaction rate constant values were reported by number of different researchers in the
literature. In many cases ks values were obtained by fitting the proposed model to the
experimental data. Since there are differences in models proposed, some differences in ks were
observed in different work. For instance the ks value reported by Hartman and Coughlin (1976)
is 6.6xlO- 1O mls while 2.2x10-4 mls is reported by Wen and Ishida (1973) at the same
temperature. Some of the ks values were calculated from the initial rate data obtained with very
small particles of a few microns. For such particles pore diffusion limitations were neglected.
Variation of ks values with temperature is illustrated in Figure 7. The activation energy from this
figure is reported in Table 2.4. together with reported activation energies from the literature.
482
A Co. lcu latod froM data of v ChristMan-Edgar , 19B3

Borgwardt-Bruce.1986 ... Bbiltla-PerlMutter ,1961
o Hartl'!an-Tranka .1900 o Bbiltia-PerlMutter ,1961
T RaMachandran-SM I tb .1977
1E-15 .----------------------------------------------.
.....
.....'en 1E-16
'., 0
0
1E-17
0
.i'
• en
1E-1B ...
'" l!. ~
1E-19
7 B 9 10 11
104 .... T nK -1)
Figure 6. Temperature dependence of D', Ko.
o Bbatla-PerIMutter.1OO1 c Borgwardt-Hilrvey.l972
A ~ Hartl'l<ln-Trilnkil.190o
Calculilted fral'! data of
Borgwardt-Bruce,l986 • Cbristnan-Edgar.1903
Y S Il'IOns et a 1 • 19B7 v Calculated frOM data of
• Ar et 0.1.1991 Milrsb-Ulricbson.1985
1.9E-2 r---------------------------~~~ Snow et ill,l988______-,
or
..
.
c
I
u; J>.
A . "YA
i:: 1.0E-3
<> ",A",
,.,.en •
V
1.BE-4
7.5 B.B B.S 9.B 9.5 10.0 HI.S 11.0
l .... T ) H HI-4 ~
Figure 7. Temperature dependence of surface reaction rate constant

483
TABLE 2.4. Activation Energies of Surface Reaction Rate Constant, k,
Activation Reference
Energy
MJ/kmol
56.4 Bhatia, Perlmutter (1981)
53.5 Orbey, Dogu, Dogu (1982)
57.7 Ferguson, Rissman (1970)
54.3 Dogu (1981)
56.2 Simons, Garman (1986) (Using data of
Borgwardt and Harvey, 1972)
141.0 Simons (1988, 1987)
64.0 Snow et al (1988)
67.0 From Figure 7.
Basing on the data reported in Figure 7, the surface reaction rate constant for S~-CaO reaction
can be expressed as
8055
(2.53)
k, = 1.26 e ----r, (mls)
The value of activation energy for the surface reaction rate constant is about half the activation
energy for the diffusion coefficient of S02 through the product layer. Recently, some kinetic
information was reported by Dam Johansen et al (1991c) and Dennis and Hayhurst (1990) related
to the mechanism of surface reaction between SOx and CaO. The role of oxygen on the reaction
mechanism and the elementary steps in the reaction mechanism were discussed in these papers.
Dennis and Hayhurst (1990) reported that ultimate uptake of S02 was decreased by an increase
in the concentration of O2 ,
Another important parameter is the deactivation rate constant {3 which appear in the
deactivation models. Its value was reported to vary between 10-3 - 10-4 S-l. This constant was also
reported to depend upon temperature. Of course, its value might also depend upon the physical
and chemical properties of the limestone. The activation energy of the deactivation constant {3 is
tabulated in Table 2.5.
TABLE 2.5. Activation Energies for the Deactivation Constant,{3
Activation Energy Reference

MJ/kmol
50.2 Dogu (1981)

55.2 Orbey et al (1982)
484
Some numerical values of (3 reported in the literature are given in Table 2.6. The values
reported by Zheng et al (1982) are about one order of magnitude greater than the others. This
is probably due to the neglection of pore diffusion resistence in that work.
TABLE 2.6. Values of Deactivation Constant, (3, from Literature
(3, 1xW, 1/s Temperature, ·C Reference

3.37 - 6.35 800 Zheng et al (1982)
2.86 - 5.27 850 Zheng et al (1982)
0.60 850 Dogu (1981)
0.64 900 Dogu (1981)
0.78 1000 Dogu (1981)
0.42 800 Orbey (1982)
0.75 900 Orbey (1981)
1.01 950 Dogu (1982)
0.73 700 Koyuncu (1985)
2.5. MAXIMUM CONVERSION OF CALCIUM OXIDE TO CALCIUM SULFATE
Conversion of calcium oxide to calcium sulfate is limited by the plugging of the pores. A relation
was reported between the conversion and porosity by Eq.2.26. That equation was written for a
pure CaO particle. Eq.2.26 was modified for the presence of components other than CaO in the
limestone.
pO
E = Eo - (-y - l)wc X (r!) (2.54)
c
The theoretical value of CaO density was reported in the literature as 3.3 g/cm3 (Milne et al,
1990, Christman and Edgar, 1983).
Using the deactivation model, Dogu(1981) found an expression for the variation of local
porosity with respect to time.
dE = (1 - "() Me pO So k exp( -(3t)C (2.55)

dt Pc p g ,
By substituting C from Eq.2.33 into Eq.2.55, and carrying out the integration, an expression can
be found for the porosity. By taking C = Co and integrating Eq.2.55, the following expression
was obtained for the variation of porosity at the external surface of the particle.
485
fl = fo + .!....:...1
p
po
p
So k C Me (1 - exp( -pt»
g' 0 Pc
(2.56)
At the instant of pore mouth closure f' becomes zero. For this case Eq.2.56 takes the following
form:
1 - exp( -Pt,,.,)
(2.57)
P
As it was shown by Dogu (1981), the term exp(-pt..) was much smaller than one and
consequently, the value of P can be estimated from Eq.2.57. Combining Eqs.2.36, 2.37 with
Eq.2.57 maximum conversion expressions were obtained for the kinetics and diffusion controlling
regimes: All these equations were derived for a pure CaO particle. For a limestone which also
contains species other than CaO the modified maximum conversion expressions are as follows:
Kinetics controlling: (<1>0 < < 0.3)
(2.58)
Diffusion controlling: (<1>0 > > 3)
(2.59)
Maximum conversion is a function of Thiele Modulus. Increase of particle size causes an increase
in diffusion resistence and consequently maximum conversion decreases. For a particle with a
porosity of 0.45, expected maximum possible conversion is around 0.48 even in the absence of
diffusional limitations. For negligible pore diffusion resistance, <1>0 should be small. For a
temperature of 850"C, taking the k, and D, values from Eq. 2.53 and Table 2.2 respectively, the
relation for negligible pore diffusion resistance on initial sorption rate of S02 can be written as
RJpp S/YI2 <0.1 (m Il2 ). This relation predicts that if S/=5 m2/g, Ro should be less than about 35
/Lm and if S/=20 m2/g, Ro should be less than about 18 /Lm for negligible pore diffusion
resistance on the initial rate. For particles larger than 100 /Lm; maximum conversion values
reported in the literature are generally less than 0.5 for limestones (Fan et al,1984; Zarkanitis
and Sotirchos, 1989; Orbey et aI, 1983; Christman and Edgar, 1983; Hartman and Coughlin, 1986).
For large particles most important parameter for the maximum conversion is the porosity of CaO.
It was reported by Hartman et al (1978) that conversion increases with an increase in porosity
of natural stone. Higher conversion levels were reported for dolomites containing significant
amounts of MgC03 (Chang and Thodos, 1984; Fan et aI, 1984). This is also predicted by
Eqn.2.58 and 2.59. Reaction of S02 with magnesium oxide is limited by equilibrium over 650°C.
This allows more available pore volume for CaS04 at temperatures over 800°C (Thibault et aI,
1982). For CaO particles of a few microns in size Eq.2.58 and 2.59 fail because, in the
derivation of these equations particle swelling was not considered and for very small particles,
this effect can not be neglected. For very small particles, reaction takes place essentially at the
external surface. As it was illustrated by Borgwardt and Bruce (1986) for very small particles
486
maximum conversion increases with an increase in surface area. Dependence of maximum

conversion on surface area is given in Table 2.7.
TABLE 2.7. Relation Between Ultimate Conversion and Surface Area for Particles of 1ILm
in Size (Borgwardt and Bruce,1986)(T=800"C)
Maximum Conversion 0.15 0.52 0.63 0.70 0.84

Surface Area S., m2/g 2.1 11.5 21.0 25.0 63.0
2.6. STRUCTURAL PARAMETERS AND MECHANISM
The possible rate limiting steps and the importance of pore structure on the reaction rate and
ultimate conversion were discussed in the previous sections. Koyuncu (1985) and Ar (1991)
reported experimental data for the variation of pore size distribution and surface area with
reaction extent. Typical results showing the variation of porosity and pore size distribution curves
with conversion are given in Figures 8 and 9 respectively.
EI.6E1 r----------------------------------------------,
o 45E1 0C
o t:. SEIEI oc
EI.55 o 7E1E1 oc
EI.5E1
[J
:!)
::: EI.45
(f)
cfl: EI.49
9.35 A
o
El.3El
El.25 ~~~~~~~~~~~~~~~~~~~~~~~~
El.ElEl El.El2 El.El4 El.El6 El.ElS El.iEl El.12 El.14 El.16 El.iS El.2El El.22
COl'lversiol'l, x
Figure 8. Variation of porosity with conversion.
These results indicated that decrease of porosity with conversion agreed well with the prediction
of Eq.2.26. Also it was concluded that, first the smallest pores were clogged and the reactivity
of the solid decreased with a decrease in active surface area associated with small pores. In the
following analysis, experimental structural information was used for the understanding of the
controlling mechanism of CaO-S02 reaction. The rate expression for the deactivation model
487
B.3S
A
tn
"-
(Y') B.3B CONVERSION B
Ii:
(J
A EI.BBB C
Q) B.2S B B.B16 D
c
..:! C B.BB3
B.2B D B.172
~ E B.2B2
Q)
F B.2BS E
'"'
0
"'"'
B.1S
Q)
.~
F
~
B. lEi
!!
::s
Ii:
::s EI.BS
u
B.BB
EI.Bm B . BlB B.Um 1.BBB lB. BBEI
Pore Rddius. Micro Meter
Figure 9. Pore size distribution at different conversion levels to CaS04 T=700·C,
(Kurucasile Limestone).
(Eq.2.31) can be reexpressed by combining with the expression obtained for S02 concentration
at the reaction interphase from the grain model (Eq.2.5).
- R s = P°p So g ks C = (pp S)
e-~t . k Cs Ir;r~
g achve s
C (2.60)
= (pp S) k--
gocliv, '1 + /)
(2.61)
This relation gives the following expression for the ratio of active surface area at any time to
initial surface area.
(2.62)
Combining this equation with Equations 2.7,2.22,2.25 and writing
(Pp Sg)ocliv, = (~)2 (2.63)

pop SOg rg
the following expression was obtained

488
Y = 1 + cJ>p Z (2.64)
where
(2.65)
(2.66)
(2.67)
The dimensionless group cJ>p gives information about the relative importance of surface
reaction rate to diffusion rate through the product layer. Using the experimental pore structure
variation data (Figure 8) and {j values reported by Koyuncu (1985) the variation of Y with Z was
plotted (Figure 10). This figure showed that the linear relation proposed by Eq.2.64 was obtained
BB
7B o 45B °c
" 6BB °c
6B CJ 7BB °c
~
1:'.1....
x 5B
.!.
4B
....
I"ICI)
3B
::><
2B
ta
B
B.BO B.B2 E1.B4 B.B6 B.BB O.ta B.12 B.14
z
Figure 10. Grain-deactivation model predictions using the pore structure data.
for high values of Z. Such Z values corresponded to conversion levels greater than 0.05. On the
other hand, for smaller conversion values, Y approached to one. This result indicated that the
reaction mechanism was composed of two stages. At low conversions, only the surface reaction
and pore diffusion resistences become significant. After a conversion level of about 0.05 reaction
489
is controlled by diffusion through the product layer. The iI>p value calculated from the slope of
Yversus Z curve at high conversions is 1.5xl<P at 600"C. Estimating the Ie. value from Figure
7, and grain radius from Eq.2.14 (rg =5.6xlO-8m) the value of diffusion coefficient of S02 in the
CaS04 layer was then calculated using the slope of this curve. This value is around Ix 10-14 m2/s.
The order of magnitude of this DB value is in aggreement with the prediction that can be made
from Fig.5.
Experimental data obtained by Ar (1991) for the variation of surface area with conversion is
reported in Table 2.8.
TABLE 2.8 Variation of structural properties of the solid with conversion of CaO to CaS04
(Ar, 1991) (Killik Limestone, T=950°C)
Fractional Surface
Conversion Area, S,
X (m2/g)
0.00 25.7
0.014 23.6
0.071 21.0
0.091 15.9
0.210 11.0
0.459 8.4
This data showed that measured surface area of solid decreased with reaction extent. A grain
model which do not consider grain overlap would not predict this behaviour. Results indicated
that overlapping grain models or distributed pore models would be a better representation of this
reaction system.
3. Sulfur Dioxide - Activated Soda Reaction
The major drawback of using limestone or dolomite in desulfurization processes is the low
conversion of the solid when reacted with S02' On the other hand, with activated soda ash upto
100% conversion was reported. Soda shows much higher reactivity towards S02 than magnesium
and calcium carbonates and it reacts with S02 at much lower temperatures.
Marecek et al (1970), Hartman (1978), Dogu (1984) showed that optimum temperature for this
reaction is between 120 - 200"C. The rate of reaction of S02 with activated soda in this
temperature range was reported to be greater by one to two orders of magnitude than S~
limestone reaction rate at temperatures around 800"C. The molal volumes of N3zS03 and N3zS04
are only 1.14 and 1.27 times greater than the molal volume of N3zC03' Also, the product layer
formed over the active surfaces is not nonporous (Dogu et al, 1988; Dogu, 1984). As a result,
rapid activity decrease which is caused by pore mouth closure in CaO-SOz reaction does not play
a significant role in S02-activated soda reaction. Experimental work of Erdos (1967) showed that
the rate of reaction between gaseous S02 and solid NazC03 can be written as:
490
R• = k PSO, X 1l2 (1-X)3/2 (3.1)
According to this rate expression, reaction rate increases with conversion upto a conversion level
of about 0.3, then it decreases.
When NaHC03 is heated to temperatures over l00"C it decomposes and gives a porous
reactive product which is called activated soda.
(3.2)
Kinetics of this decomposition reaction was studied by Wang Hu et aI (1986). It was shown by
Dogu (1984) that by increasing the activation temperature (in the range 150-3oo"C),
microporosity and the active surface area of the solid decreased. As a result, the activity of soda
for S02 sorption was also found to decrease with an increase in the activation temperature. Some
typical values of porosity and surface area reported at different temperatures are given in Table
3.1.
TABLE 3.1. Physical Properties of Activated Soda Obtained at Different

Temperatures (Dogu,1984). (Total Porosity = 0.51)
Activation E/E Micropore Surface Average

Temperature, Area, cm2/g Micropore
("C) Radius, !-1m
150 0.75 1.12x1()5 0.057
200 0.73 1.ooxl05 0.063
250 0.67 0.68x1()5 0.088
300 0.64 0.54x1()5 0.104
350 0.62 0.45x105 0.117
A detailed thermogravimetric study was reported by Kimura and Smith (1987) for the reaction
of S02 with activated soda in the absence of oxygen
(3.3)
Their results indicated that Na2S03 was formed by two parallel paths, namely by direct reaction
and adsorption of S02 followed by surface reaction. It was shown by Agca (1981) that some of
the N~S03 was converted to N~S04 in the presence of oxygen over 120"C.
(3.4)
Formation of N~S04 causes a resistence for the transport of S02 to the reaction surface and
slows down the rate. It was shown by Genco and Rosenberg (1976) that the activation step is
reversible and some NaHC03 may form in the presence of CO2 and moisture. On the other hand,
Maracek et aI (1970) claimed that CO2 has no effect on the course of sorption. Another important
491
parameter which effects the S~ sorption rate on activated soda is the moisture content of the gas.
It is reported that the rate constant was increased with an increase in moisture content.
It was reported in the literature (Blaykher and Laryushkina, 1972; Dogu et ai, 1988) that some
N~S205 was also formed during the reaction.
(3.5)
This reaction becomes significant especially at temperatures lower than l00"C.
3.1. SINGLE PELLET MOMENT METHOD FOR THE ANALYSIS OF

S02 - ACTIVATED SODA REACTION KINETICS
The single pellet moment technique which was originally developed by Dogu and Smith
(1975,1976) for the evaluation of diffusion and adsorption parameters in porous solids, was
extended to reaction systems and used for the kinetic analysis of S~-activated soda reaction
(Dogu et ai, 1986). In this technique, an inert carrier gas (helium) flowed over two end faces of
a cylindrical soda pellet placed into the single pellet reactor (Figure 11).
SO pul se
2
He
tHe
Figure 11. Schematic diagram of single pellet reactor.
Details of the experimental set up were reported elsewhere (Dogu et aI, 1986). Sulfur dioxide
was introduced as pulses into the stream entering the upper chamber. Part of the carbon dioxide
formed by the reaction of S~ with activated soda left the pellet from the lower face and was
detected at the exit of lower flow stream with a TC detector. It was shown that no unreacted S02
left the pellet from the lower end face at the initial stages of the reaction. The response peaks of
CO2 were then analyzed to determine the rate parameters of the reaction system using the
moment technique. Other sets of pulse response experiments were repeated with N2 and CO2
492
tracers to evaluate the tortuosity and adsorption equilibrium constant of CO2 • The mass
conservation equations for the product gas CO2 and the reactant S02 in the cylindrical activated
soda pellet are given below:
S02 conservation equation:

acsa a2c (3.6)
'--;u-'= D....~
(e + pp K) aX? - Pp
k Cso,
CO2 conservation equation:
aCeo aCeO
2
(3.7)
(e + Pp
K)--'
c at = D<.c -aX?
-'+ pP k Cso,
Solution of these equations in Laplace domain with the boundary conditions of the single pellet
system gave the moment expressions. Results indicated that reaction of S02 with activated soda
is very fast and some S02 was adsorbed on NazS03 and migrated over the surface. It was
reported that about 30 % of the diffusion flux of S02 was due to surface diffusion. This technique
was further developed by Dogu et al (1988) to investigate the changes of diffusion and adsorption
parameters during the reaction. It was shown that the initial value of the Thiele Modulus was 8.6
with a pellet of 3 cm in length and porosity 0.56 at 200"C. The pore structure of the pellet was
considerably altered during the reaction and as a result, the effective diffusion coefficients of both
S02 and CO2 were decreased to about one third of their initial values at the end of the reaction.
The initial value of effective diffusion coefficient of S02 at 200"C and 1 atm pressure was 0.23
cm2/s while its value decreased to 0.072 cm2/s at the end of the reaction. Results of these studies
showed that structural variations caused significant changes in adsorption characteristics of S02
and CO2 as well as in diffusion resistence during the reaction.
4. Dry Processes For S02 Removal
The dry S02 scrubbing processes have gained importance in recent years due to their simplicity,
lower capital costs, less operational difficulties and less power requirements compared to
conventional wet scrubbing systems. One of the most common dry processes is the use of
limestone in the fluidized bed combustors. Use of deactivation model for S02 removal in
fluidized beds is mentioned in Section 2.
Dry injection of limestone and hydrated lime particles in desulfurization processes is currently
under active development (Stouffer et ai, 1986; Weinstein, 1989; Yoon et ai, 1986). Furnace dry
sorbent injection for S02 control consists of injecting a dry pulverized calcium based material
directly into furnace cavity of a coal fired boiler. The product CaS04 and unreacted sorbent
particles are removed from the furnace together with fly ash. Fan and Satija (1984), Milne et al
(1990b) Krammer and Staudinger (1991) reported kinetic data and model expressions which are
applicable to dry injection systems.
Dry injection of activated soda (trona or nahcolite) after the combustor is an attractive
alternative due to its much higher reactivity at typical flue gas temperatures (l50°C). This allows
the use of bag filters to be used for collection of particles as well as further sorption of S~ on
493
activated soda. Research is under progress for the post furnace S02 removal by dry injection of
calcium based sorbents. In this case, a high relative humidity is required at the point of injection.
Use of spray driers for S02 scrubbing is another dry process which found wide industrial use.
The most important parameter for limestone based spray drier scrubbing of S02 is the relative
humidity. It is reported in the literature that over 90% S02 removal can be achieved in a spray
drier if the relative humidity is over 70% (Stromberg and Karlson, 1988; Kaplan and Felsvang,
1980; Sahar and Kehat 1991). Another important parameter is the Ca/S ratio. Usually this ratio
is chosen between 1.5-2.0. In spray drier scrubbers slaked lime, limestone, dolomite or soda ash
may be used as absorbents (Felsvang, 1986). In a recent study it was shown by U"ar and Dogu
(1990) that natural soda can be very effectively used in a spray drier scrubber to achieve SOz
removal efficiencies reaching to 100 % at much lower relative humidities than limestone
processes.
An economical comparison of dry proceses with conventional regenerable and nonregerenable
processes indicated that (Dogu et al 1988) the capital costs of dry processes are lower. The
capital cost of dry injection was estimated to be about 1/5 th of the conventional wet lime
scrubbing system. Fixed cost of spray drier scrubbers was found to be about 20% less than the
conventional non-regenerable systems. Regenerable wet processes have much higher capital costs.
S02 reduction cost of a spray drier scrubbing unit was also estimated to be about 20% less than
the corresponding cost of a conventional wet lime scrubbing system is around 0.15$/kg of S~
removed. Among all the processes dry injection was found to be the least dependent on the load
factor.
In recent years number of studies were reported in the literature for the simultaneous removal
of S02 and NO, from flue gases. Centi et al (1990) reported kinetic study conducted using a
copper based sorbent catalyst. Simultaneous S02 and NO, control was also achieved in a
circulating fluidized bed by the injection of Ca(OH)2 sorbent and iron sulfate catalysts
(Weisweiller et aI, 1991). Number of other catalytic processes were also reported.
Acknowledgements: Partial support of NATO SFS Grant through NATO-TU Air Pollut Project
is gratefully acknowledged. The authors also wish to acknowledge the contributions of
Mr.G.Olmez, Mr.I.Ar and Mr.M.Balbasi in the preparation of this manuscript.
Nomenclature
a : activity defined by Eq.2.32

ac :unit cell size (Eq.2.48)
ap :pore radius
a 'p : radius corresponding to reaction interphase (pore model)
C : gas phase concentration of S02 in pores
Co : bulk concentration gas concentration of S02
C. : defined by Eq.2.13
C, : solid phase concentration of S02
C,o : solid phase S02 concentration at r=rgt
D. : effective pore diffusion coefficient
D, : diffusion coefficient of S02 through product layer
D', : true solid pahse diffusivity of S02
494
DT : combined diffusivity (Eq.2.40)

DSA : molecular diffusivity of S02
D KS : Knudsen diffusivity of S02
E : activation energy (Eq.2.S1)

F : reaction interphase-area per unit pellet volume (Eq.2.19)
k. : surface reaction rate constant (m/s)
K'o : equilibrium constant (Eq.2.12)
Ko : equilibrium constant (Eq.2.11)
Me : molecular weight of CaO
M. : molecular weight of CaS0 4
Mee : molecular weight of CaC0 3
rp : radial coordinate in the pore model
r : radial coordinate in grain
re : core radius
rg : initial grain radius
rgl : grain radius at time t
R : radial coordinate in pellet

Ro : pellet radius
R. : reaction rate (moles/time pellet volume)
R'. : surface reaction rate (moles/time. area)
Sg : surface area per mass of solid
SOg : initial surface area per mass of solid
We : weight fraction of CaO in calcined stone
X : local fractional conversion
X : average fractional conversion
Y : defined by Eq.2.6S
Z : defined by Eq.2.66
Greek Letters
(3 : deactivation rate constant (Eq.2.33)

I: : pellet porosity
1:' : pellet porosity at R=Ro
I:j : micropore porosity
1:. : porosity of CaS04 layer

fo : initial value of pellet porosity
'Y : defined by Eq.2.23
7]. : local effectiveness factor in the pellet
T : tortuosity factor
Ppo : initial value of pellet density
Pp : pellet density
Pe : density of CaO
P. : density of CaS04
<1>0 : initial value of Thiele modulus (Eq.2.34)
<l>p : defined by Eq.2.67
495
REFERENCES
Ar,i.(1991) "Kinetics of S02 capture with limestone", continuing Ph.D.Study, Gazi Uni.,
Ankara
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Bhatia, S.K. (1985) "Analysis of distributed pore closure in gas-solid reactions", AIChEI, 31,
642-8.
Bhatia, S.K. and Perlmutter, D.D. (1980) "A random pore model for fluid-solid reactions",
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Bhatia, S.K. and Perlmutter, D.D. (1981) "Effect of pore structure on fluid-fluid reaction:
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(1972) "Properties of carbonate rocks related to S02 reactivity", Environ. Science Techol.,
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Centi, G., Riva, A., Passarini, N., BrambiIIa, G., Handett, B.K., Delman, B. and Ruwet,
M. (1990) "Simultaneous removal of S02/NOx from flue gases. Sorbent/calatyst design and
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limestones or dolomites",Chem.EngJ., 28, 151-62.
Fan, L.S., Satija, S., Kim., B.C. and Nack, H. (1984) "Limestone/dolomite sulfation in a
vertical pneumatic transport reactor", Ind. Eng. Chern. Process Des. Dev., 23, 538-45.
Felsvang, K. et al (1988) " Update on Spray drier FGD experience in Europe and in the
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Missouri.
Ferguson, O.L. and Rissmann, E.F. (1970), 2nd Int. Clean Air Congr., Washington.
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solid reaction", Chern. Eng. Sci., 34, 1072.
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Kaplan, S.M. and Felsvang, K. (1981) "Spray drier absorption of S02 from industrial boiler
flue gases', AIChEl Symp. Ser., 54, 23.
Kimura, S. and Smith I.M. (1987) "Kinetics of the sodium carbonate-sulfur dioxide
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Koyuncu, D. (1985) "A kinetic study for the sorption of S02 on calcined limestone", M.S.
Thesis, METU, Ankara.
Krammer, G. and Staudinger, G. (1991) "S02 removal from flue gas with dry limestone",
Conf. Gas Separation and Purification Int., Austin Texas, 22 April.
Lee, D.C., Hodges, I.L. and Georgakis, C. (1980) "Modelling SClz emmisions from fluidized
bed coal combustors", Chern. Eng. Sci., 35, 302-6.
497
Lee, D.C. and Georgakis, C. (1981) "A single Particle-Size Model for Sulfur Retention in
Fluidized Bed Coal Combustors", AIChEJ, 27, 472-81.
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calcium oxide with sulfur dioxide", Chern. Eng. Sci., 40, 423-433.
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498
in the circulating fluidized bed", Fourth World Congress of Chemical Engineering

Preprints, p. 3.5-14, Karlsruhe, Germany.
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in a fluidized coal combustor", Chern. Eng. Sci., 37, 167-74.
REMOVAL OF S02 WITH LIME SLURRY IN A SPRAY DRYER
GULSEN DOOU, GOKHAN OLMEZ

Gazi University
06570 - Ankara - TORJ(jYE
TIMUR DOOU
06531 - Ankara - TORKIYE
ABSTRACT. Due to its lower capital cost, lower energy consumption and less operational and waste
disposal problems, spray drier scrubbers gained importance in recent years for flue gas desulphurization.
In this work, S02 removal efficiency of a spray drier was investigated at different relative humidities and
for different Ca/S mole ratios. The experimental results showed that increase of both relative humidity and
Ca/S ratio caused significant improvements in S02 removal. Over 75 % S02 removal was achieved at a
contact time of less than a second at a relative humidity of 65 % for a Ca/S ratio of two. Addition of some
additives such as H20 2 and FeS04 caused a significant decrease in CaS03/CaS04 ratio in the product.
1. Introduction
There are hundreds of desulfurization processes proposed in the literature. These processes may
be classified as wet and dry (patkar, 1981). Spray drier absorption is a semi-wet system in
which an alkali slurry is fed to the unit and the reaction product is collected dry. This process
is generally applied to power stations. It is reported by Felsvang et al (1988) that spray drier
scrubbers are in operation in power plants of over 10,000 MWe in different parts of the world.
These absorbers are generally coupled with fabric filters or electrostatic precipitators to collect
particulates. Spray drier absorption is experienced as a wet-dry system with different reagents
such as lime, limestone, trona (natural soda) and ammonia.
Sulfur dioxide scrubbing with a spray drier has attracted wide interest in the world due to its
ease in operation and its lower operating and investment costs than the conventional wet
scrubbers (Kaplan and Felsvang, 1980). Also, the dry product of this process creates a smaller
disposal problem than the disposal of wet sludge from a wet system. Lime is a commercial
reagent for S~ scrubbing in the spray drier utility industry. Lime is more expensive than
limestone, so that the cost of the lime changes between five to ten times that of limestone
(Klingspor et ai, 1984). In spite of this advantage, most of the spray drier absorbers consume
lime due to its higher reactivity. Additionally, the effect of fly ash on the removal of S~ was
499
H.l. de Lasa et al. (eds.). Chemical Reactor Technology for Environmentally Safe Reactors and Products. 499-505.
© 1993 Kluwer Academic Puhlishers.
500
investigated by Peterson and Karlsson (1988) and reported that fly ash does not play an important
role. One of the earlier commercial dry flue gas desulphurization processes was operated by
MikroPuI Corp. (Reninauer et ai, 1983) using lime slurry with a fabric filter. The removal
capacity was 97% with a Ca/S ratio of over 2.6.
Stromberg and Karlsson (1988) reported that S02 scrubbing using limestone reached up to 85%
efficiency. These efficiencies correspond to the overall removal of S02 in the spray drier and the
fabric filter. To increase the removal of S02 and to decrease the consumption of lime, effects of
some additives were also investigated. Tom and Peterson (1988) worked with fly ash addition
to lime slurry. According to their results, when the relative humidity is over 60% and solid
content is close to 15%, S02 removal in flue gas is around 70%. On the other hand, chlorine
plays an important role in consumption of lime (Blythe et ai, 1983). It was reported by Karlsson
et al (1983) that when calcium chloride was present in lime slurry, an increase in the removal
of S02 was observed. It was also shown that the initial reaction rate increased when calcium
chloride content increased. S02 removal efficiency reached 100 % for a Ca/S of 1 using lime
slurry with calcium chloride of 10 % by weight when the spray drier is followed by a fabric
filter. Therefore, calcium chloride is proposed as the most important candidate for S02 scrubbing
in wet-dry systems.
One of the important stages for a successful operation of a spray drier scrubber is slurry
preparation in lime processes. As lime cannot be simply dissolved in water it must be ground.
Particle size and slaking temperature are important parameters. Sahar and Kehat (1991) give
1.46Jlm as recommended average particle size for the lime slurry to be fed to the system. Unless
the slurry is in a homogeneous form, the extensive surface area required for a complete gas-solid
contact cannot be achieved by atomization. Plugging problems may occur in pipes in which lime
slurry flows.
Feeding, atomization, droplet-gas contact, evaporation and product collection constitute spray
drying absorption. Slurry is fed to the top of the drier and atomization is provided by a nozzle.
Droplets having high surface area contact the S02 around the nozzle in a hot medium. Reaction
and evaporation occur simultaneously. In spite of the very short contact time, S02 removal
efficiency is high. Petersen et.a!. (1988) suggests 11 seconds as the time given for a pilot plant
operation. If a bag filter is used after the spray drier, further sorption is achieved. Air flow rate
determines the residence time in the unit, and it is a very important parameter. One of the
parameters effecting the removal efficiency is relative humidity, provided lime is used as the
reagent. Another alternative reagent is trona (natural soda). Trona has higher reactivity than lime
and limestone. When trona is used for S02 scrubbing in the spray drier, the gas-solid reaction
does not require high relative humidity during the operation. In this case, relative humidity is not
a very important factor. It was shown by Ucar et al (1990) that the removal efficiency of S02
in the spray drier without bag filter reached 100% at a relative humidity of less than 5% with
a Na/S ratio of 2.5. This is due to the rapid reaction of S02 with soda ash in dry form at around
100"C.
Another important parameter is the Ca/S ratio in the spray drier. Formation of CaSO) and
CaS0 4 causes pore plugging and conversion of CaO into products stops before all the reactant
is depleted. In S02 removal with CaO in a dry system (fluidized beds etc.) at high temperatures,
the Ca/S ratio was usually selected between two and three. On the other hand, in a spray drier
high conversions were achieved in the presence of moisture, and the Ca/S ratio is generally kept
below two.
This paper presents data on the removal of S02 with lime in a spray drier. The effect of some
chemicals added into the slurry on CaSO/CaS04 ratio in the product was also investigated.
501
2. Experimental
In this study, the limestone used was obtained from the Goynuk region of Bolu in Turkey.
Limestone was ground to about 1 mm in diameter before calcination. Calcination was carried out
at 900"C in a muffle furnace then the calcined solid was further ground. Chemical composition
of the limestone used in this work is given in Table 1.
Table 1. Chemical composition of limestone used.
Species Weight (%)

CaO 53.1
MgO 1.1
R20 3 0.2
Si02 2.2
Drying & Ignition Loss 43.4
Sulfur dioxide removal experiments were performed in a laboratory scale spray drier (Lab-
Plant SD-04). The air flow rate was kept constant at 16.3 m3Jh during all experiments. The S02
content of the gas was adjusted to 0.2 %. Simulated flue gas was prepared by mixing pure S02
with air. Relative humidity in the spray drier was adjusted by changing the flow rate and
composition of the liquid feed rate. The lime slurry was prepared by mixing the mixture on a hot
plate at 90"C for about an hour. A schematic diagram of the unit is given in Figure 1. The
COMPRESSOR
TO VEHT
ROTAMETER
~
HOT PLATE:
Figure 1. A schematic diagram of the unit used

502
diameter of the nozzle used for droplet formation was 1 mm. Hot gas containing S02 reacted with
humidified lime particles around the nozzle. Dry product was collected in a bottle. A cyclone
connected to the drier was used to collect the particulates. Experimental conditions are given in
Table 2.
Table 2. Data sheet for the scrubbing of SOz
Specifications of spray drier used
Height (mm) 1010

Width (rom) 660
Power rating (kW) 3.1
Nozzle (mm) 1
Compressor speed (m3/h) 1.13 - 1.181
Air flow rate (m 3 Jh) 16.3
Maximum air temperature("C) 250
Experimental conditions
Solid wt fraction in the slurry 6-19

Outlet temperature ("C) 60 - 87
Adiabatic sat. temp.("C) 43 - 56
Slurry feed rate (mIls) 0.204 - 0.505
S02 concentration in air (%) 0.2
Chemical analyses of products were performed by means of using a gravimetric method. A

Leco sulfur determinator was used to analyze total sulfur in the product.
3. Results and Discussions
The experimental data clearly showed that relative humidity and Ca/S molar ratio played very
important role on the removal of S02 with lime slurry at given experimental conditions. It was
shown that the relative humidity is one of the most important parameters in lime-based scrubbing
of S02. An increase of the relative humidity caused a significant increase in the removal of S02.
This variation is shown in Figure 2. For a contact time of less than one second in the scrubber,
S02 removal efficiency reached 76% at a relative humidity of 65% and a Ca/S molar ratio of
2.0. The ratio of Ca/S was also found to be an important parameter, especially at high relative
humidities.
The dependence of S02 removal on Ca/S mole ratio is illustrated in Figure 3 for two different
relative humidities. At low values of relative humidity, the effect of Ca/S ratio is small. For a
relative humidity of about 9%, S02 removal efficiency remained below 30% even for a Ca/S
ratio of 3. On the other hand, for higher relative humidities a significant increase is S02 removal
was achieved with an increase in Ca/S ratio.
Comparison of effects of these two parameters indicated that the effect of relative humidity is
higher than the effect of Ca/S ratio on spray drier S02 sorption efficiency. The reaction between
sulfur dioxide and lime requires a certain amount of humidity. It means that this gas-solid
503
reaction occurs in a wet medium. This reaction does not proceed at an appreciable rate at spray
drier temperatures in a completely dry system.
The outlet temperature of the spray drier is between 60" and l00"C. In this temperature range
the most abundant product is CaS03 • The ratio of CaS03 to CaS04 was found to be around 3 in
most experiments. This result is consistent with the results reported by Stromberg and Karlsson
(1988). Further studies illustrated that the CaSO/CaS04 ratio could be decreased with additives
in the lime slurry. Addition of some chemicals such as H 20 2, FeS04 , or V20 S into the slurry
caused a decrease in CaSO/CaS04 ratio in the product. With H 20 2 addition this ratio was
decreased from approximately 3 to 0.15 (Figure 4).
In the experiments conducted with additives the amount of additive was kept around 10 % of
the solid material. From the point of view of solid waste disposal and possible utilization of this
product, the CaS03 /CaS0 4 ratio plays an important role. In general, CaS03 is not desired in the
product. The contact time in the spray drier was less than one second. On the other hand,
residence time in a conventional spray drier is between 5 and 12 seconds. Results of this work
showed that over 70% S02 removal could be achieved in such a short contact time. This indicates
that most of the sorption reaction takes place in a small region around the nozzle. Reaction
between S02 and droplets takes place with a simultaneous evaporation. After the drying is
completed the reaction probably continues, but at a relatively slower rate in the presence of
moisture. If the relative humidity is not sufficiently high, no further sorption of SOz can be
expected after completion of the evaporation step.
100
." C<J/S: 1.9 - 2.0

S02!( 02"
A.F.R.: 16.am~/h
60
o
70
~
60
-' 0
~
::.
00
w .j()
0
0::
N 30
0 0
V) 0
20
0
10
0
0 10 20 30 .j() ro 00 70 00 90 100
Relative Humidity (51;)
Figure 2. The effect of relative humidity on the removal efficiency of SOz

504
100
90 <>
R.H. : 9"
g 80 Tout - Twa : -43OC
0
0
70
-'
<l:
R.H. : 60 - 71 ~
> 60 Tout - lwet ( t2°C

0
:::< 50 0
w
0::: 40 0
N 30 <)
0 <>
(f) 20
0 <>
<}
10
<> <>
0
0.0 0.5 1.0 1.5 2.0 2.5 3.0
Ca/S
Figure 3. Effect of Ca/S ratio on S02 Scrubbing.
NO
ADDITIVE
-
"
0
:g
a::
.".
0
if> 2
"
U
"'-
"> FeS04 v2 0 S
0
'"
0 .---- r-
u
H202
0
r----l
Figure 4. The effect of additivies on CaSOiCaS04 ratio.
4. Conclusions
As a result of this experimental study on the removal efficiency of S02, it was concluded that the
relative humidity should be greater than 60% and the difference between outlet temperature of
505
the drier and adiabatic saturation temperature should be less than 1000C for high S02 removal
efficiencies. In the mean time, the CaS03 /CaS0 4 ratio in the product can be significantly
decreased by using appropriate additives such as H20 z. It is also concluded that most of the
reaction took place in a narrow region near the nozzle.
ACKNOWLEDGEMENTS: Partial support of NATO SFS Grant through NA TO-TU Air Pollut
Project is gratefully acknowledged.
REFERENCES
Blythe, Gary et al (1983) "Field Evaluation of Utility Dry Scrubbing System", EPA/EPRI
FGD Symp., New Orleans, Louisiana
Felsvang, K. et al (1988) "Update on Spray drier FGD experience in Europe and in the
people's Republic of China', 1st Combined FGD and Dry S02 Control Symp.St. LOUIS,
Missouri.
Felsvang, K. (1986) "Flue Gas Desulphurization by Spray Dryer Absorbtion - a Flexible
and Worldwide Applicable Technology", China Enviro 86, Beijing, China
Kaplan, M.S. and Felsvang, K. (1980) "Spray Dryer Absorbtion of SOz from Industrial
Boiler Flue Gas", AIChE Symp. Ser., 201, 76.
Karlsson, H.T., Klingspor, J., Linne, M. and Bjerle, I. (1983) "Activated Wet-Dry
Scrubbing of S02'" APCA Journal, 33, 1, 23-28.
Klingspor, 1., Karlsson, H.T. and Bjerle, I. (1983) "A Kinetic Study of the Dry S02-
Limestone Reaction at Low Temperature", Chem.Eng.Commun., 22, 81-103.
Klingspor, J., Stromberg, A., Karlsson, H.T. and Bjerle, I. (1984) "Similarities between
Lime and Limestone in Wet-Dry Scrubbing", Chem.Eng.Process., 18, 239-247.
Patkar, N., A. and Kothari, S., P. (1981) "An Evaluation of SOz Control Systems for Steam
Generators at California Oil Fuels", AIChE Symp. Ser., 211, 77, 27-39.
Petersen, T., Peterson, J., Karlsson, H.T. and Bjerle, I. (1988) " Physical and Chemical
Activation of Fly Ash to Produce Reagent for Dry FGD Processes", First Combined FGD
and Dry SOz Control Symp., St. LOUIS, Missouri.
Petersen, T. and Karlsson, T. (1988) "The Significance of Fly Ash in Wet-dry Scrubbing of
S02 ", Chem.Eng.Techno!., 11,298-305.
Reinauer, T.U., Monat, J.P. and Mutsakis, M. (1983) "Dry FGD on an Industrial Boiler",
AIChE Symp. Sec., 74-81.
Sahar, A. and Kehat, E. (1991) "S02 Removal from Hot Flue Gases by Lime Suspension
Spray in a Tube", Ind.Eng.Chem.Res., 30, 435-440.
Stromberg, A., Karlsson, H.T. (1988) "Limestone Based Spray Dry Scrubbing of SDz",
Chem.Eng.Sci., 43(8), 2095-2102.
Uear, C. and Dogu, G. (1990) "Mechanism of S02 scrubbing with trona solution in a spray
drier", 40th Can. Chern. Eng. Conf., Halifax, Canada.
ENGINEERING ASPECTS OF RECIRCULATING FLUIDISED BED COMBUSTION
C.BRERETON, J.R.GRACE, C.J.LIM AND J.ZHU

University of British Columbia
2216 Main Mall, Vancouver,
British Columbia, Canada
V6T 1Z4
ABSTRACT. Circulating fluidised bed combustors are increasingly commonly used for environmentally
sound steam generation from fossil fuels and other low value energy sources. Low uniform combustion
temperatures and air staging produce low NO, emissions, while sulphur oxides may be scrubbed cheaply
by in-bed sorbent addition. However, optimal design of circulating fluidised bed boilers for maximum
multi fuel capability and turndown is hindered by a lack of fundamental understanding of the fluid and
particle mechanics. This paper discusses how an understanding of the fluid mechanics may be used to
scale-up from pilot plant systems to full scale combustors. Key engineering aspects, geometric optimisation,
fluid mechanics scale-up, and heat transfer coefficient prediction are each discussed. Observed pollutant
formation trends are also rationalised in terms of the solids distributions in the circulating fluidised bed.
1. Introduction
Circulating fluidized bed combustion (CFBC) has attracted considerable attention during the past
decade. CFB boilers are now capturing a significant fraction of the market for industrial and
utility scale boilers. At the same time, there is widespread interest in application of circulating
bed boilers for combustion of a wide variety of unusual fuels and waste materials.
Circulating fluidized bed combustors differ from conventional (bubbling) fluidized bed
combustors in having higher superficial gas velocities (typically 5-10 mls as compared with
1-3 m/s) and higher overall voidages (typically 0.9 to 0.98 compared with 0.6 to 0.75). In
addition, the particles are finer (typically 200 to 350 micron in mean size compared with 1 to 3
mm for bubbling fluidized bed combustion operations). In view of the finer particles and higher
superficial gas velocities, there is considerably more carryover of particles from the reaction
chamber of circulating beds, and it is therefore essential to provide for continuous and efficient
return of solids to the base of the reactor. The return system, usually consisting of a primary
cyclone and a sealed return line such as a fluoseal or L-valve, is an integral part of the reactor.
Because of the high velocities, erosion of the tube surfaces would be a severe problem for any
horizontal surfaces inside the reactor chamber. Hence, internal surfaces are avoided low down
in the reactor and heat is extracted via membrane waterwall surfaces forming the containing
surface.
Circulating fluidized beds share a number of advantages with bubbling beds. These include the
following:
507
508
(a) Sorbent materials like limestone or dolomite can be used as bed materials to capture sulphur
in situ, reducing the emissions of S02 and S03.
(b) Because of the low temperature of combustion (typically 750-950°C), emissions of NOx are
also reduced considerably compared to e.g. pulverised firing.
(c) Heat transfer coefficients are high between the bed or suspension and cooling surfaces,
leading to compact equipment.
(d) The combustors are able to handle a wide variety of fuels (particulate, liquid or gaseous) in
a flexible and interchangeable manner.
In addition, CFBC units have been claimed to have a number of advantages over bubbling beds,
in particular:
(a) Combustion efficiencies are said to be higher, typically 98-99% compared with 90-96%.
(b) Because of the finer sorbent particles, sulphur capture is generally better.
(c) Improved lateral mixing of solids leads to a requirement for fewer feed points, a major
source of expense and engineering difficulties for underbed-fed bubbling bed boilers.
(d) The use of staged air introduction in CFB boilers leads to further reductions in NO,
emissions.
(e) Turndown and load following are claimed to be superior in CFBC units. Turndown can be
achieved either by means of varying the suspension density for membrane surfaces on the wall
of the reactor or by varying the proportion of solids circulated to an external cooler.
(t) The higher superficial velocities in CFBC units lead to a requirement for smaller combustor
cross-sectional areas, although this is offset by the need for greater height. There are overall cost
advantages for large utility boilers but not for smaller scale industrial units.
Disadvantages of circulating beds appear to be that they require more solids preparation due to
the finer materials required and that capital costs tend to be somewhat higher in some cases.
The original impetus for CFBC units and much of the development work have come from
Europe, especially West Germany, Sweden and Finland. However, CFBC units are now being
marketed vigorously in North America, Japan and worldwide. Units as large as 150 MWe have
been installed and are under construction.
The study of CFB combustion at UBC has progressed from study of generalised low
temperature hydrodynamics to fuel specific combustion studies in a high temperature pilot plant
unit. The low temperature unit is shown in Figure 1. It comprises a 152 mm ID by 9.3 m tall
plexiglas riser transporting the solids from the distributor (1) to the riser exit (2). Gas and solids
leaving the riser section pass to a modified cyclone (3) which permits extremely high solids fluxes
by elimination of the conical section. The solids fall into a storage zone which may be either a
gently fluidised or a packed bed. From this storage zone an L-valve, penetrating into the storage
zone, and forming an "L" from points (4) to (5) to (1) permits solids reintroduction to the riser.
The flow rate of solids is controlled by aeration at a single point (1). Gases leaving the primary
cyclone undergo further cleaning in a secondary cyclone before discharge to atmosphere. This
simple plexiglas unit has provided much of the fundamental hydrodynamic data which is discussed
in this paper. More details about this set up can be found in Brereton and Grace (1992), or
Brereton (1987).
The high temperature combustion pilot plant is shown in Figure 2. It has a 152 mm by 152 mm
square cross section and a height of 7 m. Thoroughly instrumented with pressure transducers,
thermocouples and gas sampling probes along its axis, it permits high temperature hydrodynamic
studies in addition to fuel testing. This unit is described in detail by Grace et al (1990). In essence
it consists of the same components as the cold unit; however, the storage bed found in the cold
unit is eliminated and changes in inventory in the riser are matched by variations in the solids
level in the L-valve. The principal components in the primary circulation loop are: the main riser
509
Ai,-Out
Exit
Impact
Flow
Meter
Riser
Column Modified
Butterfly
Valve
Storage
Bed
l·Valve
Secondary Tangential
Air Opposed
5 l·Valve
Aeration
Blower
Air
Figure 1. Schematic of the cold recirculating tluidised bed hydrodynamic test unit. The unit is
0.152 m dia. with a total height of 9.3 m.
510
(i) THERMOCOUPLE
o PRESSURE TAP
----------
Figure 2. Schematic diagram of the recirculating fluidised bed combust

ion pilot plant. To the
left are the feed systems, in the centre are the 0.152 mm square riser,
hot cyclone and L-valve
return, on the right are flue gas coolers and a baghouse for particulate
removal.
5ll
combustion section (1); the primary cyclone (2); and the L-valve (3). Gas exiting the primary
cyclone is cleaned by the secondary cyclone (4), and then passes through heat exchange surfaces
(5) into a baghouse (6) for final dust removal prior to discharging into a stack. Solids captured
by the secondary cyclone are picked up by a venturi eductor (7) and returned pneumatically to
the reactor. The same pneumatic air picks up the feed solids (usually coal and limestone), which
are fed from the hoppers (8) by metering rotary valves (9).
2. Fluid Mechanics of Circulating Fluidised Beds
In the remainder of this paper key engineering findings regarding circulating fluidised bed
combustion as revealed by these pilot units, are discussed. In particular the paper focuses upon
the elucidation of microscale and macroscale flow structures and will indicate:
(i) how these can be predicted,

(ii) how they can be used to explain and predict other key parameters such as heat transfer rates
and pollutant emissions.
2.1. MACROSCALE HYDRODYNAMICS OF CIRCULATING FLUIDISED BEDS
In studying circulating bed fluid mechanics, new terms arise which are not relevant to either
packed or bubbling fluidised bed reactor design. In particular considerable effort has been spent
on forming a picture of how solids are distributed axially and radially over the reactor; this
distribution is called the suspended solids density profile. For catalytic reactors it is a key to the
contacting pattern of gas with solids. In combustion reactors the density profile gives the
distribution of burning coal particles necessary to establish heat release rates, heat transfer rates
and pollutant formation. In both cases it allows the overall pressure drop to be determined so that
gas moving equipment can be sized.
2.1.1. Radially Averaged Suspended Solids Density Profiles. In a bubbling bed with its relatively
well defined bed surface, although there are complex gas movement patterns through bubbles,
clouds and dense phase, it is at least clear where the solids are located and where the bulk of
gas-solids contacting occurs. This is not intended to diminish consideration of the possible
importance of freeboard reactions or heat transfer, which can sometimes be of considerable
importance e.g. see de Lasa and Grace (1979), George and Grace (1982). However, most of the
gas-solid reaction is confined to the bed in bubbling bed reactors. Hence, while significant
attention has been given to the role of the freeboard region, the basic discussions of fluid
mechanics focus upon the bubble and dense phases and their interaction. In contrast, in a
circulating fluidised bed there is no bed surface. Instead there is a gradual decay of the solids
loading with height as in the region below the TDH in the freeboard of a bubbling bed, but with
a much higher particulate loading, and stretching over the entire height of the reactor. This major
difference in underlying fluid mechanics creates a significant difference in approach to
characterisation of the system. The whole description process is one of describing the axially
variant transport flow through the reactor.
It is common to describe the axial distribution of solids in the CFB by a graph of radially
averaged suspended solids density versus height, commonly called the "density profile". It is
generally found by measurement of the distribution of pressure along the riser and recognition
that the suspended solids constitute the major contributor to the pressure drop. Assuming this to
512
be true, we can write:

Suspension density = - (lIg)(dP/dZ) (1)
where g is the acceleration due to gravity and (dP/dZ) is the axial pressure gradient. This
ignores accelerational effects and gas wall friction, but is accurate to within +- 15 % over much
of the riser. Detailed studies of the validity of the pressure gradient to density conversion have
been made by comparison of the results with e.g. capacitance probes and show good agreement,
except in the region where the solids enter and are subject to rapid acceleration (Weinstein and
Li, 1989). Unfortunately, the density profile tells us nothing about the radial variation in solids
loading.
In a transport system such as a circulating fluidised bed, for a fixed particle and system
geometry the independent variables are the gas velocity and the rate at which solids are fed or
returned to the base of the riser system. In a circulating bed the latter is conventionally called the
"solids circulation rate". It is important to be able to characterise the hydrodynamics as a function
of these two independent variables.
As discussed by Kobro and Brereton (1986), there are two practical types of CFBC design. In
the first, typified by the Lurgi and Ahlstrom systems, there is no controllable solids storage
inventory in the return systems. This is called a "Fixed Inventory System" and is shown in
Figure 3.
Solids separator
Solids separator
Dilute bed Dilute bed
Solids storage
hopper Secondary air
Secondary air
-t-----r- -1----1 Return line
wnh no
capacity for
solids return line
solids storage
i eg.l-valve
primatalr
or control of
Primary air return rate
Variable Inventory System Fixed Inventory System
Figure 3. Schematic diagram showing circulating fluidised beds operating on the Fixed and
Variable Inventory systems, (Kobro and Brereton, 1986).
In this case the circulation rate is not a controlled variable but is a function of the total system
inventory, the gas velocity and the ratio of primary-to-secondary air flow (often called the "air
split"). Whatever solids leave the top of the reactor are immediately returned to the base via a
cyclone (or other separation device) and return system. If the suspended solids density is
increased at the top of the unit, e.g. by increasing the total amount of solids in the system or
varying the gas velocity, then there is a resulting net increase in circulation rate.
The variable inventory system is somewhat different. In this case there is a particle storage
vessel located external to the riser which can hold the complete inventory of the CFB system. The
513
recirculation rate from this system can be controlled by a mechanical or non-mechanical valve.
The rate of solids flow to the riser can be controlled at any desired rate, which has some
advantages for control of certain reactions.
While there are practical differences between the operation of the two configurations,
mathematically they are similar because either system has fixed degrees of freedom. In the Fixed
Inventory System, setting the gas velocity and the system inventory establishes the density profile
and circulation rate. In the Variable Inventory System, fixing the gas velocity and the external
circulation rate establishes the riser inventory and density profile.
In this paper the discussion focuses largely upon systems where the gas velocity and circulation
rate are the independent variables. The results may be applied to Fixed Inventory systems by
crossplots of the variables.
Studies of density profiles in circulating fluidised beds have been made by many authors. e.g.
Li and Kwauk (1980), Yerushalmi and Avidan (1985). Typical density profiles in CFB systems
are shown in Figure 4.
,
Solids IRON CONCENTRATE ALUMINA FCC CATALYST PYRITE CINDER
circulation, 1J5 129
7J
kg/M2· sec
top 0
N
2
....
.s:: 3
on
.,..,
Q) 4
:0::
"0 5 ;>.
Q) ....
.,..,
p:) <.J
6 o ()
..... Q)
Q) Ol
:>--
:>C
7
til
OJ -
0111'\0-
•••• "'0'"
" 0 ..,..,fIlt\.4n ~ ~«
bottom 1.0 <l.e 0.9 1.0
0.8 0.9 1.00.' 0.9 La 0 •• 0.9
Va ida g e , £
Figure 4. Sigmoidal profiles of voidage versus height for different solids in circulating fluidised
bed. For each plot solids circulation rate is constant, gas velocity is the parameter, (Li and
Kwauk, 1980).
In all the cases shown the density decreases monotonically from the base of the reactor to the
exit. It is clear that at a fixed gas velocity an increase in the circulation flux of solids causes an
increase in the density of solids throughout the reactor, but particularly in the upper regions. The
lower part of the reactor appears to contain a denser phase whose density is less sensitive to
circulation rate variations. At a fixed circulation rate an increase in gas velocity causes a decrease
in solids hold up throughout the unit.
514
In an attempt to quantify this information in a design format, based on a semi-mechanistic

approach, Li and Kwauk (1980) proposed an equation for the voidage profile of the form:
In{( E - E. )/( E' - E)} = (-1/Zo) * ( Z - Z; ) (2)
where E is the voidage at distance Z from the top of reactor, Zo is a characteristic length, Zj is
the height of the point of inflection of the curve, and E. and E' the limiting voidage of the dense
phase and dilute phase, respectively.
This relationship adequately correlated the general sigmoidal form of the density profile found
by authors up to that time. However, it has proved to be limited in application to small units
within the range of available experimental data.
Experimental results of Brereton (1987) indicate that the sigmoidal approach is not always
applicable. Results from both the cold unit (0.15 m dia.) and the square hot combustor showed
startling effects of the riser exit configuration upon the hydrodynamics of the system. Figure 5
shows typical results illustrating this effect. This figure shows how, under identical conditions
of circulation rate and gas velocity, a change in the construction of the riser exit may drastically
affect the density profile. By restricting the exit it proved to be possible to create an internal
separation within the unit resulting in massively enhanced solids recirculation within the riser.
An immediately apparent effect of this is to disrupt the sigmoidal profile and create an increase
in solids density at the top of the reactor. Less apparent, but just as significant, is that the impact
of the exit is not restricted to its immediate vicinity; the exit affects the hydrodynamics all the
way to the reactor base. This has significant reactor design implications which are discussed later.
HEIGHT ABOVE DISTRIBUTOR • m

o°r-~ __~__~u~~__~__~~~~__~~~
Figure 5. A figure illustrating the impact of exit effects in circulating fluidised bed systems. The
lines show density profiles for identical conditions of gas velocity (7.1 m/s) and circulation rate
(73 kg/m2s) for an abrupt exit (circles) and a smooth exit (triangles). The solids are returned
1.98 m above the gas distributor causing the "nose" in the profile, (Brereton, 1987).
515
The exit effect results make it clear that a simple sigmoidal model for the density profile is not
sufficient to describe the physical reality. Rather, there are complex geometric effects which are
also important.
2.1.2. Practical Impacts of Exit Effects in Circulating Fluidised Bed Reactors. Exit effects in
circulating fluidised bed reactors have significance beyond their immediate influence on the
density profile and fan sizing. Properly understood, they have the potential to be used to optimise
CFB performance and minimise cost. This has been discussed by Brereton (1987). The arguments
are summarised below.
(i) CFB combustors from different suppliers utilise different strategies for control. In one design,
heat transfer surfaces are located in a bubbling bed heat exchanger located in the solids
recirculation loop external to the main combustor unit. A substantial fraction, or even all of the
heat, can be removed in this way. A key component of the operability of this design is to be able
to achieve high external circulation rates to supply heat to these exchangers. This can best be
achieved by providing a riser exit which minimises the internal reflection at the top of the riser.
If the exit promotes substantial internal circulation, then the necessary external recirculation will
not be achieved without extremely high pressure drops within the reactor; large fans are then
required. However, some internal circulation is desirable to promote aggressive solids mixing
within the riser. The exit must be designed to compromise between these two conflicting
demands.
Units such as the Studsvik Energy or Ahlstrom license systems do not possess external heat
transfer surfaces. In these cases the cost of the unit can be minimised by reducing the external
recycle of solids. This is best served by design of a very abrupt exit (or even an internal
separator) to maximise internal refluxing of particles. This requires a different exit design than
the previous case, with no conflicting demands other than erosion tendencies of the increased
internally refluxing stream.
(ii) Through its effect on the hydrodynamics, the exit also affects gas and solids mixing, key
parameters in catalytic reactor design. From a solids mixing perspective, at constant circulation
rate the smooth exit promotes a more uniform plug flow of solids while the abrupt exit generates
higher densities and backmixing.
Gas backmixing in a circulating bed is a complicated phenomenon, (Brereton et ai, 1988; Bader
et ai, 1988). In general, single parameter models, such as axially dispersed plug flow models,
have not proved adequate to describe the mixing behaviour accurately; however, they provide
good qualitative indicators of trends in mixing behaviour. Figure 6 (Brereton et aI, 1988) shows
the effect of exit type upon gas backmixing. Here, the total amount of axial mixing over the
length of a CFB column is described by a dispersion coefficient calculated from the variance of
the gas residence time distribution. Gas velocity was constant in the experiments. In catalytic
reactors what is often key is the amount of contacting occurring with the catalyst. This is closely
related to the total solids hold up or pressure drop over the reactor which is plotted as the
ordinate in Figure 6. This figure shows that for the conditions in question, for a given degree of
contacting, gas backmixing is minimised by use of an abrupt exit. This is rationalised by study
of Figure 7 which shows density profiles for abrupt and smoother exit systems with the same total
pressure drop. The smooth exit system is characterised by a dense phase at the base which
contributes disproportionally to the gas mixing and generates the observed behaviour.
In summary, there are many important effects of exit geometry for practical design of CFB
reactors. Some of the major impacts are shown in Table 1. As well as exit effects, the reactor
design is complicated by less significant impacts of gas and solid entrance locations and
516
20
0 ABRUPT EXI T
0
o SMOOTH EXIT
16
N
0
/
or-
>< 12
,-~~ 0 0
--2-
8
0
0
/
4
~
i
0/ C
00 20 40 60 80
Total Pressure Drop (mm Hg)
Figure 6. Plot of pseudo vessel dispersion number (D/UgL) for axial mixing versus total
pressure drop in a recirculating bed with two types of exits. (D = axial dispersion coefficient,
Ug = gas velocity, L = column length), (Brereton et aI, 1988).
DlSt.nl>ulor
Chok~d
dense
phllse
1000
Suspended Sohds Density (kUm3)
Figure 7. Diagram showing how similar total pressure drops in smooth and abrupt exit columns
result in different profile shapes. The smooth exit unit has a choked dense phase at the base
which may be a zone of increased gas backmixing.
517
Table 1. A tabulation of the impacts caused by exit geometry modifications upon reactor
performance.
Exit Geometry Effects In Circulating Fluidised Beds
Promotes high solids circulation rate (external) with a

uniform RTD (plug flow) at a low pressure drop.
Smooth Exit Ideal for certain catalytic reactions involving catalyst

deactivation; e.g. fluid catalytic cracking.
Also suited for flash pyrolysis.
Promotes vigorous internal mixing and high uniform

suspension densities at low external solids circulation
rates.
Abrupt Exit
Ideal for minimising recycle loop sizes and maximising
temperature unifomity and heat transfer in certain
CFB combustion systems.
Intermediate mixing, circulation rate, and suspension

density characteristics.
Intermediate Ideal for combustion units requiring external heat

transfer for control purposes; e.g. the Lurgi units
Geometry Exit which may require high external solids fluxes, but also
require good internal mixing for combustion efficiency
reasons.
geometries. These are discussed by Brereton (1987) and are not presented in detail here since the
effects are less significant with respect to design of environmentally friendly combustion reactors.
2.2. THE MICROSTRUCTURE OF CIRCULATING FLUIDISED BED COMBUSTORS
While the bulk density profile, characterised as a function of gas velocity, solids circulation rate
and exit geometry, contains sufficient information for fan sizing, it gives no true insight into heat
518
transfer or pollutant formation. These are related to microstructural aspects of the CFB system
and radial distribution of solids.
There are both gas and solids aspects to the microstructure of a CFB. The gas can be
characterised by the local velocity vector and the turbulent structure. The solids microstructure
is characterised by the local solids velocity and concentration, and by their variation with time.
Here we focus on the instantaneous measurement of local solids density and the interpretation of
those results. Other quantities are discussed in less detail.
Instantaneous local solids densities have been successfully measured in fluidised systems using
capacitance probes or fibre optic sensors, e.g. Hartge et al (1988), Herb et al (1989). The fibre
optic systems can also be used to measure local solids velocities, although the interpretation is
not entirely unambiguous.
Figure 8 shows a typical needle capacitance probe. An oscillating electric field is applied
between the needle and the grounded sheath which is part of the capacitance of a self tuning
resonant L-C circuit. The tuning frequency is of the order of MHz and self-tunes at a rate just
an order of magnitude less. Since the resonant frequency varies with the capacitance,
measurement of this frequency leads to measurement of the capacitance itself. The capacitance
in turn varies with the dielectric constant of the medium between the needle and the sheath,
providing an extremely rapid measurement of the nature of this medium. A large difference
between the dielectric constant of air and most fluid bed particulates allows the capacitance probe
to be calibrated to provide a fast response (> kHz) readout of the local suspension density.
Probe
320 ,I
I
3·2mmOD Sheoth
.Ifill 11
6.4mmOD Sheoth
Conductive
Transition Ceramic
Insulator
Figure 8. Section through a needle capacitance probe to show the basis of construction.
A capacitance probe was developed in our work (Brereton and Grace, 1992) based upon a
DISA capacitative pressure transducer system. It effectively measures the instantaneous
suspension density in an approximately 5 mm cubic zone surrounding the exposed needle. The
capacitance probe was used to study radial variations and the form of solids flow structures
present in the developing region of a cold circulating bed. Sand particles with a mean diameter
519
of approximately 180 microns, a size typical of circulating fluidised bed combustion inerts, were
used as bed solids.
A key part of the study was to attempt to resolve why slip velocities in a CFB may exceed
particle terminal velocities by several orders of magnitude. The most popular early theory was
that this occurs because of a hydrodynamic agglomeration phenomenon called "clustering"
(Yerushalmi et al, 1978). According to this model, particles do not behave individually but as
dynamic clusters of particles constantly forming and disintegrating. CFB phenomena have also
been explained by considering the structure as core-annular in nature. According to this model,
a core exists in which particles are transported vertically with slip velocities approximately equal
to their terminal velocities, while annular downflow occurs on the wall due to a wall effect. These
two contrasting theories of CFB hydrodynamics are illustrated in Figure 9.
C I.USl [H INC Con[ ANNUll\n
-~J~_ ..
': . I" ..":-
I
I'
'."
.; / -.-
annulus
-+- , t
[
lntermittenc y Intermittency
I
I [
Index
y I
I
Index
y [
I , I
o j o .;-t-'-:'
R R
Radius Radius
Figure 9. Idealised clustering and core-annular flow patterns and the corresponding plots of
intermittency index versus radius' (Brereton and Grace, 1992b).
Figure 10 shows how radial profiles of density develop along the first three metres of the
laboratory CFB unit. This is the region in which the flow structures are developing. The figures
show strong gradients in density from a maximum at the wall to a minimum on the centreline of
the circular cross-section unit. While this is partially consistent with a core-annular structure, the
nature of the solids flow at a point is not clear. The time averaged profiles do not distinguish
between a flow structure in which the density is steady with time and a flow in which particles
pass the probe as denser less frequent aggregrates. In order to make this distinction, the
instantaneous data were characterised in terms of an "intermittency index" defined as follows:
520
Standard deviation of density

fluctuations at a given point
Intermittency Index = _____________ (3)
Standard deviation of density
fluctuations for fully segregated
two-phase flow with identical
time mean density at the same point
The intermittency index defined above varies from a value of zero, for a uniform steady flow
of any mean density, to a value of unity for a flow of the same density in which the flow consists
of clusters of particles, at loose packed density, surrounded by particle free gas. Figure 11 plots
the intermittency index versus radial position and height in the developing flow region. Figure 12
shows instantaneous traces from the capacitance probe signal.
700
00 Symbol Height 1m)

600 \ 0 0·533
(
o
0
Symbol
l,gend
Uglm/sjGs(kg/m2s)
'1500
--
Ol
-'"
D. \ ~ ;i:~ j
° 0 6·5 62 400
~. ( o \
o,~
~ 0 V>
", I C
.\
'" 300
°
~ ~:. i
o
1
1
x I ·0200
~:
0..
\ 0 0 _____ 1
100
6\6\
o~ "-g---
°_____.0 ~R::::.Q=:::::::::~
',~~,~~~=~~~~~~=-~. 00
SUSP(HOEO SOLIDS D(NSfT'f • kg/m3
20 40 60 76
Distance From Wall (m m)
Figure 10. Development of radial profiles of point solids suspension density in a circulating
fluidised bed (Gas velocity = 6.5 mis, solids circulation rate = 62 kg/m2s). The left hand plot
shows the development of the radially averaged profile, (Brereton and Grace, 1992).
Figure 11 allows us to draw some important conclusions about the true nature of the CFB fluid
mechanics. From it we can infer that the overall flow structures are as shown in Figure 13. A
core-annular flow structure dominates, with particles carried up in the central core and travelling
down at the column walls. Along the height of the unit there is a net particle transfer from core
to annulus which creates the decrease in overall bulk density with height. Superimposed upon the
internal structure is a net flux through the unit which, depending upon the particles, gas velocity,
solids flux, and exit employed, may be large or small compared to the net internal circulation.
Typically, it is desirable that it be small to assure temperature uniformity. However, in reactions
where plug flow of solids is desirable, this may not be the case.
521
O\j
;>..
0·5
1] I
!04~\~ I
~
::::
0.3 ~6~6 0 /'
E o ____&.-
.e
I
0·2 "----0_'
C
Symbol Height (m)
o 0·533
0·1
o 1·448
6 2.362
oL-~-L~ __L - - L - i__~
o 20 40 60 76
Distance From Wall (mm)
Figure 11. Development of radial profiles of intermittency index for the profiles of Figure 10,
Brereton and Grace, 1992).
Underlying the overall core-annular flow structure is a complex developing microstructure. At

the base of the column, where the solids enter and are accelerated, the intermittency index is high
across the unit. This implies that, even in the more dilute core, hydrodynamic agglomerates are
forming and being destroyed. The density of these "clusters" approaches loose packed voidage
values. With increasing height in the CFB unit, as the radially averaged density decreases, the
clusters found in the core at the base are rapidly destroyed, giving way to a uniform dilute phase
core, as in a pneumatic transport reactor. The wall layer maintains a somewhat segregated
appearance, although it too becomes more uniform with increasing height. High in the reactor
the structure is a well developed core-annulus flow, but with intermittency maintained in the wall
layer. It is also important to note that cluster-type structures in the wall layer have a density
considerably lower than loose packed.
The above experiments show that CFB riser flow for group B particles consists of a complex
developing structure, with elements of cluster type flows at the base giving way to a distinct core
annular structure over the bulk of the unit. These results are reinforced by measurements of gas
velocity and solids velocity. Gas velocity profiles show strong radial gradients with gas
channelling up the dilute low-resistance core. Solids velocity measurements illustrated in
Figure 14 (Yang et al, 1991) show pronounced downflow at the wall and upflow in the centre.
It is important to understand the limitations of the above results. The experimental density
profiles have been developed for group B solids which are typical of those found in CFB
combustors and gasifiers. Group A particles such as fluid cracking catalysts may be circulated
with net fluxes an order of magnitude higher than group B particles. In these cases high radially
averaged solids densities are found throughout the length of the riser and, superimposed upon the
core annular structure, there is likely to be a clustering behaviour from top to bottom. The
522
situation throughout the column of group A solids is more like the base of the riser for the group
B case.
Distance Distance
From Wall. From Wall.
mm mm
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';12 ,;12
M M
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Figure 12. Traces of instantaneous density fluctuations at different distances from the wall for
profiles of Figure 10, height = 1.448 m, (Brereton and Grace, 1992).
523
DOWNFLOW UPFLOW CORE

WALL
LAYER
Net external
sOlids flux
Solids layer
with zero
thickness _
Developing
solids
layer
Solids
feed at
external
flux
Figure 13. Schematic diagram showing overall net flow patterns for solids in a circulating
fluidised bed. The diagram is simplified in only showing a unidirectional flux of solids from core
to wall at the top rather than a net flux in this direction.
10 .--------b-_c-I.90::-:-"'--. 10 10 b-6.21m
b -2.1Sm
G!Kg/m l . $]
o 6.1
o 2.9
q. 12.9
o 9 .•
o 15.-'
• 2-4.6
• 25.3
-IL-_L-_L-_L-_L-~
0.0 0.2 0.4 0.6 0.1 1.0 0.0 0.2 0.4 0.6 0.1 1.0 0.0 0.2 0.4 0.6 0.1 1.0
r/R r/R r/R
Figure 14. Mean solids velocity profiles in circulating fluidised beds in the developing flow
region. The profiles shown are for various circulation rates (Gs) at constant gas velocity (Ut).
Solids used were FCC with a mean diameter of 69 microns, (Yang et ai, 1991).
524
3. Fundamental Aspects Of Heat Transfer In Circulating Fluidised

Bed Combustion Systems
Heat transfer in circulating fluidised bed boilers occurs on two types of surfaces. The bulk of heat
transfer from the combustion side to the water side occurs on planar membrane wall surfaces
which shape the furnace. Heat may also be transferred to horizontal tubes located in external
bubbling bed heat exchangers. The latter may be treated using conventional bubbling bed heat
transfer correlations. These two surface locations are shown in Figure 15. This discussion focuses
entirely upon heat transfer to vertical membrane wall type surfaces. These are identical to the
surfaces found in more conventional boilers such as pulverised coal, oil fired and stoker systems.
Convection
Pass
Furnace
Heat remOV3 I
Water
Wall
fraction - F3
Heat remova I
fraction - Fl
Optional Fluid
---j'-"'V'VVV'--f---i> Bed Hea t
Exchanger
Heat removal
fraction - F2
Design Type FI F2 F3
Batelle-Riley 0.0 0.5 0.5
Lurgi/CE 0.0-0.5 0.0-0.5 0.5
Studsvik!B&W 0.5 0.0 0.5
Figure 15. Possible locations for heat transfer surfaces in industrial circulating fluidised bed
boilers and different commercial configurations. (Brereton, 1987).
Heat transfer in circulating beds occurs by a combination of mechanisms: solids convection,

gas convection, and radiation. Solids convection is dominant at low temperature with radiation
becoming dominant at high temperature and low suspension densities. Gas convection is a small
component of the total heat transfer for the particle sizes currently used.
525
The mechanisms of heat transfer are intimately related to the circulating bed fluid and particle
mechanics. Heat is released by reaction throughout the combustor volume. It is carried to the
steam-raising surfaces largely by convective flows of solids which have considerably higher
thermal capacity than the low density gas phase. Transfer of heat then occurs by contact of the
solids with the heat transfer surface in what is generally a downflowing wall layer.
Initial studies of circulating fluidised bed heat transfer show the importance of the solids in the
heat transfer process. Kobro and Brereton (1986) presented results for CFBC sized solids at
intermediate and combustion temperatures. These results suggest an approximately linear
dependence of the heat transfer coefficient for a short annular calorimetric section upon the local
suspension density. These results appear in Figure 16. Simple correlations for heat transfer
coefficients may be based upon this type of data, with radiation accounting for most of the
difference in heat transfer coefficient at elevated and ambient temperatures (WU et al' 1989a).
Assuming that the gas radiates as a grey cloud accounts for the radiation contribution adequately.
Simple correlations based on data from small probes, and in which heat transfer coefficients
are considered only as a function of suspension density and temperature, can lead to substantial
overprediction of the heat transfer coefficients for commercial boilers. This is because of a
neglect of the underlying hydrodynamics. The downflowing wall layer in a CFB, if it flows
substantially undisturbed for distances of the order of the length of the heat transfer surface,
generates a significant thermal boundary layer on the wall. This leads to a reduction in the local
and overall heat transfer coefficient from a short probe value. This is shown clearly in Figure 17
(WU et al, 1987) which iIIustrates how the heat transfer coefficient decreases from top to bottom
of a 1.53 m long membrane wall heat transfer surface, although suspension density remains
approximately constant, actually decreasing somewhat from bottom to top. Further data appear
in Figure 18, again suggesting complicated interactions of suspension density and distance along
the membrane wall.
Fundamental studies of the heat transfer process show the important relationship between heat
transfer processes and convective solids motion. Wu et al (1989b), made simultaneous
instantaneous measurements of heat transfer coefficients and solids density on plane wall surfaces.
Typical results appear in Figure 19, and these show the strong correlation between peaks in the
trace of heat transfer coefficient and peaks in the wall suspension density created by the arrival
of packets of particles at the heat transfer surface. Wu et al (1991) also made inferences of the
average residence times of clusters on the walI by cross-correlating signals from verticalIy
displaced probes to gain further insight into the wall layer.
It is natural to compare circulating bed heat transfer with bubbling bed heat transfer which has
been studied in considerable detail. This is an interesting comparison which provokes directions
for future development. Key points are:
1. The macroscopic flow structure in the circulating fluidised bed appears to be less stochastic
than in the bubbling bed and hence more amenable to fluid mechanic description by fundamental
means.
Expanding upon this idea, the direction of particle motion in a bubbling bed, while governed
by reasonably well-defined gulf stream motion, is not definitively in one direction at one point.
Hence, the heat transfer created on a surface due to this motion must reflect such variations and
is best simply described by an empirically derived mean contact time correlated, for example,
with the bubble frequency which is clearly related to renewal frequency. On the other hand, a
CFB has more clearly defined patterns of internal circulation over much of its height. Although
not steady, these flow patterns are better defined over much of the CFB than in a bubbling bed.
This has been shown by the relatively good fit of hydrodynamic models built on visualising the
526
,00
170 I'm
;;:
N
--"
2-
c
0
u
~
200
u
0
u
.e
~
c
"u
f-<
~
0
100
o ~--~----~--~----~--~
o 20 100 60 BO 100
Local bulkdensity Pb (kg/m3)
Figure 16. Variation of heat transfer coefficent to a 10 cm long calorimetric heat transfer probe
at two different temperatures and for two different particle sizes, (Kobro and Brereton, 1986).
800
~
~ Tsusp(C)
E 0 0 860
~ 0 0 407
X 0
...c 0
100 0
0
0 00
0
0 0 0
30 r I
30 100 1000 3000

Z , mm
Figure 17. Variation of heat transfer coefficient along the length of a membrane wall heat transfer
in the pilot plant CFB combustor section at two different temperatures. Z is the distance from the
top of the membrane surface, suspension density is approximately constant over the length of the
wall, (WU et aI, 1987).
527
~
N
E
} 400 I I
-____ l
t--
• -,
.- . ".
ill
., ,
U
.-.........
-.,'
u.. /
u.. .'
..." ...
~.
.--------.
/
•
._._.-./
UJ
0 100 1- " ~. /
U /
'
"
.
~ ".
UJ '. "-
"•
'.
u.. "- '
Lf) ,,
"-
Z
<t "-
"-
~
I- e
I-
<t 20
UJ
I
300
(OJ
~
O'l
.:x
-----0
--
lI
>-
I-
100 -=1
Vl
--- -1
z ]
UJ
0 I
Z ---
] -- ]
I
0 -'
J
--- .- --- r
Vl
z I
ill
CL
Lf)
I
::J
Lf)
101 I I I! I I I I I 1 I ! I I
0.2 1.0 1.5 0.2 1.0 1.5
Z.m Z.m
(0) UPPER SURFACE (b) LOWER SURFACE
Figure 18. Variation oflocal heat transfer coefficient with operating conditions for two membrane
wall surfaces in the pilot plant CFB combustor, (Wu et ai, 1987).
528
350 -
250
~;;~;J~~ 1.0
~~~~~:;~J
150 5
~
~.
E
3
2 4 6 8 10 0
350 0
(b)
- H.T. Probe
(,J
.-
...c
250
150
1.0
05
...
I
250 ...;;0'---_ _2"'---_---'4_ _ _6=--_~~_~
50 Cap. Probe - 05
Time s
Figure 19. Variation of the instantaneous local heat transfer coefficient and the point voidage with
time on the wall of the cold model circulating fluidised bed combustor. The signals are seen to
be strongly cross-correlated. The cross sectionally area averaged suspension densities are from
top to bottom, 46.7 kg/m3, 32.0 kg/m3,15.3 kg/m3, (WU et aI, 1991).
529
CFB as having an upflow core and a downflow annulus. The success of such a model suggests
that less empiricism is necessary to describe the age distribution on the surface of a circulating
bed heat transfer surface than has traditionally been needed for bubbling beds.
2. The structures present on the heat transfer surfaces of circulating fluidised beds are much less
well understood, and have been the subject of much less experimental characterisation, than
bubbling bed structures.
In a bubbling fluidised bed of a group B powder, such as a sand or other inerts, the microscale
hydrodynamic environment is known to vary between dilute phase (bubbles), containing little or
no solid, and which have thermal properties approximating those of a gas, and dense phase,
which is very close in properties to a loosely packed bed. Both have thermal properties which
can be described by existing correlations, ensuring a reasonable degree of confidence in this part
of the model.
In contrast, the wall structure of a circulating fluidised bed consists of clusters or streamers
whose properties are poorly understood. There is a distribution of voidages and thermal
properties, and it would be incorrect to arbitrarily ascribe loose packed bed properties to these
structures since they are expanded and likely contain many fewer particle-particle and
particle-wall contact points than a loose packed bed. The clusters are also convectively mixed by
gas and wall shear, and have complex cloud-like radiation transfer properties. In combination,
these lead to a pronounced thermal boundary layer of substantial thickness and complexity (Chen
et ai, 1988). This has been measured by Leckner (1991) and is illustrated in Figure 20.
900~--------------------------~
800
u 700
+ 5.elS m
*·Uim
e 2..a7 m
300
200+-~~~~~~~~~~--~~~~
1 10 100 1000
DISTANCE FROM FIN. mIn
Figure 20. Thermal boundary layers in the 12 MW CFB at Chalmers on a membrane wall
showing strong thermal gradients in commercial CFB wall layers. The distance from the fin may
be considered as the distance into the boundary layer from the wall surface, (Lekner, 1991).
530
Hence, while the macroscale fluid mechanics can likely be better described in a circulating
fluidised bed than in a bubbling fluidised bed, the opposite may be said of the microscale heat
transfer.
4. Mechanistic Modelling or CFB Systems
Despite the problems with microstructural descriptions of the wall layer , and the lack of tools for
describing such properties as core-annular solids transfer, it has proved possible to model some
important aspects of overall circulating fluidised bed fluid mechanics and heat transfer. Senior
and Brereton [1992] have developed a model which is one approach to solving the practical
problem of scaling from high temperature pilot plants to large high temperature combustion units
which need not be geometrically similar. The model is mechanistic, with 3 unknown parameters
which are scale-independent. These three parameters can be fitted to pilot plant data and their
values applied to predictions for large scale units.
Given the previous findings, a mechanistic approach must necessarily be based on a
core-annular, or other radially non-uniform model, with solids flow between regions described
by appropriate physically meaningful mechanisms. The approach taken was to describe
core-to-annulus transfer by a particle-particle collision mechanism. Annulus-to-core transfer was
described by analogy with entrainment in gas-liquid annular two-phase flow. This was used to
give approximate dependencies of entrainment upon the wall layer thickness and core physical
properties. Geometric differences between large and small units were characterised by a
"reflection factor" which described the ability of the combustor exit to act as an internal
separator. The mathematical details of the approach are beyond the scope of this review but are
found in Senior and Brereton (1992).
Figure 21 illustrates the ability of the mechanistic model to match complicated suspended solids
density profiles from the 152 mm x 152 mm higher temperature pilot plant. Increased suspension
densities at the top of the unit are due to considerable internal inertial separation at the exit. The
profiles are used to find best fit values of the scale independent "wall-to-core flux coefficient"
and "wall-layer disturbance factor". The model effectively predicts the variation of suspension
density with height, solids circulation rate and gas velocity using these best fit values.
Applying the scale-independent parameters to prediction of density profiles in a prototype CFB
with a thermal rating of 20 times the pilot unit, and a substantially different geometry, again
produces a good match to measured profiles, (Figure 22). This confirms the ability to scale
hydrodynamics over a wide range using mechanistic models. Work to extend the scale-up range
and to improve the mechanistic approach is ongoing.
Hydrodynamic modelling is a necessary precursor to mechanistic modelling for heat transfer.
It describes the motion of high temperature particles into the cooler wall region. If it is further
assumed that clusters travelling from core to wall maintain their identities within the wall layer,
and that the probability of stripping is independent of residence time (Senior and Brereton, 1990).
Then it is possible to predict the history of all particle clusters in the wall layer . Finally, coupling
this with a transient heat transfer model for a cluster of particles falling down the membrane wall,
produces predictions of the variation of heat transfer coefficient with height. This approach has
been developed with some success and typical results are shown in Figure 23. Here the
modelling results are matched against measurements in the Studsvik Energy 2.5 MW TH prototype
boiler. They show good correspondence both with the absolute value and with trends in the heat
transfer coefficient variation with height.
531
UBC COMBUSTOR U AIR SPL
~
1000 (m/s) PIS
SECONDARY AIR •
o
22 7.3 61/49
j
29 7.2 61/49
.
n
E ,\ o 44 7.3 61/49
......
• eo
f\\"
Ol 800 7.3 60/60
~
~, SYMBOLS - EXPERIMENTAL: CURVES - PREDICTED
>- "
!:: REFLECTION COEFlCIENT D.ee
N\o
CI)
zw eoo WALL LAYER DISTURBANCE FACTOR 310.0
Cl
"" 100" COVERAGE STREAMER THICKNESS.M o.ooeo
.,\
Z ., ANNULUS STREAMER SOLIDS VELOCITY. MIS -1.10
"
'\:\ />
0 CORE-TO-WALL FLUX COEFF •• DEVELOPED FLOW 0.20
U5 400 "6
Z '.' /
W
c..
CI)
~
<.!l 200
.\\ / /
SOLIDS R TURN·
~~~:::::----- _"_=:-=:-R::_~.B.:~~·~·~·<···""·-
~................... ................. EXIT REGION
0
0 346
HEIGHT IN RISER (m)
Figure 21. Best fit curves of the Senior and Brereton model to density profiles in the UBC CFB
pilot combustor. The roof reflection coefficient, wall layer disturbance factor, and core-to-wall
flux coefficient were adjusted to obtain the fit. (Gs = solids circulation flux, U = superficial gas
velocity), (Senior and Brereton, 1992).
, STUDSVIK PROTOTYPE
G, U AIR SPL
1200
\ HIGH SULPHUR COAL
SECONDARY AlA - -- •
(kg/m's)
44
(m/s)
8.0
PIS
72/2B
-_._-
0:;-
E 1000
......
\ j ---------.
0
0
40
91
8.0
8.0
76/25
87/33
~
Ol
~ SYMeOLS - EXPERIMENTAL: CURVES - PREDICTED
>-
~
REFLECTION COEFICIENT 0.10
800
!:: WALL LAYER DISTURBANCE FACTOR 310.0
<.!l
~
Z 100% COVERAGE STREAMER THICKNESS.M O.OOBO
W
0 ANNULUS STREAMER SOLIDS VELOCITY.M/S -1.10
eoo
z
-~
CORE·TO-WALL FLUX COEFF•• DEVELOPED FLOW 0.20
0
U5 •
Z
W
c..
400
~
CI)
~
CI) \
200
~ EXIT REGION
~~-
0
SOLIDS R URN ~-
•
0 3 4 6
HEIGHT IN RISER (m)
Figure 22. Fit of the Senior and Brereton model to density profiles from a prototype CFB 20
times bigger than the UBC pilot. A very different exit geometry is accounted for by the different
roof reflection coefficent, other hydrodynamic parameters are scale and geometry independent.
532
~ Experiment
o 0
~~oJ
120
300
'"::;:
C'<
1 M
::;:
"-
Predicted 6-
f 80 200 .;
'"
:J
=
...
V>
Z
w
\
0
40 100
J:;
\ ""--.... ,,---L:,
0 ~ 0
0 2 4 6 8
HEIGHT-M
Figure 23. Heat transfer coefficent predictions to membrane walls based on the Senior and
Brereton model compared with experimental data in the Studsvik prototype, (Senior and Brereton,
1990).
The ability of a relatively simple model to predict the complicated trends is encouraging.
However, since reasonable variations in the unknown thermal properties of clusters allow the
absolute value of heat transfer coefficient to be fixed at one point in the profile, it is only the
ability to predict direction and magnitude of trends which is worthy of remark. Of particular note
is the ability of the model to predict increased heat transfer coefficients at the top of the boiler
in a region of decreasing suspension density.
In summary, mechanistic modelling of fluid mechanics and heat transfer is still in its infancy.
However, gradual progress is being made toward practical design models.
S. Combustion Aspects of Circulating Fluidised Beds
The core-annular nature is an essential aspect of the qualitative and mathematical description of
the fluid mechanics of circulating fluidised beds. It is also key to understanding aspects of heat
release and pollutant formation within CFB combustion systems. Figures 24 and 25 (Brereton et
aI, 1991) show principal combustion product and pollutant profiles in the UBC pilot fluidised bed
combustor for combustion of a bituminous high sulphur Eastern Canadian coal. The profiles show
strong radial gradients which may be correlated with radial gradients in solids loading. Also
shown are strong axial gradients. The high solids concentration wall layer is shown to be low in
oxygen and high in reducing gases such as carbon monoxide. This is because of the presence of
char in proportion to the amount of solids. Because of this, the wall layer serves as a zone for
reduction of pollutant NOx species. In addition, a substantial amount of sulphur capture occurs
in this zone when limestone is used for capture of sulphur oxides in the CFB. While trends in
533
15
"Wall
_Half way
-Axis
12
~
zw 9
Cl
>-
x
0
6
0 7
0 2 3 4 5 6
Height, m
Figure 24. Axial and radial profiles of oxygen obtained while burning
Minto coal in the UBC CFB pilot plant, (Brereton et ai, 1991).
300
E
0..
0..
c 250
0
.-
-...
c
0
CII
v
200
C
0
U
>< 150
•
0 ... Wall
Z • Half way
-Axis
100
0 2 3 4 5 6 7
Height (m)
Figure 25. Axial and radial profiles of NO, obtained while burning Minto coal in the UBC CFB
pilot plant, (Brereton et al, 1991).
534
pollutant profiles may be explained on the basis of the core annular structure, there has been only
very preliminary work on quantifying these effects in scalable predictive models. These will
require complex gas mixing and interchange models for which there are, as yet, few data
available. Hence, scale-up of pollutant generation rates and other chemically controlled
performance values from pilot units remains a tenuous undertaking. This remains one of the
principal challenges for circulating fluidised bed designers.
6. Summary and Conclusions
The ability to describe chemical reactions and heat transfer in circulating fluidised beds depends
critically upon a sound understanding of the underlying fluid mechanics. For the case of Geldart
group B solids, such as the inerts typically used in circulating fluidised bed boiler systems, the
best simplistic view of the internal solids motion is to consider it as essentially core-annular in
nature. In the core the solids essentially act as individual particles. Although this representation
is not valid at the base of the unit, where considerable particle aggregation into hydrodynamic
clusters exists, the presence of these complex structures decays rapidly with height. Over the bulk
of the reactor, above the secondary air ports where the heat transfer surfaces are found, the
simplified core-annular model is a good engineering approximation for prediction of heat transfer
coefficients and other hydrodynamically dependent parameters.
Performance of CFB units is very strongly dependent upon geometric effects, particularly the
geometry of the exit. Abrupt exits create internal circulation and may be used to minimise the
size of external recycle loops for a given reactor hold-up. They also maximise solids backmixing
and minimise gas backmixing for a given reactor pressure drop. Smooth exits create the opposite
effects. These features may be used, within limits, to engineer specific solid and gas mixing
characteristics into CFB systems.
Modelling of CFB systems is in a period of rapid development. Practical models, based on
simplified hydrodynamic schemes such as the core-annular approach, have proved effective in
allowing hydrodynamics and heat transfer to be scaled from pilot units. More fundamental
approaches to transfer coefficient prediction should soon reduce the dependence upon empiricism,
and allow greater confidence.
Many features associated with circulating fluidised bed combustion currently defy accurate
prediction. An example is prediction of pollutant formation. While an understanding of the CFB
system allows us to qualitatively explain profiles of pollutant formation, considerable work on
many of the complex three-dimensional aspects of the CFB system, as well as improved
understanding of reaction schemes and their kinetics, are needed before such features can be
confidently predicted from first principles or scaled from pilot units. In such cases, performance
guarantees will continue to be based on experience with larger scale systems. Thus, while
circulating fluidised bed combustion systems are presently among the most environmentally
friendly means of burning fossil fuels, considerable work is required to better understand and
optimise them. This may allow scope for further improvements in both environmental and
thermal performance.
535
Notation
E Voidage (- )
E. Limiting dilute phase voidage (-)
E' Limiting dense phase voidage (-)
g Acceleration due to gravity (m/s')
P Pressure (pa)
Z Distance from top of riser in eqn. 2 (m)
Distance from base of riser in eqn. 1
Distance of inflection point in density profile from top of riser (m)
Characteristic length in density profile (m)
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APPLICATION OF A MONTE CARW METHOD TO THE SOLID FLOW PATTERN
VISUALIZATION IN CFB
B.P.A. GRANDJEAN i and J. CHAOUKF

Departments of Chemical Engineering
(1) Universite Laval
Sainte-Foy, Quebec, Canada G1K 7P4
(2) Ecole Polytechnique de Montreal
c.P. 6079 Succ. A, Montreal, Quebec, Canada H3C 3A7
ABSTRACT. Circulating Fluidized Bed has been accepted worldwide as an advanced technology for many
applications. The understanding of the solid flow pattern in CFB is of great importance in order to
successfully scale-up these reactors. This paper presents a model, based on a Monte-Carlo simulation,
which describes the solid flow pattern. Starting with the accepted description of an upward flow in the core
and a downward flow in the annulus, particles transfer is described between core and annulus in order to
account for the actual density gradient occurring in CFB. Considering a large number of particles (ie.
60 000), the model enables to track the position of any particles during its residence time in the riser. Even
though no radial mixing is considered in the middle of the riser, the model suggests a considerable
backmixing of the solid which is characterized by internal circulation loops. In order to validate this
approach, experimental and simulated RTDs are qualitatively compared.
1. Introduction
Circulating Fluidized Beds (CFBs) have been applied to the petroleum refining industry in
modern riser catalytic crackers and have been used for high temperature non-catalytic processes
such as coal combustors, alumina calciners ... (Contractor and Chaouki, 1990). However,
increasingly stringent legislation on emissions has placed an urgent need for an improved
understanding of the gas and solid flow patterns in order to design reactors which could meet the
emission requirements (Engstrom and Lee, 1990). Therefore, the challenges for researchers in
developing this technology further include the scale-up issue and the emission control strategy.
Development of new systems for measurement or visualization of the solid particles is very
important to clarify the detailed structure of CFB. For the dilute phase flow, many powerful
techniques developed for single phase flow, such as photography or Laser Doppler Velocimetry,
can be used (Hatano and Kido, 1991). However, they could not be applied to the dense phase
flow. Various kinds of probes based on different principles have been developed in the fluidized
beds. Especially, both reflective and penetrative optical fibre probes are widely used in the gas-
solid fluidization research. Recently, particles flow in the riser was visualized by Li et al. (1991)
and Hatano and Kido (1991). Micrographs were taken by using a video-camera provided with a
special probe which consists of a set of lenses and an optical fibre flashlight transmitter inserted
radially into the bed. This method gave new insight in the CFB flow structure. However, no
whole picture of the solid flow pattern can be given.
537
H.1. de Lasa et al. (eds.). Chemical Reactor Technology for Environmentally Safe Reactors and Products, 537-546.
© 1993 KlulI'er Academic Publishers.
538
The purpose of this paper is to present a model, based on a Monte-Carlo simulation, which
describes the solid flow pattern in CFB. In order to validate this approach, experimental and
simulated RTD are then compared.
2. Experimental
The CFB experimental system consists of two parallel stainless steel columns, 5 m high and
82.8 mm in diameter. Solids, injected into the riser from an L-valve located just above an orifice
plate distributor, are entrained in the upward flowing gas. The particles exit through an abrupt
reducing elbow and are separated from the gas by mean of a cyclone. They are returned to the
storage hopper and the gas passes through a knock-out drum before venting to atmosphere. Solids
circulation was determined by measuring pressure drop along the riser (patience and Chaouki,
1990). Density profile has been calculated from the pressure drop profile neglecting the
acceleration contributions. Sand with a mean diameter of 277 p,m was used as a test material.
Tracer studies entail injecting a detectable species and measuring the concentration as a function
of time at various elevation in the riser. The resultant residence time density function, commonly
referred to as the residence time distribution (RTD) curve are then obtained. This method has not
been employed extensively to study the hydrodynamics of CFBs (patience et aI. 1991). In this
investigation, the tracer is produced by irradiating a sample of sand in the fast neutron flux of
a Slowpoke nuclear reactor. Sj28 is converted to AJ28 which has an half life of 2.24 min. It emits
high energy gamma-rays that are detected with a Na-I scintillator counting in the multi-scaling
mode. The radioactive sand is injected into the reactor just above the distributor. The complete
experimental procedure is given by Patience et al. (1990). Two Nal scintillator detectors are
located at two different heights in the riser (2.30 m and 4.80 m).
3. Description of the Model
As suggested in the literature (Horio 1990, Grace 1990), the solid flow pattern in a CFB is
described by an upward flow in the core region and by a downward flow in the annulus. The
riser (height H) is partitioned in top and bottom stages and (N-2) equal stages in the middle as
shown in Figure 1. Core and annulus zones are defined on each stage except for the top and the
bottom stages where a perfect mixing is assumed.
In order to account for the actual density gradient in the riser, the numbers of particles tracked
by the model in the core and in the annulus of each stage are proportional to the actual average
density at the same elevation. A minimum number of particles in the core region, n~IN' is chosen
for the stage where the minimum density, dM'N occurs.
Then, the numbers of particles in the core region of the other stages are given by:
nc(i)= nCMlN d(i)/d MlN (1)
The number of particles in the annulus region of each stage, na(i), is assumed to be given by:
na(i)= nc(i) RAc (2)
where the coefficient RAc is assumed, for the sake of simplicity, to be constant.
539
In the top and bottom stages, the numbers of particles are respectively:
nTOp = kTOP [na(N) + nc(N)] (3)
IlsOT= kBoT[na(l) + nc(1)] (4)
where the values of the coefficients kTOP and kBOT are equal to 1 if the volume of these stages are
similar to that of the middle stages and different in other cases.
An average upward particle velocity in the core, VuP , is defined and can be obtained, making
the usual assumption that the slip velocity of the particles in the core is equal to their terminal
velocity.
In order to perform the Monte-Carlo simulation, a time step, tup, is defined by:
tup = H/(Vup N) (5)
The particles are assumed to be stationary during this time interval, and then, they are allowed
to move according to various rules.
In the core, all the particles move to the upper stage. In the lower part of the riser where the
density decreases with elevation, the particle upward jump is illustrated in Figure 2. Some of the
particles have to move in the annulus in order to respect the decrease of the particle number. For
each particle in the i-th core, the probability, Pee, to move in the upper core is given by:
Pee(i) = nc(i+ 1)/nc(i) (6)
The Monte-Carlo procedure is performed as follows: a random number is given for each
particle and, if this number is lower than Pee, particle jumps in the upper core, otherwise it
jumps in the upper annulus.
I
N
•
Figure 1 Partition of the riser Figure 2 Core particle jump in the

N stages region of decreasing density
In the upper part of the riser where the density increases with elevation, particle jumps are
shown in Figure 3. All the particles in the i··th core move in the upper core but additional
540
particles have to move from the annulus to the core in order to respect the increase of the particle
number. The probability , PAC' for a particle in the annulus to move in the core is given by:
PAC(i) = [nc(i + I)-nc(i)]/na(i + I) (7)
In the region of constant density, all the particles in the core of the i-th stage simply move up
in the core of the (i + 1)-th stage.
The upward flow of particles per second, Nup(i), leaving the i-th stage is given by:
Nup(i) = nc(i)/tup (8)
In the region of constant density, a value is assumed for the ratio (W /E)o (actual downward
particle flow, W, to the actual upward particle flow, E). In the model, the downward particle
flow, NDW, leaving an ic-th stage in the region of constant density is then given by:
(9)
and the net upward particle flow per second, NETup, is obtained:
NETup = Nup(ic-I)- NDw(ic) (10)
Knowing the net upward particle flow, the downward particle flows, NDw(i), leaving the stages
in the upper and lower part of the riser are finally calculated, applying Eq. (10) for these stages .
••
Figure 3 Particle jump in the core Figure 4 Downward particle jump in the
region of increasing density annulus
The particles in the annulus are stationary during the time step, tuP' Then, some of them can
move in the adjacent core, as previously explained. The remaining particles can also move down
in the lower annulus as shown in Figure 4 with a probability, PDW, given by:
PDw(i)=tup NDw(i)/na(i) (11)

541
This ensures the respect of the solid downward flow.

As the Monte-Carlo simulation proceeds with time, the numbers of particles in core and
annulus zones of each stage fluctuate around their initial values.
In the top stage, the particles are allowed to experience three events: to get out of the column,
to move down in the lower annulus or to stay in the top stage. The probabilities for the two first
events are respectively:
POUT = NETUP tup/nTOP (12)
(13)
where NDw(N) is calculated from Equ. (10).
•
FIGURE 5 Particle jump in the top of Figure 6 Particle jump in the bottom of
the riser the riser
In the bottom stage, the particles can move up to the upper core (see Figure 6) according to
a probability which enables the filling of the core of the second stage:
PBe = nc(2)/nBoT (14)
After each time step, tuP , additional particles are added to the bottom stage in order to account
for the entering particle flow. The number of fresh particle injected is given by:
nIN) = NETUP tup (15)
It has to be mentioned that, from the previous definitions, the values of the ratio (JV IE) in the
region of varying density and the average downward velocity of the particle in the annulus can
be calculated according to the following relations:
(16)
(17)
542
4. Tracer Simulations
Tracer simulations entail injecting labelled particles in the bottom stage during a given time and
detecting the number of these particles at different level in the column. The model enables to
track the position of any labelled particle during its residence time in the riser.
The simulations have been performed using a stage number N equal to 50 and a minimum
number of particle in the core of a stage, ncMlN , equal to 120. The ratio RcA of the number of
particles in the core to that in the annulus was assumed to be equal to 9. Such a value is in
agrement with some data reported by Berruti and Kalogerakis (1989) on the radial density
distribution. The coefficients kBOT and kTop were equal 1 and 1/3. It is however difficult to know
the actual values of these coefficients since the top and bottom zones are not well defined. The
value of the ratio CWIE)o of the downward flux to the upward flux in the region of constant
density has been chosen equal to 0.05 or 0.15 as suggested from the investigation of Milne and
Berruti (1990). The injection time of labelled particles was equal to 0.3 s or 0.6 s.
It has to be mentioned that Monte-Carlo simulations are CPU-time consuming. A typical
simulation duration (using an Apollo 3500 workstation) is equal to 2.5 hours for tracking about
60 000 particles during an interval time of 15 seconds. This is a severe limitation to investigate
extensively the effects of the previous parameters and to develop a least-square fitting procedure
in order to analyze experimental results.
5. Results and Discussions
Experimental density profile, shown in Figure 7, were first used in the simulation. However, the
simulated RTD curves shown in Figure 8 are not comparable with the experimental ones shown
in Figure 9. The simulated curves represent, at a given height, the variation with time of the ratio
of the number of labelled particles (L) at this position to the total number of labelled particle,
(Lo), injected in the riser. At an height of 2.30 m, which corresponds to the region of constant
density, all the labelled particles recorded by the simulation where located in the core.
Conversely, at an height of 4.80 m, the important value of the ratio (L/Lo) is explained by the
temporary accumulation of labelled particles in the core of a stage. These particles come from
the top according to the previous mechanism explained in Figure 5.
Density profile has been found to be a parameter of first importance in simulation. In fact,
when an average density profile within the riser is assumed as illustrated in Figure 7, the
resulting simulated RTD curves shown in Figures 10 and 11 qualitively resemble more the
experimental ones. However, the relative intensities of the simulated RTD curves at z=2.30 and
z=4.80 do not respect the experimental observations. It is believed that these differences could
be explained mainly by the fact that the model does not account for radial solid mixing in the
region of constant density. The effect of the recirculation rate CW IE)o can be observed by
comparing Figures 10 and 11. An increase of the circulation rate from 0.05 to 0.15 accelerates
significantly the responses in the top of the riser. This is due to the increase of the downward
particle velocities: the labelled particles enter the core region earlier. For the simulations shown
in Figure 10 and 11, the average downward velocity and the circulation rate, calculated using
equation 15 and 16, are given in Table 1.
If the variation of the ratio CW IE) in the riser are quite reasonable (as compared to data given
by Milne and Berruti 1990), the downward velocity appears to be very low especially in the
region of constant density. In fact, Wu et al. (1991) have measured the average falling velocity
543
of strands using high-speed cinematography and have found a value of 1.26m/s. If the injection
time is varied from 0.3 s to 0.6 s, no significant variation in the simulated RTD curves is
observed.
0.10,,--------------,
400.00 - , - - - - - - - - - - - - - - ,
n
E 0.08
1: Z=2.30 m
""- 2: Z=4.S0 m
6::300,00
2
••••• EXPERIMENTAl
~ -ASSUMED
iii
Z200.DO
W
o
w
(')
~ 100.00 '----------.//
..
W 0.02
~
1.00 2.00 J 00 4.00 '.00
500 10.00 15.00
HEIGHT (m)
TIME (s)
Figure 7 Average density profile in the riser Figure 8 Simulated RTD curves using
experimental density profile
0.10.,---------------,
200.00 . , - - - - - - - - - - - - - ,
w 2 W/E = 0.05
(j) 0.08
6 150. 00 Z=2.30 m 1: Z=2.30 m
0.. 2 2: Z=4.S0 m
(f)
w 2 Z=4.80 m
...--0.06
(t:
100.00
3
'J
(t:
§
W
'-"0.04
f--
oW 50.00
0.02
0.00
0.00
UJ~~~\-t"j.:~~~~
5.00 10.00
••
15.00
0.00 .:jJ,J~~IIIMo_1"l"f"iJ.t-Ml'~¥¥,M~~~
0.00 5 00 10.00 15.00
TIME (s) TIME (s)
Figure 9 Experimental RTD curves Figure 10 Simulated RTD curves

544
Figure Height CNIE) VDW 0.10
nO (m) m/s W/E = 0.15

0.08
2 1: Z=2.30 m
10 0.20 0.62 0.41
2: Z=4.BD m
10 2.5 CNIE)o 0.03 .--..0.05
0
---'
=0.05 ~
..............O.()4
10 4.90 0.30 0.20
11 0.20 0.66 0.44 0.02
11 2.5 CNIE)o 0.10

=0.15 0.00 TIME (~)oo
1,5,00
11 4.9 0.38 0.25

Figure 11 Simulated RTD curves
TABLE I Internal recirculation rate
and downward particle velocity
It is important to mention that the present model is in a development stage. Only qualitative
comparisons have been made between experimental RTD curves, expressed in term of the
detector response, and the simulated responses expressed in term of the ratio LILa. Further
investigations are required in order to perform a quantitative comparison between the detector
response and LILa.
6. Conclusions
A Monte-Carlo simulation has been developed in order to visualize the particle flow in CFB.
Starting with the accepted description of an upward flow in the core and a downward flow in the
annulus, particle transfers between core and annulus have been described in order to account for
the actual density gradient occurring in CFB. The model enables tracking the position in the riser
of a large number of particles (60 000 or more). Even though no radial mixing is considered in
the middle of the riser, the solids undergo considerable backmixing which is characterized by
internal circulation loops. In addition to the main loop (upward core and downward annulus),
secondary loops exist from the annulus to the core in the top region and conversely from the core
to the annulus in the bottom region.
Even though the model is in an development stage, it appears to be very attractive: RTD curves
can be computed along with the axial variations of the solid recirculation rate and of the average
downward velocity of the solid in the annulus. Various parameters have been defined in the
model, but no sensitive study has been performed extensively at this time. Only qualitative
comparisons have been made between experimental and simulated RTD curves.
In a near future, the model will be modified in order to account for the radial mixing of the
solid occurring in CFBs and the capability of the model to simulate quantitatively experimental
RTDs will be tested.
545
NOTATION
average density in the i-th stage (kg/m 3)

minimum average density occurring in the riser (kg/m3)
particle mass flux (kg/m2.s)
riser height (m)
stage numbering
ic stage numbering in a region of constant density
kBOT coefficient in eq.3
k TOP coefficient in eq.4
L number of labelled particles at an given height
Lo total number of labelled particles injected in the riser
N number of stages
NDW downward particle flow per second in the simulation
Nup upward particle flow per second in the simulation
NETup net upward particle flow per second in the simulation
na(i) number of particles in the annulus of the i-th stage
nc(i) number of particles in the core of the i-th stage
nCMIN minimum number of particles in the core region of the stage where dMiN occurs
nBOT number of particles in the bottom stage
nINJ number of fresh particles entering the riser at each time step
n TOp number of particles in the top stage
P _(i) probability for a particle in the i-th stage to experience an event
PAC probability to move radially from the annulus to the core zone
Pac probability to move from the bottom stage to the upper core zone
P cc probability to move downward from a core to the lower core zone
PDW probability to move downward from a annulus zone to the lower one
POUT probability to get out of the column
PTA probability to move from the top stage to the lower annulus zone
~ ratio of the number of particle in the core to that in the annulus
tup time step of the Monte-Carlo procedure (s)
U superficial gas velocity (m/s)
Vup average upward particle velocity in the core (m/s)
(y.I IE)o ratio of the downward particle flux to the upward particle flux in the
region of constant density
z axial position in the column (m)
REFERENCES
Berruti F. and N. Kalogerakis, "Modelling the Internal Flow Structure of Circulating Fluidized
Beds", The Can. J. of Chern. Eng., 67 1010-1014 (1989).
546
Contractor RM. and J. Chaouki, "Circulating Fluidized Bed as Catalytic Reactor", CFB III
Edited by P. Basu, M. Horio and M. Hastani, 39-48 (1990).
Engstrom F. and Y. Y. Lee, "Future Challenges of Circulating Fluidized Combustion
Technology", CFB III Edited by P. Basu, M. Horio and M. Hastani; 15-26 (1990).
Hatano H. and N. Kido, "Visualization of Solid Particles Flowing in Circulating Fluidized
Bed", Proceedings of the Int. Conf. Multiphase Flows Tsukuda, Japan, 295-299 (1991).
Li H., Y. Xia, Y. Tung and M. Kwauk, "Micro-Visualization of Clusters in a Fast Fluidized
Bed", Powder Technology, 66 (3) 225-230 (1991)
Milne B.J. and F. Berruti, "Modelling the Mixing of Solids in Circulating Fluidized Beds", CFB
III Edited by P. Basu, M. Horio and M. Hastani; 575-580 (1990).
Patience G.S. and J. Chaouki, "Solids Residence Time Distribution in CFB Reactors", CFB III
Edited by P. Basu, M. Horio and M. Hastani, 627-632 (1990).
Patience G.S., J. Chaouki and G. Kennedy, "Solids Circulation Rate Determined By Pressure
Drop Measurements", CFB III Edited by P. Basu, M. Horio and M. Hastani, 599-604 (1990).
Wu RL., C.J. Lim, J.R Grace and C.M.H. Brereton, "Instantaneous Local Heat Transfer and
Hydrodynamics in a Circulating Fluidized Bed", Int. J. Heat and Mass Transfer 3~ (8) 2019-
2027 (1991).
MODELING CATALYTIC MONOLITHS FOR AUTOMOBILE EMISSION CONTROL
J.P. LECLERC, D. SCHWEICH

Laboratoire des Sciences du Genie Chimique - CNRS
ENSIC - INPL, 1 rue Grandville, BP 451
F - 54001 Nancy cedex
ABSTRACT. Most important elementary processes governing the behaviour of the converter (chemical
reactions, heat and mass transfer processes to the catalyst surface, hydrodynamic, heat conduction and heat
loss) are first described. Next, published models are reviewed and main modeling problems are considered.
Then, the structure of a fairly general model is proposed. The behaviour of the converter at steady state
and in the transient state is reported and the sensitivity of the model to various parameters is discussed. It
is concluded that the lack of accurate data (especially kinetic data) makes the predictions with available
models only qualitative assessments. However, many design or operating improvements can be deduced
from these models.
1. Introduction
1.1. TECHNICAL ECONOMICAL BACKGROUND
Automotives are responsible for about fifty per cent of the total emission of carbon monoxide,
unburnt hydrocarbons and nitrogen oxides (see Figure 1.1) which are the origin of many health
and environmental problems (Chiron (1987), Impens (1987)). Although emission standards are
different from country to country, they are going to become in the near future more and more
restrictive. Since an economical clean engine is not available, the catalytic converter is the only
practical solution. This is the reason why a lot of research efforts have been directed to the design
and optimization of this reactor.
Automotive pollution control is a major application for Platinum group metals. In 1989,42%
of the western world demand for Platinum, 8% for Palladium and especially 81 % for Rhodium,
were for the manufacture of automotive catalysts (Steel (1990)). Because of the high cost of these
metals, the converter must be designed to obtain high pollutant conversions with a minimum
amount of metals.
The converter must also preserve the engine efficiency. Presently, monolithic catalytic
converters seem to be the most efficient because they operate with a low pressure drop.
Depending on the available space under the car, the monolith cross-section can be cylindrical,
oval or "race-track". The monolith is fitted to the inlet exhaust line by a divergent duct and to
the outlet exhaust line by a convergent duct (see Figure 1.2).
547
H.I. de Lasa et al. (eds.), Chemical Reactor Technology for EnVironmentally Safe Reactors and Products, 547-576.
548
c 8. 10 +6
~
en
0
C +6 !!!!!! Total .
~ Automotlves
C 6.10
S
.3 4. 10 +6
"0
0..
.....0 2. 10 +6
C
::l
0 +6
E 0.10
<C CD NO x He
pollutant
Figure 1.1. World annual amounts of pollutants released in the atmosphere
The radial velocity distribution in the monolith and the pressure drop across the converter
depend on the shape of the divergent and of the monolith sections. Furthermore, mass and heat
transfer and hydrodynamic properties depend on the shape of the monolith channels. Ceramic
monoliths are generally made of square, circular or triangular channels. In metallic monoliths,
channels are manufactured by rolling up a thin corrugated metal sheet.
Inlet
Monolith
Figure 1.2. Schematic of a monolithic catalytic converter
Figure 1.3 shows the time evolution of unburnt hydrocarbons with and without catalytic converter
in a European vehicle test. At cold start, the converter is cold and the reactions are very slow.
As illustrated in Figure 1.3, under those conditions, pollutant emission is high. For a car driven
in a city, about 20 to 30% of pollutant are released at cold start. After about one minute, the
converter works efficiently, however it cannot totally erase the pollutant bursts due to change of
gear, acceleration, etc. During this transient state, temperature, flowrate and composition of the
exhaust gas are very variable. At constant speed, the converter is nearly at steady state (excluding
engine pulsations), and pollutant emission is very low. This brief review of the working
conditions shows that the catalytic converter is a complex reactor because it needs to be efficient
at both transient and steady state, whereas the operating conditions (feed temperature and
composition, flowrate) are variable.
At cold start, the converter is heated by the exhaust gas. When the catalyst is sufficiently hot,
the heat generated by the reactions suddenly ignite the converter, and pollutant emissions drop
549
considerably. This phenomenon is called "light-off'. The efficiency of the catalyst is often
characterized by the "light-off temperature" which is defined by the temperature at which the
conversion of a given pollutant is 0.5. Although useful for practical applications, this definition
is very empirical, because the light-off temperature depends on the composition of the gas, the
fluid velocity and on various design criteria (adiabatic or isothermal reactor, plug flow or well
mixed, crushed catalyst or monolith sample, etc.). The light-off time is empirically defined as
the time needed for the monolith to ignite at cold-start. For some temperatures and compositions
of the feed gas, only a fraction of the monolith is ignited. The location of the ignition front in
the converter is the Iight-off point.
CONCENTRATION OF
UNBURNED HVDROCAAB0NS
1.2 -
10
O~
06
04
02 WITH CATALYTIC
cotNEFtTER
L---~~0--~--~--~~~~~~~~~~-0~6~
TIME (MINUTES)
Figure 1.3. Time evolution of unburnt hydrocarbons with and without catalytic converter during
a European test (prigent (1985».
Knowing that a car is driven for an average time often minutes in a city, reducing the light-off
time is one of the main objectives of research. Similarly, improving the efficiency at steady state
and in the transient state, improving poisoning resistance, optimizing the converter and channel
shapes are the subjects of recent research. In addition to experiments, a clear scientific
understanding of various phenomena (combined heat transport, mass transport, and reactions) is
thus required.
1.2. THE ELEMENTARY PHYSICO-CHEMICAL PROCESSES
There are a lot of competing elementary processes governing the behaviour of the converter. We
will first review the most important ones.
1.2.1. The chemical reactions. The exhaust gas composition is quite complex. In addition to
carbon dioxide (C02), nitrogen (Nz), water (H20), carbon monoxide (CO), hydrogen (H2),
nitrogen oxides (NO,), there is a mixture of residual hydrocarbons, and various components
containing phosphorus, zinc, sulphur (and sometimes lead !) originated essentially in the
lubricant. It is thus too complex to describe all of these chemical species. Most of the time, the
residual hydrocarbons are lumped into one or two equivalent hydrocarbons, for example, fast and
slow reacting hydrocarbons. In laboratory experiments and models, slow reacting hydrocarbons
are accounted for by methane, whereas fast reacting ones are represented by propene. Similarly,
550
NO. are generally represented by NO alone.

Early converters were designed to oxidize CO, H2 , and unburnt hydrocarbons (oxidizing
converters). More recently, "three-way converters" have been developed to oxidize hydrocarbons,
H2 , and CO, and reduce NO. emissions simultaneously. This goal is achieved by using a suitably
promoted Platinum-Rhodium catalyst supported on alumina and by carefully controling the
air/fuel ratio. The catalyst is a thin porous alumina layer "wash-coated" on the wall of the
monolith channels. Typically the wash-coat is about a few tens of a micrometer thick, except at
the corners of the channel where it is thicker.
Although crucial for modeling purposes, reliable kinetic rate expressions are scarce. One of the
first studies was performed by Voltz et al. (1973) and concerns exclusively oxidizing reactions.
The rate expressions were then refined by Oh and Cavendish (1981). The following reactions
were considered:
I
CO+"202 ~C02 L',Hl = -2.83105 J.mol- 1 (l.1)
1
H2 +"202~ H2O L',H2 = -1.93 105 J.mol- 1 (1.2)
9
C3 H6 + "2 02 ~ 3H20 + 3C02 L',H3 = -2.42 106 J.mol- 1 (1.3)
CH4 + 202 ~ 2H20 + CO2 L',H4 = -8.30 104 J.mol- 1 (1.4)
The rate expressions for reactions (1.1) to (1.4) are Langmuir-type expressions depending on
mole fraction of reactants:
}
_ kl s xco X02 _k\sXH2 X02
r1s- F(x) , r2s - F(x)
r - k3s xC3H6 x02 _ k4s xCH4 xo 2 (1.5)
3s - F(x) , r4s - F(x)
Inhibition due to NO is accounted for in F(x), although the reduction reaction is not considered,
and the rate of H2 oxidation is assumed to be the same as that for CO. Table 1 summarizes the
kinetic constants with reaction rates in mol S·1 m·2 of platinum.
Table I. Kinetic parameters for oxidation reactions (Oh and Cavendish (1981»
constant Arrhenius/van't Hoff law units
kls 6.699 lOLl exp(-12556/T) mol s·1 m- 2 of Pt. K-I
k3s 1.39210 15 exp(-14556/T) mol s-l m- 2 ofPt. K-l
k4s 7.326 lO10 exp (-19000/T) dimensionless
ka1 65.5 exp(961/T) dimensionless
ka2 2080 exp(361/T) dimensionless
ka] 3.98 exp(l1611/T) dimensionless
ko4 4.79 lO5 exp(-3733/T) dimensionless
551
It has to be pointed out that the heat of adsorption of NO (See k..4' Table 1) as reported by Oh
and Cavendish (1981) has the wrong sign. Moreover, the dependence ofF(x) in terms ofT seems
to be suspect. If the reactions are second-order with respect to concentrations, then T2 should
appear. This suggests that the rate expressions are not based on a clear mechanism, and that they
should be considered semiempirical. They only fit well the experimental data of the authors.
Finally, these rate expressions are valid at atmospheric pressure, an extrapolation to higher
pressures could be questionable.
Kinetic expressions for NO reduction are even more infrequent. Most studies are essentially
devoted to mechanistic considerations. Only the paper by Subramanian and Varma (1984, 1985)
may provide useful expressions.
1.2.2. The heat and mass transfer processes to the catalyst sUrface. Owing to the large cross-
section area of the monolith and to the small channel radius, the channel Reynolds number is less
than 1000, and laminar flow prevails. In a single channel, competing laminar flow, wall reaction,
and radial heat and mass transfer by diffusion can be defined with a generalized Gratez-Nusselt
problem. Although the corresponding mass balance equations can be easily derived, numerical
solutions for these equations are more time-consuming than the corresponding experiments.
Moreover this approach is so cumbersome that it is difficult to elucidate the predominant factors
governing the monolith behaviour. An alternative description of the processes is thus required.
In many situations, solution for the Graetz-Nusselt problem is closely approximated by the
"film model". In this model, radial temperature and concentration profiles are assumed to be
uniform in the bulk fluid, whereas heat and mass transfer resistances are assumed to be close to
the solid surface. Surface and bulk fluid properties being different, the specific radial mass and
heat fluxes are given respectively by
<ilOj '" kOj eTC; (Xj - Xjs) (1.7)
lJo"'h(Tc;-Ts) (1.8)
where CTO , Xj' Xj" To, and T, are the total gas phase concentration, the mole fraction of species
j in the bulk fluid and in the gas phase in contact with the channel wall, the gas temperature, and
the solid temperature respectively. kDj and h are the mass and heat transfer coefficients which are
obtained from the non dimensional Sherwood and Nusselt numbers respectively
Shj '" kOj Dh

. Dmj (1.9)
Nu '" h Dh
(1.10)
AC;
where Db, Dmj , and Ao are the hydraulic diameter of the channel, the molecular diffusivity of
species j, and the heat conductivity of the gas respectively. The hydraulic diameter is easily
obtained from channel geometry by
D _ 4 cross-section area (1.11)
h - perimeter
For a square channel, Db is the length of the channel side. In the absence of reactions and heat
transfer by radiation, and when laminar flow is fully developed, the Sherwood and Nusselt
552
numbers are constant and of the order of 2 to 5 depending on the shape of the channel.
1.2.3. Muffler geometry and residence time distribution. The diameter of the converter is larger
than the diameter of the exhaust pipe. In the exhaust pipe, flow is generally turbulent, and the
turbulent fluid enters the converter through a short divergent inlet. Due to the divergent flow and
to the backpressure induced by the monolith a complicated flow pattern develops and results in
a non-uniform radial velocity distribution at the monolith scale. Presently, it is not possible to
calculate the velocity distribution, and experiments are required.
At high flowrate, jet flow prevails in the centre of the monolith. The fluid velocity can be more
than twice the mean velocity. Conversely, fluid velocity at the monolith boundary can be much
smaller. This velocity distribution depends on the mean flowrate and on the presence of flow
deflectors in the divergent section.
Flow distribution has been essentially studied in cylindrical monoliths (Wendland and Matthes
(1986), Howitt and Sekella (1974), Lemme and Givens (1974». Elliptical and race-track
monoliths have been studied by Wendland and Matthes (1986) and Leclerc et al. (Leclerc et al.
(1989a, 1989b, 1990». The main conclusions of these authors are:
-The shape of usual small divergent inlets (about 10 cm long) does not strongly modify fluid
distribution.
-The convergent section and the downstream exhaust line and muffler do not alter the flow
distribution.
-The smaller the diameter of the inlet exhaust tube, the more non-uniform radial velocity profile
is obtained.
-Suitable flow deflectors make it possible to obtain rather flat velocity profiles in a restricted
range of flowrates.
The radial velocity distribution is reflected in the Residence Time Distribution (RTD) of the
fluid. The more distorted the velocity distribution, the broader the RTD. Then, the question is
whether a uniform or a non-uniform radial velocity distribution is beneficial. One already knows
that, for a given mean residence time at steady-state, conversion decreases when the RTD
broadens. It is thus concluded that a uniform velocity profile is beneficial at steady-state.
However, at cold-start, a jet flow in the centre of the monolith speeds up the heating process and
thus promotes an early local ignition. Due to the heat generated by the reactions, the ignited zone
propagates throughout the entire monolith. It is thus concluded that a non-uniform velocity profile
is beneficial at cold-start. These contradictory conclusions suggest that additional studies have to
be done to assess the consequences of flow distribution on converter design.
1.2.4. Heat conduction and heat loss. The monolith ignition induced by a local ignition process,
dealt with in the previous section, depends on the heat conductivity and specific heat of the solid
phase. Low specific heat favours rapid temperature rise and early light-off. Moreover, low heat
conductivity favours large temperature gradients which can be responsible for local high
temperature and thus local ignition at cold-start. It is thus concluded that low heat conductivity
and specific heat may be beneficial. However, the large temperature gradients in case oflow heat
conductivity can be responsible for thermal damage of the catalyst and of the monolithic
structure. Thermal and mechanical stability thus require fairly high heat conductivity to eliminate
large temperature gradients. Finally, a too low heat conductivity would slow down the
propagation of the locally ignited zone.
Because the converter is located below the car, the external temperature is much lower than the
553
average monolith temperature. When the monolith has a high radial heat conductivity, there are
strong heat losses and a large temperature gradient at the monolith boundary. To avoid the
possible thermal damage and extinction phenomenon at the monolith boundary, an efficient
insulator is needed. Presently, it is made of ceramic felt and is also used to protect the monolith
from mechanical vibrations. In most situations, the monolith is close to adiabatic conditions which
favour high temperature and thus high reaction rates. Unfortunately, this also favours local
overtemperatures and thus thermal degradation.
Ceramic monoliths are mostly used at present time, although metallic monoliths are now
available. The specific heat of the metal is lower than ceramic, whereas the heat conductivity is
higher. However, because of the contradictory effects discussed above, it is not known whether
metal is better than ceramic. Finally, metallic monolith seem to have a better mechanical
resistance, whereas their large thermal expansion coefficient can be responsible for wash-coat
breakage.
1.2.5. Pressure drop. The pressure drop depends on many design parameters such as tube
diameter, angles of the inlet and outlet caps, length of the monolith, size and shape of the
channels, and change of tube diameter at fittings. In order to compare different designs, it is
necessary to calculate the overall pressure drop according to the geometrical characteristics of the
muffler. The pressure drop, AP, across an element x (inlet or outlet caps, sudden change of open
cross-section area, etc.), can be obtained by
2
PG U x
L'1P = Sx---y- 0.12)
Where tx can be calculated from correlations of fluid mechanics literature (Idelick (1979),
Midoux (1985), Schliinder (1986), Shah and London (1978». Due to the the lack of accurate data
about the radial velocity distribution across the monolith, the pressure drop across the monolith
is usually calculated assuming a uniform velocity distribution. Despite this assumption,
experimental and theoretical results are in good agreement (Leclerc et al. (1989a, 1991).
At the upstream face of the monolith, the developing laminar flow is responsible for high
transfer rates to the wash-coat. Wendland (1980) suggested to use a segmented monolith to take
advantage of this improvement. Unfortunately, this can lead to a dramatic increase of pressure
drop (Leclerc (1991), Wendland (1980)).
2. Modeling the monolithic catalytic converter
Since experiments on bench test are expensive and time-consuming or lead to unexpected or
unexplained results, a lot of effort has been put on modeling. However, because of the
complexity of the problem, most available models rely on simplifying assumptions which are not
always fully justified (except by computational requirements). These assumptions may even lead
to contradictory conclusions. We will review some of the published models and try to point out
the most important modeling problems. Then, we will propose the structure of an ideal model
which would probably require advanced computational facilities to be tractable. A special
consideration will be given to the assumptions made and on the areas where work should be done
to provide a better description of some elementary processes.
554
2.1. REVIEW OF THE CLASSICAL ASSUMPTIONS
2.1.1 Physical assumptions. Early models assumed that the radial velocity profile is uniform
across the monolith (Oh and Cavendish (1981), Heck et al. (1976), Young and Finlayson
(1976a,b». In other words, the monolith is assumed to behave as a single channel when heat loss
is neglected.
Later, two- or three-dimensional models were proposed (Chen et al. (1988), Chen and Cole
(1989), Zygourakis (1989» to account for the non uniform velocity profile, radial heat conduction
and heat loss. The results obtained with the latter models are more or less puzzling. Concerning
computer requirement, Zygourakis (1989) needed 48 minutes of CRA Y X-MP to simulate 240
seconds of converter operation (CO oxidation only), whereas other authors do not give any
indication about the speed of calculation of their computer. Concerning the usefulness of these
detailed models, Chen et al. (1988) compared CO conversion-versus-time curves assuming either
uniform or non-uniform velocity distributions, and adiabatic or diabatic conditions. The curves
are so close to each other that one wonders whether a three-dimensional model is really
necessary. Conversely, Zygourakis (1989) obtained either close or much different curves
depending on the 0iCO ratio and the velocity profile. Concerning the reliability of the model,
Chen and Cole (1989) obtained a good agreement between simulations and experiments.
Unfortunately, nothing is said about the sensitivity of the calculated curves to the various
parameters, and especially the kinetic rates constants which were adjusted to fit the experiments.
There are so many poorly determined parameters, and so many coupled processes in these
models that it is difficult to understand which processes are predominant at various stages of
converter operation, and what design improvements could be implemented from simulation
results. Finally, it will be shown below that some results obtained from these models are
debatable.
At the channel scale, one may choose either a two-dimensional model accounting for the
laminar velocity profile and transverse heat and mass diffusion process (Graetz-Nusselt model),
or the film model. Young and Finlayson (1976a,b) and Heck et al. (1976) compared the two
approaches. Heck et al. suggested that the film model is as efficient as the Graetz-Nusselt model,
whereas it is much simpler to implement on the computer. Conversely, Young and Finlayson
suggested that the film model is not reliable because it may give unrealistic solutions for some
operating conditions. They supported their conclusions by a single simulation showing strongly
different temperature profiles according to the chosen model. Similar results were then presented
by Ryan et al. (1991). However, these simulations are debatable. Heck et al.(1976) showed that
these results are very sensitive to the feed temperature. Consequently, it may be argued that
Young and Finlayson's and Ryan's conclusions are essentially based on an atypical example
which do not rule out the equivalence between the film and the Graetz-Nusselt models.
Incidentally, Chen and Cole (1989) obtained good agreement between simulations and
experiments using the film model. These contradictory results show that there is no clear proof
that one model is better than the other. Although the Graetz-Nusselt model is more soundly
based, the film model is more tractable and it allows to get a better understanding of various
phenomena involved in the converter. It is on this basis that the approach will be considered in
section 2.2.
In the film model, Nusselt and Sherwood numbers need to be determined. The analogy between
heat and mass transfer suggests that Nu "" Sh. Extensive work has been devoted to the variation
of these numbers with distance, and to their asymptotic values in very long channels of various
shapes (Shah and London (1978». Heck et al. (1976) showed that upstream the light-off point,
the asymptotic wall heat flux Nusselt number must be used, whereas the asymptotic wall
555
temperature Nusselt number must be used downstream. Using a length dependent Nusselt number
they showed that the film model predictions can be bounded by the Graetz-Nusselt model by
changing the feed temperature by ± 1 K. Since the feed temperature is never determined within
± 1 K, this observation suggests that the results of the Graetz-Nusselt and film models are
probably indistinguishable in practice.
Due to the wash-coat roughness and to the more or less regular channel wall, the actual Nusselt
and Sherwood numbers are probably slightly different from theoretical values which assume an
ideal Iy smooth channel wall. The deviation could be of the order of magnitude of the difference
between the constant wall heat flux and constant wall temperature numbers. This means that
constant Nusselt and Sherwood numbers are probably sufficient for modeling purposes. This is
supported by the measurements made by Heck et al. (1974) who obtained Nusselt numbers with
an average deviation about ± 20%, although they remain close to the theoretical asymptotic
values. In contrast, Votruba et al. (1975) determined experimentally Nusselt and Sherwood
numbers which are much different from the ones obtained using theoretical asymptotic values.
They proposed the following correlations
Sh = 0.705 ( Re Dh)0.43
L SCj O.56 (2.1 )
Oh)O.66
Nli = 0.571 ( Re L at Pr = 0.74 (2.2)
where Re, SCj and Pr are the Reynolds, Schmidt and Prandtl numbers:
v
Re = 1I Oh Sc- = - Pr=~= V pg~G (2.3)
.I D ll1j
V ex AG
JI is the kinematic viscosity, u the mean gas velocity in the channel, Ci the thermal diffusivity, Po
the gas density, Cpo the heat capacity of the gas, and Ao its thermal conductivity. Correlations
(2.1) and (2.2) indicate a strong flowrate dependence. For standard monoliths and operating
conditions, Sh ranges from 0.7 to 1.6, and Nu from 0.6 to 2.7 according to the correlations
above. These correlations contradict the results of Heck et al. (1974) and other earlier authors
on one hand, and the results of the comparison between the Graetz-Nusselt and film models on
the other hand. There are several explanations to this discrepancy. As mentioned above, wall
irregularity may be invoked. However, we may also invoke a non-uniform flow distribution in
the monolith sample (Martin (1978)), or the effect of the small LlDh ratio (less than 10) and the
small diameter of the monolith sample used by Votruba et al .. Here again, we see that the gas-
solid transfer process is not fully understood, and that a refined and detailed description of this
process is not presently possible. Consequently, we think that the Nusselt and Sherwood numbers
must be considered adjustable parameters.
The mass and heat transfer coefficients are deduced from the Nusselt and Sherwood numbers
and from the heat conductivity and mass diffusivity in the gas phase. Most authors using the film
model neglect the temperature dependence of the latter parameters. Although probably secondary,
this temperature dependence can be easily accounted for, and it may explain some unexpected
simulation results (Leclerc et al. (1990)).
556
Because of the large heat capacity of the solid and the short residence time of the fluid,
transient state is essentially governed by heat storage to, and release from, the solid. This means
that the gas phase can be assumed to be at steady-state (Oh and Cavendish (1981), Young and
Finlayson (1976a,b), Chen and Cole (1989), Zygourakis (1989), Ryan et al. (1991».
Solid temperature may be above 1000 K, and thus, radiative heat transfer cannot be neglected.
Lee and Aris (1977) focused on the wall-to-wall radiation problem. They showed that this heat
transfer process is responsible for lower conversion due to lower solid temperature and smaller
temperature gradients, and that the maximum solid temperature may be about 100 K below that
calculated with a model ignoring radiative heat transfer. Unfortunately, as mentioned by these
authors, the mathematics are too complex to be incorporated in realistic models. Most
sophisticated converter models neglect the wall to wall radiative heat transfer. Chen et al. (1988,
1989) accounted for gas-solid radiative transfer toward the surrounding medium. The surface
temperature of the converter must be at least 1000 K for the radiation contribution to become
important. Ryan et al. (1991) considered radiation from the front and aft faces of the monolith,
and concluded that this process is not important.
Thermal conduction in the solid phase is a key factor, as already mentioned in section 1.2.4.
The heat conduction process is accounted for by Fourier's law in the heat balance equation which
is thus a second order partial differential equation. An efficient numerical technique is required
to avoid "numerical conduction" because the solid temperature gradient is very sharp at the Jight-
off point (see section 3.1). There is no study of this numerical problem in the literature.
However, Eigenberger (1972) studied the consequences of heat conduction on steady-state
multiplicity. He showed that the conduction process is responsible for a reduction of the number
of steady state solutions. In the example studied by Eigenberger, the steady-state solution is close
to the "highest steady state" (i.e., steady state with the temperature maximum close to reactor
inlet) without conduction because "the temperature maximum moves to the front of the reactor,
driven by the backward conduction of heat".
2.1.2. Chemical assumptions. Most authors use the kinetic expressions proposed by Voltz et al.
(1973). Generally, the frequency factors are adapted to represent the catalyst under use, whereas
the activation energies and heats of adsorption are kept unchanged. Since most available catalysts
have qualitatively the same composition, this method could lead to meaningful results. However,
the effects of promoters like CeOz, the nature of the contact between Rhodium and Platinum
(Alloy? Mixture of pure crystalites ?), and the oxidation state of Rhodium, are poorly known,
and one must be careful. Finally, one may wonder whether the kinetic rate expressions are still
valid under transient conditions, especially because CeO z is presumed to store oxygen. In the
absence of convincing results, all authors assume that the rate expressions given in section 1.2.1
can be used in the transient state.
The assumption of equal reaction rates for Hz and CO oxidation is discussed by Zygourakis and
Aris (1983). Analyzing published data, they showed that Hz oxidation is faster than CO oxidation.
Their results can easily be used to modify the expression for r:/3.
Experiments show that the catalyst deactivates slowly. Thermal aging does not seem to be dealt
with in the literature. The first theoretical study of poisoning (essentially by phosphorus
compounds) was performed by Lee and Aris (1983) who considered either selective or non
selective poisoning. According to the poisoning mechanism, the catalyst may deactivate either
from upstream or downstream. Oh and Cavendish (1983) used the non-selective poisoning model
to describe the poison profile and the conversion performance at warm-up. Although the
poisoning mechanism is not fully justified, these authors suggested many design possibilities
(wash-coat thickness, metal loading, BET surface area, etc.) to improve poison resistance.
557
Zygourakis (1989), considered the same model and included a non-uniform radial velocity
distribution. He concluded that this distribution may be at the origin of severe performance
degradations. Although the various conclusions are coherent, the lack of reliable deactivation
kinetics together with debatable rate expressions for the main reactions render these conclusions
qualitative.
Most models assume that there is no diffusion limitation in the wash-coat because "it is a thin
catalytic layer". Only Zygourakis and Aris (1983) considered this problem, and showed that the
effectiveness factor can be much smaller than one. This problem will be reviewed below.
2.2. THE PROPOSED MODEL
Based on the previous review of published results, we will present a model relying on the
following assumptions:
Al - The wash-coat thickness, w, is much smaller than Db'

A2 - The thermal conductivity and heat capacity of the wash-coat and of the monolith are
identical.
A3 - Pressure is uniform and constant.
A4 - Thermal conduction in the gas phase is neglected.
AS - The thermal conductivity of the monolith is independent of temperature.
A6 - The gas phase is ideal.
A7 - The monolith is cylindrical and it has uniform properties in a cross-section.
A8 - Heat transfer by radiation is neglected.
A9 - Transverse diffusion and laminar flow are accounted for by the film model.
AlO - The catalyst does not deactivate.
2.2.1. The mass balance equation in the gas phase. The radial diffusive mass flux is given by
equations (1.7). Because of the chemical expansion due to the chemical reactions, the mass flux
of species j is given by
(2.4)
where the cp is the total radial flux
(2.5)
Figure 2.1 illustrates the control volume over which the mass balance equations are written. The
mass balance equation for species j and the overall mass balance equation are respectively
(2.6)
(2.7)
558
where u is the fluid velocity in a channel. Combining equations (2.6) and (2.7) yields
ik 4 ik
UCTG ~ + Dh kDj CrG (Xj - Xjs) + CTG ~ =0 (2.8)
The total gas phase concentration, Cro , is calculated from the gas temperature by the perfect gas
law.
r + dr
dz
Figure 2.1. Typical control volume.
2.2.2 The mass balance equation in the wash-coat. Assuming pseudo steady state in the wash-
coat, the mass balance is
R
<Pj = - ~Pwcw LVij ris (2.9)
i=]
where {3 is the specific area of noble metal per unit mass of wash-coat, p.., is the wash-coat
density, w the wash-coat thickness, "ij the stoichiometric coefficient of species j in reaction i, and
rio the i-th apparent chemical reaction rate per unit surface area of noble metal.
2.2.3 The heat balance equation in the gas phase. Combining an enthalpy balance with the mass
balance equations gives
(2.10)
where To and T, are the gas and solid temperatures respectively. CpO is given by
CTG LXjC;, = PGCpG (2.11)

j=l
where C', is the molar heat capacity of species j.

PJ
2.2.4 The heat balance equation in the solid phase. Combining an enthalpy balance equation with
the mass balance equation in the wash-coat gives
559
(2.12)
where e is the monolith void fraction, ~Hi the i-th reaction enthalpy, Cps the heat capacity of the
solid per unit mass, Ps the real density of the matrix (channel excluded). A,. and X. (w m· l of
monolith Kl) are the effective radial and axial heat conductivities referred to monolith area.
Typical values for Corning- ceramic monoliths are:
Az = 0.38 Ar = 0.25 w m- I K-I

Cps = 1050 j kg-I K-I, Ps = 1800 kg m- 3, f= 0.76 (62 cells cm- 2)
At monolith boundary the heat balance equation is
(2.13)
where T. is the external temperature, and U the external heat transfer coefficient.
2.2.4 Non dimensional numbers and equations. Table 2 summarizes the main definitions of the
non-dimensional numbers and their order of magnitude. The non dimensional equations are then
UX Sh ax'
~ + Gr -L. (Xj - Xjs) + ~ = 0 (2.14)
u~ ~ ae
Sh
'Vj = Gr Le. (Xj - Xjs) + 'V (2.15)
J
R
'Vj = - L VijRis (2.16)
i=1
uTo + GrNu (To - Ts) + uTo
__ = 0 (2.17)
. ae
__I J
u~
L aT S ) + K' aTs + GrNu (T - To) (2.18)

y ay ue S
(2.19)
aUCTO C aCTO 0
- - + u TO'V+U--= (2.20)
u~ ae
560
Table 2. Non dimensional numbers.

Name Definition Order of magnitude
Reduced abscissa ~=zlL o to I
Reduced radius y = rlR o to I
Reduced time e = tulL variable and » I
Reynolds Re = uDhI'v a few hundreds
Nusselt number Nu = hDh/Aa 2 to 5
Sherwood number Sh = kDjDh/Dmj 2to5
Prandtl number Pr = via '" 0.7
Schmidt number SCj = v/Dmj '" 0.7 except H2: '" 0.2
AG
Lewis number Lej = ScjlPr = - - " ' - - - ",I except H2: '" 0.3
PGCpGDmj
Graetz number Gr = _4L_ = _4_L_Aa...:=:...-_ variable, but'" 1

DhRePr uDh2PGCpG
Heat capacity factor K' = 1-£ PsC ps

'" 4000
£ PGCpG (cordieri te )
Axial thermal Peelet variable'" 104

(cordierite)
_ uL(l-£)psC ps (~)2
Radial themlal Peelet Per - L variable'" 103
Ar (cordierite)
Reduced flux
Adiabatic temperature J * = CTG( -t.Hj)

rise of pure reactant 1
Reduced reaction rate
Remarks:
1. GrSh/Lej varies with the gas temperature owing to the mass transfer coefficient ~ and
the gas velocity u.
2. Similarly GrNu varies with To.
3. K' varies with To owing to PoCpo , and with Ts owing to Cps'
4. Pee and Pez are assumed to be constant.
561
2.2.5 Consistency of the model. Comparing equations (2.14) and (2.20), the gas-solid mass
transfer fluxes must satisfy
L xiLe;is=L xiDm~is=o
N N
(2.21)
j=1 j=l
where N is the number of species. This equation is an extra constraint resulting from the
simplified description of the transverse diffusion process. Using the Graetz-Nusselt model
together with Stefan-Maxwell equation for diffusion would eliminate the problem. Unfortunately
the equations become intractable.
To avoid the possible inconsistency, we will exclusively focus on the reacting species, and we
assume that the inert species make equation (2.21) to be satisfied.
2.3. SIMPLIFICATION OF THE MODEL
In general, the reacting species are much diluted by an inert gas. Consequently, the chemical
expansion flux, r/J, is expected to be negligible with respect to the diffusion flux, and as a
consequence of this:
(2.22)
As discussed in section 2.2.1, the accumulation rate in the gas phase is negligible (except when
the engine stops !) and thus the gas phase accumulation terms are zero. This assumption allows
to write equations (2.14) and (2.17) as
OX' Sh (2.23)
~ + Gr Lej (Xj - Xjs) = 0
oTG + GrNu (TG - Ts) 0 (2.24)

o~ . =
With the above described assumptions, equation (2.20) becomes
~_u_CIG = 0 (2.25)
o~
Equation (2.25) means that the molar flowrate depends on time and radial position exclusively.
2.4. ESTIMATING THE PHYSICAL PARAMETERS
Most of the physical parameters can be estimated from Reid et al. (1977). Calculation of Dmj
would require to use Stefan-Maxwell equation which leads to composition-dependent diffusivity
(Froment and Bischoff (1979». Although this equation can be easily implemented in a computer
code, we believe that this detailed calculation is unnecessary in the case of the film model.
562
Moreover, assuming that the reacting species are diluted in a single inert species (nitrogen for
instance), Dmj is the binary j-nitrogen diffusivity. Table 3 summarizes typical values of the
physical parameters.
Table 3. T:'iJ2icall2hysicall2arameters at various teml2eratures.
T(K) 300 500 700 900
C; (N2, cal mol- I K-I) 7.0 7.1 7.4 7.7
C p (N2, J kg-I K-I) 1045 1060 1104 1150
lQ4DN2-eo (m2 s-I) 0.204 0.490 0.863 l.31
v (N2, m 2 s-I) 1.51 10- 5 3.61 10-5 6.30 10-5 9.55 10- 5
11 (N2, kg m- I s-I) 1.72 10- 5 2.4610- 5 3.07 10-5 3.62 10-5
A. (N2, w nrl K-I) 2.61 10- 2 3.78 10-2 4.8910- 2 5.99 10- 2
From these values and the asymptotic Sherwood and Nusselt numbers, the heat and mass transfer
coefficients can be calculated, provided the film temperature is known. Here, we are facing one
of the main difficulties while applying the film model: at which temperature should the mass
transfer parameters be estimated, the one of the gas, the one of the solid, or at an average
temperature ? In section 3 we will see that numerical simulations based on various assumptions
lead to similar results. Consequently, it seems that the results are fairly insensitive to the
assumptions made.
2.5 THE EFFECTIVENESS FACTOR
r
We will only focus on the effectiveness factor for CO oxidation in a stoichiometric mixture.
Using the general definition of Froment and Bischoff (1979), one has
~,~ w ,)c,) [ mej(e) de (2.26)
where Cc is the concentration at the wash-coat/substrate interface. It is implicitly given by
__ IDc~C' dC"
w - "V "2 1/2 (2.27)
[dr(C') 1
C"
dC'
Cc
The reaction rate is given by
r(C) = k Ceo C02 (2.28)

(1 + K Ceo)2 2(I+KC)2
where C = Ceo = 2C02 ' and r(C) is expressed in mol S-1 m") of wash-coat. The kinetic constants
are taken from Heck et al. (1976):
k(P/RTs )2 = 4.14 10 16 exp( -12600rrs) mol m- 3 of wash-coat s-I (2.29)

563
K(PIRT s) = 65.5 exp(96lffs) (2.30)
The wash-coat is made of microporous alumina particles with an average pore radius of about
10-8 m. The internal diffusion process is thus governed by molecular and Knudsen diffusion. The
molecular and Knudsen diffusivities are calculated by
D = DO (Tffo)1.75, TO = 500 K, DO = 5 10- 5 m 2.s- 1 (231)
2 R 8 R T 1/2
DK =~ ( - - ) = 4.1 10-6 (Tffo)I/2 m 2.s- 1, TO = 500 K (2.32)
3 1t Meo
Since Knudsen diffusivity is ten times smaller than molecular diffusivity at 500 K, we will ignore
the molecular contribution. The internal porosity, Pi> is close to 0.5. Assuming the tortuosity
factor T to be about 2, the effective diffusivity is given by
~.
Dc =--1 DK = 1.1 10-6 (Tffo) 1/2 m2.s- l , To = 500 K (2.33)
T
Table 4 gives the generalized Thiele modulus <Ps = l/11s(C c=O) for various surface CO mole
fractions and various surface temperatures, assuming a wash-coat thickness of 10-5 m.
Table 4. Generalized Thiele modulus

Ts(K) 700 800 900 1000 1100
xeos
0.05 0.25 0.9 2.7 6.1 12.1
O.D1 0.5 1.9 5.1 1l.5 22.2
D.OOI 0.55 1.9 4.7 10 18.4
(WOOl 0.22 0.7 1.8 3.8 6.9
The classical Thiele modulus is defined by
(2.34)
together with n = 2. Table 5 presents values of CPs for various conditions.
Table 5. Classical Thiele modulus.

Ts(K) 700 800 900 1000 1100
XCOs
0.05 0.4 1.4 4 9 17.7
0.01 0.7 2.4 6.4 14.2 27.2
(l.00l 0.6 2 4.9 10.4 19.1
0.0001 0.2 0.7 l.8 3.8 6.9
Two main conclusions can be drawn:

1 - Above 900 K, the reaction is diffusion-limited on the basis of the rough estimates of the
effective diffusivity.
2 - The classical Thiele modulus gives a fairly satisfactory estimate of the generalized Thiele
564
modulus. This is most valuable because it allows to estimate the effectiveness factor more simply
than by equations (2.26) and (2.27).
Although these calculations suggest that the reaction is diffusion-limited, quantitative estimates
of the effectiveness factor are still questionable. The wash-coat is made of alumina particles with
widely distributed radii. Assuming an average particle diameter of about 6. 10.6 m, the wash-coat
becomes two-particles thick on the average. Consequently, there is still uncertainty whether mass
transfer in this layer is controled by diffusion, or induced by fluid flow. If mass transfer is not
limiting in the macroporosity of the wash-coat, then the above calculations should be made
substituting wllO for w in the Thiele modulus, increasing noticeably the effectiveness factor.
3. Typical results
We will first deal with CO oxidation to understand the main processes taking place in monoliths.
Then, we will deal with the more general case of competing reactions.
3.1. CO OXIDATION
Studying converter behaviour for a single reaction at steady state helps to understand the main
features of the process. For the sake of simplicity, we will assume that the monolith is adiabatic,
that there is neither heat conduction, nor internal diffusion limitations, and that the radial velocity
profile is uniform. The kinetic rate expression is taken from Heck et al. (1976) (See also (2.28 -
30».
The operating conditions are represented by the Gas Hourly Space Velocity (GHSV) which is
defined by the ratio of the volumetric flowrate at feed temperature to the volume of the monolith.
Figure 3.1 illustrates typical mole fractions and temperature profiles in the bulk gas and at the
channel wall for an oxidizing mixture and a monolith operated at a GHSV of 75 000. The light-
off point is located close to z/L = 0.25. The solid temperature reaches a limiting value, whereas
the solid mole fraction drops close to zero. This observation can be easily explained as follows.
In an adiabatic monolith with a single chemical reaction at steady state, equation (2.18) becomes
(3.1 )
Combining (3.1) with (2.22), (2.23), and (2.24) gives
(3.2)
when Sh = Nu and Ltj = 1, equation (3.2) becomes
(3.3)
Equation (3.3) is valid for most gases except Hz. If Xeo. is close to zero, then T, is the feed
temperature plus the adiabatic temperature rise xco(O) J ;0'
We will discuss in the following
565
section why X co• drops to a level close to zero at light-off.

Hegedus (1975) studied the case where the ratio Sh/(Nu Ll1) differs from unity. For H2 , the
ratio is greater than unity (See Table 2 assuming Nu = Sh), and this results in a local
temperature overshoot at the light-off point. This phenomenon has been experimentally
confirmed, and it must be accounted for in the models because it can be at the origin of thermal
degradation of the monolith. This also means that reliable estimates of Sh, Nu and Ll1 are
necessary.
800 .::-.::'.::.:;......... r····..············..············ 20x1O-3
"', 'C
"j
750 ~I ......... T solid 15 
r- i \ P>
i GHSV 75 000 h· 1
650 .~
~
5 o·~
::l
...............,.,.••.....
600 0
0.0 0.2 0.4 0.6 0.8 1.0
zlL
Figure 3.1. Temperature and mole fraction profiles. Inlet temperature 593 K, feed composition
2%CO + 2% 02'
Figure 3.1 shows that downstream of the light -off point Xco• is at the most 2 10-4 whereas T.
,., 800 K. Moreover, and referring to the results of section 2.5 (Table 4), we concluded that
internal diffusion limitations are negligible. However, increasing CO mole fraction in the feed
would result in higher Xco• and T. making diffusion limitations presumably more important.
Light-off is essentially due to steady state multiplicity, and it has been simply explained by
Heck et al. (1976). Assuming Nu = Sh and Lej = 1, equation (3.2) allows to express T. as a
function of XCOs' When there is an excess of oxygen, X02 can be assumed to be constant.
Consequently, r depends exclusively on Xco. (see left-hand side equality of (2.28». Figure 3.2
illustrates r as the thick curve. Ignoring the temperature dependence of CTQ, equations (2.15) and
(2.16) define parallel straight operating lines, relating the kinetic rate to the local wall and bulk
gas concentrations. These lines intercept the horizontal axis at Xco = Xco•. Three situations are
illustrated in Figure 3.2 according to the bulk gas concentration.
The continuous line (xco = 0.04) illustrates a point close to the monolith inlet, and there are
three possible steady state solutions (points A, B, and C). Only points A and C are stable.
Depending on the past history of the system, either point A or C can be actually observed. When
steady state is reached after cold-start, the cold point A is obtained. Moving downstream the
monolith, the intercept of the operating line with the horizontal axis moves toward the left, and
point A moves smoothly along the rate curve from A to D where the operating line is tangent to
the rate curve. Further downstream (dashed line) there is a single steady state solution (point F).
Thus, just downstream the location represented by D, the monolith state is defined by E. Points
D and E define the two states adjacent to the light-off point. This point is characterized by a
discontinuity of Xco• (abscissa of points D and E), whereas Xco is continuous (intercept of the
dotted line with the horizontal axis). At the light-off point, the wash-coat temperature and
concentration vary discontinuously, whereas they vary smoothly (from E to F) further
downstream. The discontinuity D - E explains why Xco. suddenly drops dramatically at light-off.
566
0.10 - kinetic rate 1000

..... T,
----
'§
~
0.08 Operating lines 900

;>, •••••• - xeo = 0.040
§ 0.06 B····. .. . . . Xco = 0.029 800
:0 •.. '41.....
-. .----. xeo = 0020
.
E.- 0.04 ....... 4r
'''''.,.
....
'.,
... .. 700
<l)
~ 0.02 '.'
'
O. 00 "i------,---.....:.:.:.:;-----..::::::::::;::==~~ 600
o 2 3 4xlO· 2
Figure 3.2. Light-off and steady state multiplicity.
Figure 3.3 compares the CO mole fractions in the bulk gas and in the wash-coat. The GHSVs
are chosen to obtain light-off (steepest part of the curves) about z/L = 0.2.
~
100
c
y
..c
~ GHSV (h- I )
;;.
0 10 ----- 75000
~
.......... 50 000
r/J
cO - 25 000
OIl
0
u
1
0.0 0.2 0.4 0.6 0.8 l.0
z/L
Figure 3.3. xco/xcos versus abscissa. Downstream the light-off point the reaction is governed by
mass and heat transfer. Inlet temperature 593 K, feed composition 2% CO + 2% Oz.
Upstream the light-off point, the catalyst works in the chemical regime (i.e., xco/xcos ::::: 1).
Downstream the light-off point, the reaction is governed by mass and heat transfer through the
film (xco/xcos ::::: 100), and the reaction kinetics become first-order. When the monolith is fully
ignited (high feed temperature and light-offpoint at the inlet), most authors have concluded that
the converter works under transfer limitations exclusively. This conclusion being true for an
oxidizing feed mixture, is not correct for a stoichiometric mixture. Figure 3.4 illustrates the
concentration and temperature profiles for a stoichiometric feed, and Figure 3.5 compares the CO
mole fractions in the gas and the wash-coat.
567
800 ................... =- .......................... . 20xl0-3

• '=-'='::-'::-'::-'::-'':-''::,~ ,(
750 .......... T solid I
15 0
(J
\:,i, S
g 700
-Tgas
00_.- CO solid I 10 2-
E-< . - - CO gas ! '- ::j>
""
~
650 GHSV 50 000 h- 1 .f \\ o·
=
. . =-.. ._. . ._. . . . . . _. . ._.,-,.-=::::.:.:.~~==.l-
........ 5 ::l
600 ~::::::::.::
.....::
......;::....
0
0.0 0.2 0.4 0.6 0.8 1.0
zlL
Figure 3.4. Concentration and temperature profiles. Inlet temperature 593 K, feed composition
2% CO + 1 % Oz.
0.0 0.2 0.4 0.6 0.8 1.0

zlL
Figure 3.5. xeo/xeos versus abscissa. Downstream light-off the reaction is governed by chemical
kinetics. Inlet temperature 593 K, feed composition 2% CO + 1 % Oz.
External heat and mass transfer processes are exclusively competing with the chemical reaction
in a narrow region close to the light-off point. Upstream and downstream of the light-off point,
chemical regime prevails. The difference between the stoichiometric and non-stoichiometric
behaviour downstream of the light-off point can be explained quite easily. The mass transfer
process is a linear process. In an Oz-rich mixture, X 02 remains approximately constant. If the
inhibition term of the rate expression is ignored, then the reaction becomes pseudo first-order.
Consequently, the rate limiting process is independent of the concentration level. Conversely, in
a stoichiometric mixture, the rate expression becomes pseudo second-order (see right-hand
equality of (2.28». When concentration decreases, the reaction rate is more influenced by this
effect than the transfer rate, and as a consequence chemical regime dominates.
3.2. TRANSIENT STATE AND COMPETING REACTIONS
We will now investigate the behaviour of the monolith in the transient state considering oxidation
of CO, C3 H6 , and H2 and inhibition by NO. We will only assume that there is no diffusion
limitations in the wash-coat, that the monolith is adiabatic, and that there is no radial heat
568
conduction. Finding a numerical solution for equations (2.14) - (2.20) is an overwhelming task.
We will thus present the results based on the mixing ceIl in series approach as already proposed
by Kuo et aI. (1971). This approach consists of using a first-order space discretization of the mass
balance equations. The number of space increments, J, should be wisely chosen so as to avoid
numerical dispersion. Unfortunately, due to the sharp gradients at light-off, numerical dispersion
is somewhat unavoidable. The number of space increments has thus been chosen to avoid
excessive dispersion while allowing calculations to be conducted in acceptable computing time.
The effect of various parameters, assumptions, and of J will be discussed below.
3.2.11he balance equations. The discrete model is based on assumptions Al to AlO of section
2.2. Let k be the index of the mixing-cell. The mass balance in the bulk gas and solid phases are
respectively
C ( 4
lIk TGk Xj,k - Xj,k-I) + Dh kDj,kCTGk(Xj,k - Xjs,k) + CTGk
ax' k = 0
T (3.4)
R D R
j,k = - ~kPwcW ~>ij fis,k = - 4h akLvij fis,k (3.5)
1=1 i=1
with (:Jk allowing for the specific area of noble metal to change from one cell to the other. This
allows to simulate in a simple fashion a deactivated monolith, or the influence of a non-uniform
activity distribution. Moreover, ak is a specific activity parameter defined as the surface area of
noble metal per unit volume of gas phase.
Concerning the heat balance equations, they are given as follows
4£
+-Dh h(Tsk-TGk) (3.7)
' ,
where hz is a heat transfer coefficient equivalent to heat conductivity. Comparing equations (2.12)
and (3.7) it results
hz = Az t (3.8)
At the monolith inlet k = 1, and at the monolith outlet k = J. At the monolith inlet and outlet,
the heat conduction terms are given by
hATs,k+1 - 2Ts,k +Ts,k-I) = h z (Ts ,2 - Ts,l) when k = I (3.9)

and
hz(Ts,k+1 - 2Ts,k +Ts,k-I) = hz(Ts,J - Ts,J-I) when k =J (3,10)
To simulate a non-uniform radial velocity distribution, the monolith is assumed to be composed

of several macrochannels placed in parallel where fluid velocity is uniform. Fluid velocity varies
from one macrochannel to another. Since radial heat conduction is ignored, the full model is
569
composed of as many sets of equations (3.4) - (3.7) as macrochannels. Here again, the number
of macro channels has to be limited in order to save computer time.
As mentioned in the introduction, the catalytic converter is operated in the transient state with
respect to feed composition, flow rate, and temperature. Then, in order to study the effect of
various parameters, we will vary some of them within the ranges given in Table 6.
Table 6. Standard parameters for the simulations

Feed composition Monolith Feed properties
xCO = 0.015 X02 = 0.03 Mass: 1.08 kg a=5000 m 2.m-3 Tinlet = 700 K
XC3H6 = (W005 XC02 = 0.1 Gas volume: 1.25 10- 3 m 3 Flat velocity profile
xNO = 0.0005 xH20 = 0.1 Wash-coat area: 4.5 m 2 Flow rate: 2 mol s-l
XH2 = 0.005 XN2 = 0.749 Number of mixing cells 1=9
hz = 0
Our first goal is to test the sensitivity of the model to the parameter J. Light-off times and
residual pollutant mole fractions are sensitive to J when it is smaller than 20. Consequently, a low
value of J describes the trend of the process only. When axial heat conduction in the solid is
accounted for, and if J is smaller than 20, then simulation results are nearly independent of b..
This means that, with small J values, the mixing-cell-in-series model is unable to account for
axial heat conduction. Unfortunately, large J values result in an unacceptable computer time.
Consequently, we will present results assuming hz = 0, and J = 9 which has been found to give
a fairly good compromise between computer time and reliability of simulations. These results,
not describing the process accurately, allow to observe the predominating governing factors and
the main behaviours only. It has to be pointed out that only reactions (1.1) to (1.3) will be
considered in these simulations.
3.2.2. The oxidizing converter. As mentioned in section 3.1, the converter works under heat and
mass transfer control downstream of the light-off point, whereas kinetics control upstream. Since
pollutants are essentially burnt downstream of the light-off point, steady state conversions are
much sensitive to the heat and mass transfer parameters and show little sensitivity to kinetic
parameters. Conversely, being the Iight-off point at the border of the chemical and transfer
regimes, its characteristics depend both on transfer and kinetic parameters. Accurate Nusselt and
Sherwood numbers are therefore required for obtaining good quantitative prediction of oxidizing
converter performance. This also means that the wash-coating procedure must be carefully
controlled, since it can modify the shape of the channels and then the heat and mass transfer
characteristics.
We will first study the sensitivity of the model to the temperature dependence of the transfer
parameters. It has been found that using either To, or T., or the arithmetic mean for estimating
the heat and mass transfer parameters, gives nearly the same results. Conversely, the temperature
dependence of the molecular diffusivity seems to be important. Two models were compared, one
assuming constant diffusivities, the other assuming a temperature dependence given by
OCT)
J
= O'(T
J 0
) (2.)1.75
TO (3.11 )
570
With the constant diffusivity, light-off time and conversions at steady state are underestimated,
and artificial temperature overshoots and concentration undershoots are observed in the transient
state (Leclerc et al. (1990».
Furthermore, the effect of the velocity distribution can be studied assuming simple stepwise
distributions:
-Uniform distribution modeled with a single macrochannel.
-Two identical macro channels with U l = O.5u, and U 2 = 1.5u.
-Three identical macrochannels with U l = 0.5 u, Uz = u, and U3 = 1.5u.
As expected, a slightly earlier light-off occurs when there are channels with high gas velocity.
Conversely, steady state conversions decrease when the velocity is not uniform. For non uniform
velocity distributions, at steady state the maximum temperature difference between adjacent
channels is about 25 K. Given that the model ignores heat conduction in the solid, the actual
temperature difference is probably much smaller except at monolith boundary.
Knowing that gas temperature decreases by about 100 K per meter of exhaust tube, the location
of the converter can be simulated using different feed temperatures. Figure 3.6 illustrates typical
solid temperatures at steady state. For high feed temperatures, the monolith is fully ignited. Due
to the presence of H2 which has a low Lewis number, a small temperature overshoot is observed
at the inlet (see discussion section 3.1). As long as the feed temperature decreases (Le., the
converter is placed away from the engine), the light-off front moves downstream. Between 660
and 560 K the light-off front is located somewhere in the monolith. The associated large
temperature gradient can be responsible for thermal damage of the substrate and the catalyst.
900.--------------,
g
~ 800
a -e- Tinlet=550K
~
...
-M- Tinlet=580K
E 700
<l)
00- Tinlet=590K
Tinlel=600K
~
-Q::::=-----
:-g 006- Tinlel=650K
-0 600
if)
123456789
Axial coordinate (mixing cell number)
Figure 3.6. Effect of feed temperature on solid temperature profile. Oxidizing converter.
Stepwise catalytic activity distributions has also been simulated assuming the same average
activity whatever the distribution. Since the converter operates under transfer control at steady
state, steady state conversions are nearly independent of the distribution. However, high upstream
activity is responsible for slightly earlier light-off.
3.2.3. The three-way converter. Since the concentration of NOx is very small, the heat generated
by the reduction reaction is expected to have a minor effect on temperature and conversion
predictions (Chen et al. (1988». Owing to the absence of accurate data on NOx reduction
kinetics, a preliminary approach to three-way catalytic converters consists of simulating only
oxidation reactions under stoichiometric conditions. The standard parameters used in the
simulations are given in Table 6 except that the feed mole fraction of O2 and N2 are now 0.01225
571
and 0.76675 respectively. Contrary to the oxidizing converter, the three-way converter is
sensitive to kinetic parameters at steady state. Whatever the feed temperature, the solid
temperature gradient at light-off is much smaller than in an oxidizing converter (see Figure 3.6)
and there is no temperature overshoot due to H2 •
g 800
+ Tinlel=600K
-0- Tinlet=620K
.... Tinlet=650K
"*" Tinlet=700K
I 2 3 4 5 678 9
Axial coordinate (mixing cell number)
Figure 3.7. Effect of feed temperature on solid temperature profile. Three-way converter.
Similarly to CO oxidation (see section 3.1), chemical reactions and external heat and mass
transfer are competing everywhere in the monolith. Consequently, catalyst deactivation is
responsible for a dramatic performance drop. Since deactivation is generally not uniform
throughout the monolith, a simple method to partially recover high activity would be to reverse
the monolith.
A non uniform activity, decreasing from inlet to outlet, is responsible for slightly smaller light-
off times and for a slight increase of conversions.
The non uniform velocity distribution represented by two macro channels dealt with in section
3.2.2 gives nearly the same light-off time as a uniform velocity distribution when the kinetic rate
constants are increased by 10%. This clearly shows that various parameters of different physical
origin can compensate each other. This indicates that it is impossible to accurately predict
conversions in three-way converters due to the lack of reliable kinetic data.
4. Conclusions
Monolithic catalytic converters are now of wide use on automotives, however their efficiency and
their resistance to thermal shocks, poisons, misfiring, etc., must be improved. Beside new
catalyst formulations and experimental tests, modeling and understanding of the main physical
and chemical processes can help to suggest design improvements.
Unfortunately, the many time-dependent operating parameters (feed composition, flowrate, and
temperature), the limited knowledge of the basic processes (kinetic rates, poisoning, gas velocity
distribution, heat and mass transfer, etc.), and finally the possibility of steady state multiplicity,
make modeling of the converter an overwhelming task.
We believe that most models are trend models and that simulation results are indicative at best.
Performance predictions can be used to test various assumptions concerning the basic processes
against experiments. They can also be used to assess model sensitivity to the basic parameters.
572
Presently, few studies have been devoted to sensitivity analysis which should be considered in
more detail in the future. Eventually, careful attention should be paid to the numerical procedures
used to solve the equations. This is crucial for a clear understanding of the effect of the heat
conduction in the solid and to clarify the advantages of metallic monoliths over ceramic
monoliths.
In the oxidizing converter, it has been accepted that heat and mass transfer processes are the
main controlling steps except at cold start. An analysis of the converter behaviour at
stoichiometric conditions shows that this conclusion is not a general one, and that transfer
processes and chemical reactions are competing in three-way converters. This suggests that more
reliable kinetic rate expressions are required to obtain reliable simulation results.
Chemical engineering literature is mainly focused on modeling the converter as a whole.
However, a lot of work remains to be done at the catalyst level. Are the available kinetic
expressions valid in the transient state? What is the effect of oxygen storage in Ce02 ? What is
the effect of oxidation state of Rhodium ? All these questions should be answered to obtain
reliable model predictions.
Finally, few comparisons between simulations and experimental results are available from the
literature. Does it mean that the comparisons failed? If yes, it would be of prime importance to
track the wrong model assumption(s) responsible for the failure. If not, it is time to improve
prediction reliability to progressively substitute some expensive and time consuming engine tests
for cheaper computer simulations. Destruction of the converter in the computer is less costly than
on the bench test!
Acknowledgements
The "Groupement Scientifique Pot Catalytique" of the Institut Francais du Petrole, the PIRSEM
(Programme Interdisciplinaire de Recherches sur les Sciences pour I'Energie et les Matieres
premieres), and the Chemistry Department of the CNRS are gratefully acknowledged for their
help.
List of symbols
ak specific activity (m2 of noble metal m·3 of gas)

Cpo heat capacity of the gas (J kg- 1 Kl)
Cp; molar heat capacity (cal mol- 1 Kl)
Cc concentration at the wash-coat/substrate interface (moI.m-3)
C, wall surface concentration (mol m-3)
CTO total gas phase concentration (mol m-3)
Do molecular diffusivity at To (m2 S-I)
De effective diffusivity (m2 S-I)
Dh hydraulic diameter of a channel (m)
DK Knudsen diffusivity (m2 S-I)
Dmj molecular diffusivity of species j (m2 S-I)
F(x) defined by (1.6)
GHSV gas hourly space velocity (h-l)
Gr Graetz number
h heat transfer coefficient (w m-2 Kl)
hz equivalent axial heat transfer coefficient (w m-2 Kl)
573
J number of mixing cells in series

J;' adiabatic temperature rise for pure species j
K' heat capacity factor
k..j , K adsorption constant of species j, of CO
k Dj mass transfer coefficient of species j (m S-I)
ki" k kinetic constant (mol m-2 of noble metal S-I KI), (mol S-1 m-30f wash-coat)
L length of the monolith (m)
Lej Lewis number
Mea molecular weight of CO (kg mol-I)
N number of species
n reaction order
Nu Nusselt number
Pez axial thermal Peclet number
Per radial thermal Peclet number
Pr Prandtl number
qD specific heat conduction flux (w m-2)
R number of reactions, radius of the monolith (m)
~ pore radius (m)
Re Reynolds number
Ri , reduced reaction rate
r radial coordinate (m)
r reaction rate (mol S-I m-3 of wash-coat)
reaction rate in the solid catalytic phase (mol m-2 of noble metal S-I)
Schmidt number of species j
Sherwood number of species j
external temperature (K)
gas temperature (K)
solid temperature (K)
time (s)
external heat transfer coefficient (w m-2 KI)
mean velocity of the fluid in the monolith or in a channel(m S-I)
mean velocity of the fluid in macrochannel i (m S-I)
mean velocity in element x (m S-I)
wash-coat thickness (m)
mol fraction of species j in the bulk gas phase
mol fraction of species j in the wash-coat
reduced radial coordinate
axial coordinate (m)
Subscripts
j species j
i reaction i
k cell k
574
Greek symbols
a thermal diffusivity (m2 S·I)
f1 specific area of noble metal per unit mass of wash-coat (m2 kg· l )
f1i internal porosity of the catalyst
L\Hi enthalpy of reaction i (J mol· l )
L\P pressure drop (pa)
e void fraction
~. generalized Thiele modulus
rP. classical Thiele modulus
rP total specific diffusive mass flux (mol S·I m'~
rPj overall specific diffusive mass flux of species j (mol S·I m·2)
rPDj specific diffusion flux (mol S·I m·2)
11. internal effectiveness factor
(J reduced time
An heat conductivity of the gas (w m· 1 KI)
A. axial effective heat conductivity of the monolith (w m· 1 of monolith KI)
"" radial effective heat conductivity of the monolith (w m· 1 of monolith KI)
JL dynamic viscosity (kg m· 1 S·I)
v kinematic viscosity (m2 S·I)
vij stoichiometric coefficient of species j in reaction i
Po density of the gas (kg m·3)
P. density of the matrix (kg m·3)
Pwc wash-coat density (kg m·3)
T tortuosity factor
l/;j reduced diffusion flux
l/; reduced overall diffusion flux
~ reduced axial coordinate
tx pressure drop coefficient for element x
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575
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pp. 518-524.
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in race-track monolithic catalytic converters - A theoretical and experimental study', AIChE
1990 spring national meeting, 18-22 mars 1990, Orlando, Floride, USA.
Leclerc, J.P. (1991) Contribution it l'etude du fonctionnement des pots catalytiques, PhD thesis,
Institut National Polytechnique de Lorraine, Nancy, France.
Lee S. T., and R. Aris (1977) 'On the effect of radiative heat transfer in monoliths', Chern. Eng.
Sci., 32, 827-837.
Lee S.T., and R. Aris (1978) 'Poisoning in monolithic catalysts', ACS Symp. Series, 65,
pp. 110-121.
Lemme C.D., and W.R. Givens (1974) 'Flow through catalytic converters. An analytical and
experimental treatment', Paper SAE 740243.
Martin H. (1978) 'Low Peclet number particle to fluid heat and mass transfer in packed beds',
Chern. Eng. Sci. 33, 913.
Midoux, N. (1985) Mecanique et rheologie des flu ides en genie chimique, Technique et
documentation, Lavoisier Ed., Paris.
Oh S.H., and J. Cavendish (1981) 'Transients of monolithic catalytic converters: response to
step changes in feed stream temperatures as related to controling automobile emissions', Ind.
Eng. Chern. Proc. Des. Devel., 21, 29-37.
Oh S.H., and J.C. Cavendish (1983) 'Design aspects of poison-resistant automobile monolithic
catalysts', Ind. Eng. Chern. Prod. Res. Dev., 509-518.
Prigent M. (1985) 'Apercu sur les problemes de catalyse dans les pots catalytiques
d'automobiles', Revue de l'institut Francais du petrole, 40, 3, 393-409.
Reid R.C., J.M. Prausnitz, and T.K. Sherwood (1977) The properties of gases and liquids,
McGraw Hill, 3rd edition.
Ryan M.J., E.R. Becker, and K. Zygourakis (1991) 'Light-off performance of catalytic
converters: the effect of heat/mass transfer characteristics', SAE Paper 910610.
576
Schliinder, E. U. (1986) 'Fluid mechanics and heat transfer', Heat design handbook 2 ,
VDI-Verlag, DUsseldorf.
Shah R.K., and T.C. London (1978) Flow forced convection in ducts. Advances in heat
transfer-Laminar., Academic Press, New-York.
Steel M.C.F. (1990) 'Supply and demand of precious metals for automotive and others uses',
in A. Crucq (ed), Catalyst and automotive pollution control II, Studies in surface science and
°
catalysis, 71, Elsevier Sciences Publishers, Amsterdam, pp. 105-114.
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PHOTOCATALYTIC PROCESSES FOR DESTRUCTION OF ORGANIC WATER
CONTAMINANTS
E.PELIZZETII, C.MINERO and E.PRAMAURO

Dept. of Analytical Chemistry - University of Torino
via P.Giuria 5 - 10125 Torino - Italy
ABSTRACT. Photooxidationof many organic compounds (e.g., haloorganics, surfactants, pesticides, etc.)
dissolved in aqueous systems over illuminated semiconductor materials (e.g., TiO~ leads in almost all cases
to quantitative formation of carbon dioxide and, eventually, of inorganic acids (e.g., HCl from chlorinated
compounds). The possible application in the treatment of both waste waters and drinking water is
illustrated.
1. Organic Pollutants in the Aquatic Environment
The Chemical Abstract Service Registry lists over 5,000,000 known substances, and this
does not include all the naturally occurring substances or intermediate degradation
products. Approximately 70,000 chemicals are used world-wide. It has, also been
estimated that 1000 new chemicals go into commercial production every year.
Most organic pollutants originate from the following industrial categories: petroleum
refining, organic chemicals and synthetic industries, milling and coal conversion, textile
processing, and pulp and paper milling. These industries, however, are not the sole
sources of pollutants. Consumers also play a not insignificant role in polluting the
environment. Utilization of fuels for transportation and heating, use of pesticides and
fertilizers, use of detergents, aerosol sprays, among others, all lead to the release of
pollutants directly into the environment. Other routes of aquatic environment
contamination arise from effluents from wastewater treatment plants, accidental spills,
and uncontrolled or poorly chosen landfill hazardous waste sites [1]. Consequently, more
than 700 specific compounds, many of them proven or potentially hazardous, have been
identified in sources of drinking water in the United States [2] and elsewhere. Also
noteworthy is the broad range of compounds that can be transformed into potentially
hazardous substances during water treatment, particularly by halogenation: for example,
the formation of chloroform [3]. The situation of groundwater deserves similar concern
because of the time associated with the migration and subsequent appearance of
pollutants after the initial entry of the substance [4, 5].
577
H.l. de Lasa el af. (eds.), Chemical Reactor Technology/or Environmentally Sate Reactors and Products, 577-608.
578
Some 10 years ago, the U.S. Environmental Protection Agency (EPA) focussed on 129
substances and elements from 65 pollutant classes. These compounds and elements are
frequently referred to as priority pollutants; 114 organic compounds are included and the
breakdown into nine general groups is presented in Table 1.
TABLE 1. U.S. Environmental Protection Priority Pollutants.
Number of
Compounds Compounds
Organics
Pesticides and metabolites 21

Polychlorinated biphenyls (PCBs) and related 7
compoundsa
Halogenated aliphatics 6
Ethers 7
Monocyclic aromatics b 12
Phenols and cresols 11
Phthalate esters 6
Polycyclic aromatics 16
Nitrosamines and 7
other nitrogen-containing compounds
In organics
Metals 13
Asbestos
Cyanides
Source: Adapted from Ref.[6]. apCBs and 2-chloronaphthalene.

bExcludes phenols, cresols, and phthalates.
2. Heterogeneous Photocatalysis in Water Purification
In recent years, research on new methods for water purification has moved from
processes involving phase transfer of a contaminant (e.g., from liquid to solid such as
activated carbon, or from liquid to gas in the case of air stripping of volatile
contaminants) toward processes involving chemical destruction of the contaminant. The
advantages of the established processes, especially that of adsorption on carbon, rest
largely on the generality of the process concept, the attainment of a satisfactory design
basis for a number of applications, and the economic feasibility of the concept.
Heterogeneous photocatalysis is a process in which illumination of an oxide
semiconductor, usually the anatase form of titanium dioxide, produces photoexcited
579
electrons (e-) and holes (h+) that can migrate to the oxide surface and participate in half
cell reactions that are part of a closed, catalytic cycle. In aqueous phase, the illuminated
surface is widely regarded as a producer of hydroxyl radicals, e.g., by h+ + OH- ->
·OH, and these and other highly oxidizing initial products of this indirect
photochemistry go on to attack oxidizable contaminants.
In the last six years since the appearance of the first review on photocatalysis applied
to water purification [7], there have been two NATO ASI Courses [8,9] and a NATO
workshop [10], one monograph [II], chapters of books [12] and reviews [13,14] that
summarize the hundreds of papers published on the topic.
Like its closely related photo-oxidation processes employing (light + ozone) or (light +
hydrogen peroxide) or (light/03/H202), potential interest in application of
photocatalysis is driven by legislation in developed industrialized countries that strongly
encourages both water purification (decontamination, detoxification, decolorization,
deodorization, etc.) and simultaneous contaminant destruction. While light alone or
oxidant alone (H202, 03) produces partial contaminant destruction, only the
simultaneous use of light and an oxidant (03, H202 and/or 02) has routinely been
shown to yield complete mineralization of organic carbon to carbon dioxide, hence the
central advantage of photo-oxidative approaches to water treatment.
The present chapter highlights recent developments in photocatalysis that are pertinent
to its potential process applicability in water treatment for organic contaminants:
specifically, (i) mechanism understanding, intermediates and stoichiometry of the overall
process; (ii) its generality for complete contaminant destruction (mineralization); (iii)
some specific contaminant classes of interest (chlorinated aromatics, surfactants,
herbicides and pesticides); (iv) kinetics (equations, surface vs. bulk reactions); (v)
influence of additional oxidants; (vi) use of solar vs. artificial illumination; (vii)
different catalysts and catalyst's forms (suspended vs. immobilized); (viii) photoreactor
design; (ix) comparison with other techniques using oxidants and light, with care to the
evaluation of efficiency and economics.
The chapter is meant largely to be illustrative rather than exhaustive, and will draw
strongly on the research work of the three coauthors and the colleagues with which a
long and successful cooperation in the field is operating.
3. Mechanism of the Photocatalytic Process
A suitable definition of homogeneous and heterogeneous photocatalysis has been a

matter of debate for sometime [15]. Suffices here to note that for a truly ideal
heterogeneous photocatalyst used in a chemical transformation of reactants to products,
(i) the catalytic entity (here Ti02) should remain unaltered at process completion, (ii)
the reaction should be exoergic and should only be accelerated by the entity, (iii)
electrons and holes, generated on the photocatalyst, are needed by the process, and (iv)
products are formed with high specificity and are different from those obtained in
homogeneous phase [16].
Photocatalysis over irradiated semiconductor dispersions provides a method that can
lead to a highly effective, spatially controlled oxidation and reduction of organic and
580
inorganic substrates, respectively. Ti02 particulates have proven excellent catalysts in

the photo-oxidation of a variety of organic substrates and will be the focus of the
present chapter.
cooductloo
bond
ILUJIII NATED
SEIIICONDUCTOR ELECTROlYTE
CA) CB)
Figure 1. (A) Schematic representation of electron-hole formation and

electron transfer reaction at the semiconductor particle. (B) Thermodynamic
constraints for electron exchange at illuminated semiconductor-electrolyte
interfaces (A=electron acceptor, D=electron donor).
The primary photochemical act, following near- UV light absorption by Ti02 particles
(wavelengths < 380 nm), is the generation of electron/hole pairs whose separation into
conduction band electrons (e- CB) and valence band holes (h+VB) is helped by the electric
field gradient in the space charge region (eqn.I).
(I)
e- + h+ ----> Ti02 + heat and/or hv' (2)
Both charge carriers migrate rapidly [16,17] to the surface ( see Fig.!) where they are
ultimately trapped by intrinsic sub-surface energy traps (Ti IV -0 2 --Ti IV) for the hole
and by surface traps (-Ti IV_) for the electrons (eqs.3,4) [18], and/or by extrinsic surface
traps via interfacial electron transfer with adsorbed electron donors (Red2,ads) and
acceptors (Ox I ,ads), respectively (eqs. 5,6).
(3)
(-TiIV-)surface + e- CB ----> (-Ti"'-)surface (4)
(5)
(6)
58l
Physi- or chemisorption of species on a heterogeneous surface alters their redox

potential. For example, the redox potential of the chemisorbed OH·/OH- couple on Ti02
has been estimated at ca. +1.5 V [19].
There are virtually two possible oxidizing species when a semiconductor particle is
illuminated with photon energies greater or equal to its bandgap energy. For a metal
oxide semiconductor, the species are the photogene rated holes and the OH· radical.
Recent studies have appeared that addressed the issue of direct hole vs OR radical
oxidation. A thorough discussion on the present views has been recently reported [19].
Briefly, no distinction exists between a photogenerated trapped hole and an OH· radical
formed on the particle surface [20].
Rapid electron/hole recombination (eqn.2) requires that Red2 and OX} be pre-
adsorbed prior to light excitation of the Ti02 photocatalyst. Adsorbed redox-active
solvents also act as electron donors and acceptors. For a hydrated and hydroxylated Ti02
anatase surface, hole trapping by interfacial electron transfer yields surface-bound OH·
radicals. It is a major route of formation of OH· radicals (eqn.7). They can also be
formed from H202 via the superoxide 02-· radical anion (eqns. 8 and 9), and by
photolysis of H202 (eqn.IO).
(7a)
(7b)
When irradiation is carried out under direct or simulated sunlight ( > 340 nm),
02(ads) + e- ----> 02-·(ads) (8)
(9)
H202 + hv ----> 2 OH· (10)
reaction (10) is precluded as a major source of hydroxyl radicals since the concentration
of H202 formed is small [21J.
It should be emphasized that even trapped electrons and holes can rapidly recombine
on the particle surface (eqn.2). To prevent recombination of holes and electrons, the
latter carrier is scavenged by pre-adsorbed (and photoadsorbed) molecular oxygen to
give the superoxide radical anion, 02·- (ads)' (eqn.8) that can be reduced further to the
peroxide dianion, 022- (ads). Alternatively, surface peroxo species can be formed [22].
Several years ago, it was pointed out that both 02 and H20 are essential species in the
photomineralization process of 4-chlorophenol in the presence of irradiated Ti02 [23J.
No photodegradation occurs in the absence of either 02 or H20, or both [23,24].
Adsorbed oxygen traps e- (eqn.8) thereby delaying electron/hole recombination (eq.2).
Whatever the routes of formation, these oxidizing species, and in particular ·OH
radicals, are known to react rapidly with most organic solutes. In aromatic compounds,
hydroxylation of aromatic moiety occurs and successive oxidation / addition steps lead
to ring opening. Resulting aldehydes and carboxylic acids (formed also in the reactions
with aliphatics) are further decarboxylated, and finally produce C02.
582
4. Generality of the Degradation Process. Demonstrated Mineralization.
All advanced oxidation processes have the potential to carry the original organic
contaminant, through a series of increasingly oxidized intermediates, to carbon dioxide.
As complete mineralization is usually desirable in a water polishing operation, increased
attention has been drawn to demonstrating not only reactant disappearance but also
carbon dioxide appearance kinetics. The C02 evolution and Total Organic Carbon (TOC)
measurements give the mass balance of the overall degradation process. For example, the
complete mineralization of simple and complex chlorinated derivatives of alkanes,
carboxylic acids, alkenes, and aromatics has repeatedly been demonstrated to occur (see
[14,25] for summary) according to the expected stoichiometry:
(II)
So far the only chlorinated molecule resistant to initial photocatalytic attack is the
saturated molecule with no abstractable hydrogen: carbon tetrachloride £1]. Even
trichloroacetic acid can be dechlorinated photocatalytically [26]. In so far has been
demonstrated that organic compounds containing phosphorous, sulphur and halogen
heteroatoms may be oxidized quantitatively yielding phosphate (P043-), sulphate (S04=)
and halide (X-), respectively [14,27]. Nitrogen containing compounds presents the most
complex results [27]. The photo catalyzed conversion of rings containing a single nitrogen
atom results in early appearance of inorganic nitrogen as ammonia, and later as nitrate
[27]. Interestingly, ammonia appears as the first product of oxidation, but its production
halts shortly after disappearance of all organic carbon. Nitrate, a presumed secondary
product, appears last but eventually dominates the product spectra. A peculiar behavior
is presented by substituted s-triazine ring. Many molecules belonging to this class are
used as herbicides. The ring is very stable toward photocatalytic and chemical oxidation,
forming as final product the trihydroxy-s-triazine [28].
Actual water treatment challenges will characteristically be multicomponent in several
senses. First, multiple organic contaminants (benzene, toluene, xylenes ) or halogenated
solvent (perchloroethylene (PCE), trichloroethylene (TCE» are routinely expected in e.g.
gasoline tank leakage into underground or surface waters. Second, during mineralization
of any organic contaminant, oxidation will logically involve a series of intermediates of
progressively higher oxygen-to-carbon ratios on the way to C02. Such intermediates
make the conversion process muIticomponent, even if only a single contaminant exists in
the feed. Therefore, demonstration of the formation and elimination of intermediates is
also important in demonstration of complete removal of undesirable compounds.
5. Examples of Photocatalyzed Degradations
Almost every major class of organic or halo-organic water contaminants has now been
examined, at least initially, for the possible degradation ( partial or to complete
mineralization) or removal from the liquid phase (see ref.[14] and [29] for an exhaustive
583
list). The examples cited below include (a) fluorophenols, (b) surfactants and (c)
pesticides.
1.0 .4
c
..;:::;0 ...,
-...
til
c
CD
u
c
0.8
0.6
.3
I»
iii"
~.
<
I»
0 "C
u .2 I»
I»
"C ;00-
CD 0.4
N ...,
I»
til I»
...
E
0
0.2
,,
, ,0
.1 I»
c
'I:]
0.0 0
0 5 10 15 20 25 30
irradiation time (min)
1.0
c _-------A---ll
..;:::;0 _------;0,
-
CO 2
...
l'1li 0.8
c
CD
u 0.6
c
0
U
"C
CD 0.4
.~
IV
...0E 0.2
c
0.0
0 30 60 90 120 150 180
irradiation time (min)
Figure 2. (Upper) Photodecomposition of 2-fluorophenol and the nearly

concomitant formation of fluoride as a function of the irradiation time. Ti02
50 mg/L. The relative peak area (right) for three of the identified
intermediates (fluorohydroquinone, fluorocathecol and cathecol) is also
reported. (Lower) Formation of fluoride and carbon dioxide in the
degradation of 2-fluorophenol. Adapted from ref.[30].
584
5.1. FLUOROPHENOLS
Under irradiation and in the presence of Ti02 suspension, the three monofluorophenol
isomers and difluorophenols rapidly disappear. Fig.2 depicts also the formation of
fluoride and of the ultimate product, C02, which confirms the complete mineralization.
The great number of intermediate products identified for the fluorinated phenols also
permits a description of the plausible pathways for their ultimate photo-oxidation to
carbon dioxide and fluoride [30]. Scheme 1 summarizes the events that lead to formation
of the aromatic intermediates.
O· J-;;r 0
·OH
~~F._I + HF
~F'.~~ o~F'.~
[
A [ 2: J
~F,,,,, ~ F~ +
OH 1.,,1
·OH
~ F. 1.,,1
~~H
(al HF
; ' °h
OHI."I
(4tHF
[A
~ F._I
(6)~ ~F._I
] /AOH OH (OHI. 1.,,1
OHI."I ~A
·O,H ~F._I
OH 1.,,1
Scheme 1. Primary events and intermediates in the photocatalyzed

degradation of fluorophenols. Adapted from ref.[30].
5.2. SURFACTANTS.
Earlier studies [31] of anionic, cationic and non-ionic surfactants suggested that aromatic
(benzyl) and hydrophilic moieties (e.g. R-S03Na) are relatively easily attacked and, for
benzyl groups, fully mineralized, whereas the long chain hydrocarbon was converted
slowly. Importantly, virtually complete loss of surface active behavior was demonstrated
in parallel to loss of benzyl groups, a rare example in photocatalysis where elimination
of the nuisance or hazard value of the reactant did not require complete reactant
mineralization.
585
0'
:::J
«i
N>
8.2.... ,,
,
u.-
,
0.8 ,,
,,
G
o E
a..~
d Ilgepal eO-72ol
u· .2 0.6
o~
..
Q ..
.... I
I
I
~ 0.4 I
«i
.:: poe " I
/~
0.2 I "
" I.',
O./~,~~--'=-~~:-=-=-~-=-=-=-~==~==.u
o 2 3
irradiation time (hours)
Figure 3. Evolution of carbon dioxide and variation of Dissolved (DOC) and

Particulate (POC) Organic Carbon as a function of irradiation time for the
mixture of non-ionic surfactants Igepal CO-720. Mixtures containing shorter
ethoxylated chains (lgepal CO-520 and Igepal CO-210) have similar
behavior. Ti02 2 giL. Adapted from ref.[32].
Recently [32] photocatalyzed degradation of alkyl phenols and the nonionic

nonylphenol ethoxylate were examined. Here the surfactant and alkyl phenols were
susceptible to complete mineralization, as showed by the important demonstration of a
carbon balance all the way to carbon dioxide (Fig.3) for polyethoxylated 4-nonylphenols
with average numbers of 2, 5, and 12 ethoxy units.
A schematic representation of the degradation process is depicted in Scheme 2.
5.3. HERBICIDES AND PESTICIDES
Complete disappearance of 2,4,5-trichlorophenoxy-acetic acid (2,4,5-T) and 2,4,5-

trichlorophenol (TCP) as well as ca. 100% recovery of initial chlorine as free chloride
ion in the final state (30-90 minutes) was demonstrated [33]. The ratio of free chloride
to TCP converted was always 3: I, suggesting a very rapid mineralization and absence of
appreciable accumulated intermediates. Attack of 2,4,5-T released stoichiometric halide
more slowly than reactant disappearance could allow, and major detected intermediates
were 2,4,5-TCP and 2,4,5-trichlorophenyl formate. These and other results show slow to
586
moderate attack of ring compounds, followed by rapid mineralization once simple

phenolics or opened rings have been achieved.
DDT is one of the most complicated chlorocarbons examined in photocatalysis:
complete dechlorination of I ppm solutions is reported [34] with a half life of ca. 40
minutes. An initially rapid DDT disappearance (>50% in I hr) was followed by much
slower final disappearance and chloride recovery, as expected for a reactant with several
important kinetic intermediates.
The herbicide bentazon (3-isopropyl-2,1,3-benzo-thiadiazin-4-one-2,2-dioxide) is
efficiently converted to give near quantitative yield of sulphur as sulphate ion and
carbon as carbon dioxide; dissolved and particulate organic carbon measurements also
support nearly complete mineralization [35].
The s-triazine herbicides (atrazine, simazine, trietazine, prometone and prometryne)
are degradable but are singularly resistant to complete mineralization. In all cases, the
starting material is degraded to the very stable six membered ring cyanuric acid
(compound XI of Scheme 3). Virtually stoichiometric recovery of nitrogen, sulphur, and
chlorine in ring side groups was demonstrated as nitrate, sulphate and chloride ions [28].
Pathways for atrazine may include dehalogenation, dealkylation and deamination [28] as
summarized in Scheme 3. As cyanuric acid has a very low toxicity, these partial
conversion results are nonetheless encouraging. Complete disappearance has been
demonstrated even at ppb levels [28].
PHOTOCAT AL YTIC DEGRADATION OF CgH12-00-(CH2CH20lnH
OH attack on the OH attack on the

aromatic ring ethoxylated chain
+ +
R-OO-(CH 2CH 2OlpH R' -o0-(CH2CH 2OlmH I PEG,
+ HOCH2CH2OH
oxidation
cleavage of the
aromatic ring
p=m,n,1 1<m<nl
~9r oxidation
IACIDIC UNITS + PEG I

further oxidation
CO 2
Scheme 2. Photodegradation routes for nonylphenol-polyoxyethylene

surfactants. Degradation of the aliphatic chain is omitted. Adapted from
ref.[32].
587
a
NAN
H:zN~)lNHC~
(V)
CI
NAN
HO~NJ-OH
(X)
Scheme 3. Proposed degradation pathways for atrazine under illumination of

Ti02 slurries. All compounds were experimentally identified during the
degradation process and their kinetics of appearance and of subsequent
disappearance was measured. Adapted from ref.[28,57].
6. Kinetics of Heterogeneously Photocatalyzed Conversions
In analyzing the kinetic data of photocatalyzed oxidations (and reductions), mediated by

photo-activated semiconductor particles, several studies have fitted the results to the
simple rate expression of the form of eqn.12 [25,37,38]:
588
rinitial = k K C/(1 + K C) (12)
Determination of initial rates of oxidation as a function of increased concentration of

organic substrate, for a given photocatalyst loading, commonly yields the type of plots
illustrated in Fig.4 .
6,-----------------------------------~
Monochloroacetic acid
-
!-..
5
~
--
"ij
u Dichloroethane
I
4
C)
E 3
a.
a.
-
I 2
CD
&'II
a: Perchloroethylene
o 0.02 0.04 0.06 0.08 0.10
[Reactant- 1] ppm- 1
Figure 4. Reciprocal initial rate versus reciprocal initial reactant

concentration for compounds indicated. Straight lines suggest that eqn.12
holds. Adapted from ref.[7] .
As the reaction becomes more complex, so that passage through one or more
kinetically important intermediates occurs, the rate must include competitive adsorption
by solvent and by intermediates, which slows the disappearance of reactant according to
eqn.13 [37,38]:
dC - kKC
(13)
dt 1 + KC + L:
(all
intermediates)
as well as that of each intermediate, Cj:
-kiKiCi + k i - 1 Ki-1 Ci-1

(14)
1 + KC + L: KiCi
(all
intermediates)
589
The similarities of eqs.12-14 to a Langmuir adsorption isotherm have led to inference

that the mineralization process takes place on the photocatalyst's surface. Turchi and
Ollis [39] have shown that regardless of whether both, one only, or neither of oxidant
(·OH) and reductant (pollutant) are adsorbed on the catalyst at the moment of radical
attack, the overall rate equation will still follow an apparent Langmuir-Hinshelwood
form if there is only one dominant reaction mechanism.
Clearly, kinetic studies alone are silent as to photo-oxidations are surface processes or
solution processes. Some studies have sought chemical evidence and inferences to
ascertain whether or not the oxidation is a surface process. A considerable fraction of
pollutant degradation may occur by ·OH radical desorption from the photocatalyst
surface [40-43]. By contrast, recent pulse radio lysis studies [20] and experiments on
photocatalytic degradation of tenaciously adsorbed compounds on inert materials [44]
strongly support that major oxidants are adsorbed ·OH radicals. Free hydroxy radicals
probably playa minor role, if any.
"? 0
0
'"
..-
U
OJ
0 .
a
a
~
0
"- E
~
'"0
0 .3
c 0
'" N
0
0
u0 .., 0 U
., 0 0
N "0
0
'" '"
.,;
0
0
I-
a 20 .0 60 80 .100
illumination time (min)
0
~ 0
0
..-
N
OJ
0
o c:-
U 0
ci ~
"- E
.::. '"
0
0
:l..
c
~
.,; N N
0
0
u0 .., 0
0 .,
0
0
"0
'"'" ..
Ob) "0
"! 0
0
>-
30 60 90 120 150
illumination time (min)
Figure 5. (a) Photocatalyzed mineralization of perchloroethylene (PCE) vs.

time. PCE (0), product C02 eX). Solid curves: kinetic model for PCE
disappearance; carbon mass balance for C02 appearance. [PCE o ] = 207 MM.
(b) Photocatalyzed benzene mineralization vs. time. Benzene (D), product
C02 (X). Solid curves: kinetic model for benzene disappearance assuming no
one, one, and two important intermediates. Taken from [38].
590
When reactant mineralization is the treatment goal (no residual dissolved organic
material), a useful measure of reaction lifetime might be achievement of a satisfactory
mineralization, e.g., 95% generation of maximum possible C02. For simple reactants
such as PCE, this corresponds essentially to the same reaction time as 95% PCE
disappearance (see Fig.5). For more complex reactants, such as benzene and all other
aromatics in particular (phenols, halophenols, PCBs, etc), the time required for 95%
appearance of final C02 may be several multiples of the reactant 95% disappearance
time. This same point was emphasized recently by Matthews [45].
6.1. COMPETITIVE ADSORPTION
In addition to a given reactant, many other molecules (solvent, reaction intermediate,

reaction product, other reactants, and other nonreactive solution components) may
simultaneously adsorb on the surface. As found in other more classical areas of
heterogeneous catalysis, these simultaneous adsorptions will influence the observed
reaction kinetics. Their influence requires quantification if reactor design in this domain
is to arrive eventually at the same level of analytic treatment as practiced in
heterogeneous reactor design in processes with well-established kinetics.
Eqs.(13) and (14) predict the kinetic behavior for degradation of multicomponent
systems, including the competing intermediates [37,38].
The effect of inorganic anions that can adsorb competitively has been extensively
investigated. Inhibition effect of species such as chloride, sulphate, phosphate has been
observed [46-48], whereas perchlorate and nitrate have little effect [47]. Rigeneration of
the catalyst through washing with NaHC03 solution has been established [48].
6.2. OXIDANT KINETIC INFLUENCE
Literature results appear to provide a consensus regarding the influence of oxygen; it is

necessary for the complete continued mineralization and it appears not to be competitive
with the reactant during adsorption.
Three different studies of dissolved oxygen influence on the rate of photocatalyzed
degradation have appeared [49-51], and all provide the same rate form. Adsorption of
oxygen in a nondissociated form, on a separate site from that for hydrocarbon or
halocarbon, would provide a rate function of the form
rate = k f(organic) g(oxygen) (15)
In all three cases, a form for the function of a Langmuir type has been proposed:
g (16 )
Reported values of K02 on (different) Ti02 are:

0.0182 kPa- 1 [49], 0.11 kPa- 1 [50] and 1.1 kPa- I [51].
591
6.3. OTHER PARAMETERS INFLUENCING THE RATE OF DEGRADATION
6.3.1. pH. The pH of the solution can affect either the surface properties of the
photocatalyst and the chemical form of the substrate. Ti02 has an amphoteric character
with a point of zero charge around pH=6 [52], and the substrate can undergo acid-base
equilibria. Consequently, also the adsorption of the substrate may be affected, strongly
influencing the degradation rate [53].
6.3.2. Temperature. Recent investigations have shown that there is only a small
temperature effect connected with photocatalyzed TOC diminution. Consequently, the
use of solar photochemical reactors in this application would not yield a great advantage
over the presently used designs based on artificial light sources. Solar captors enhancing
the incident irradiance could, however, be an economic factor when operational costs
have to be compared with those of artificial light sources of high electrical power.
6.3.3. Rate enhancement by peroxycompounds and oxidizing inorganic species.

Photo catalyzed reactions have been reported to exhibit appreciable, even substantial rate
increases when H202 is added to an aqueous photocatalyst slurry. Examples showing
increased rates include trichloroethylene and perchloroethylene [54], chloral hydrate [55]
and phenol [56]. The latter study found that the photocatalyzed oxidation rates increased
according to 02 < H202 < (H202 + 02)·
In other processes the effect was less relevant and even inhibitory [57]. The role of
hydrogen peroxide may be multiple acting as both an accelerator and inhibitor, as
recently discussed [41,58].
Other oxidants, such as peroxydisulfate and periodate, have also been shown to
enhance dramatically the overall reaction rate [57]. As with H202, these may participate
either to trap surface electrons (rate enhancement by prevention of recombination of
electrons and holes) or to participate directly in an oxidative step. The resolution of the
various possible heterogeneous steps, as well as the inclusion of any homogeneous phase
chemistry, remains to be accomplished, as does an economic analysis of optimal oxidant
addition levels.
7. Photocatalytic Materials
Several materials have been investigated for their photocatalytic properties [11,59-64]
and increasing attention is now devoted to the preparation of new semiconductors
[65,66]. This could allow to improve the light response and the overall efficiency of the
process.
So far quite few materials have been used in photocatalytic degradation of pollutants.
Where such comparisons have been reported, the results almost invariably show that
Ti02, followed by ZnO, are the two most active catalysts [67,68]. Because Ti02 is fairly
stable over a large range of pH and it is a cheap material, most of the investigations or
degradations have been carried out with this material [14].
592
Since, for example, the reported maximum quantum yield for the destruction of
salicylic acid over a thin film of Ti02 is 0.022 [68] it appears that there is an interesting
possibility for considerable improvement of the efficiency of the process.
Amongst the several factors that influence the behavior of the photocatalytic material,
we can cite (literature is quoted simply for exemplification purposes):
- structure: amorphous vs crystalline [69-72], rutile vs anatase for Ti02 [70]
- particle size and surface properties, including the effect of surface hydroxyl density
[73-75]. The effect of the thermal treatment of Ti02 powder toward the degradation of
2,4,5-T is shown in Fig.6 [67]. The effect of surface modifications is also discussed [76].
- preparation: starting materials [77,78], techniques such as sol-gel [79], thermal
hydrolysis [78], additives.
- chemical etching and mechanical stressing [80].
- doping (influencing spectral response and Fermi level position, electron/hole
recombination) with transition metals [81-83], or alkaline ions [84,85]. The effect of
Cr(IlI) doping of Ti02 on phenol degradation has been investigated; the presence of the
dopant decreases the activity of the catalyst [86,87].
- spectral sensitization (influencing the spectral response) [81,88,89].
- mixed compositions:
-- mixture of different powders [90-92].
-- coprecipitation [93,94].
-- thin layer deposition and supported photocatalyst on non semiconductors
materials: silica [95,96], clays [97], zeolites [98], polymers [99],
nafion [96], vycor glass [100], glass mesh [101].
-- loading of noble metals and oxides [102].
Little effect has been observed when Pt is deposited
onto Ti02 toward degradation of some pollutants [33,103].
~
E
o
.
1 0
~
f- ,
'"~ 0.5
('oj
o
o 1 2 3
IRRADIATION TIME (hours)
Figure 6. Effect of the thermal pretreatment of Ti02 powder (P25 Degussa)

on the photocatalyzed decomposition of 2,4,5-T at pH;3. Adapted from
ref.[67].
593
Ti02 in anatase form has characteristically been observed to provide an active catalyst,
stable over very long irradiation times. ZnO, another appreciably active material, has a
restricted range of stability in aqueous solutions.
8. Irradiation and Spectral Characteristics
8.1. THE PHOTOCATALYST ACTION SPECTRUM. SOLAR VS. ARTIFICIAL ILLUMINATION.
As the vast majority of existent data concerns use of the anatase form titanium dioxide
(Ti02), focus on its properties as both pertinent and illustrative has been carefully
reported by Ollis [58]. The absorption spectrum of Ti02 is characterized by a strong
band gap edge at about 360 nm, with an exponential tail dropping to zero at about 400
nm. In consequence, no more than 1.5-2.0% of the sea level solar spectrum is available
for photocatalysis as summarized in Table 2.
TABLE 2. (from ref[58]).
light source near UV (300-400 nm)

Power (W /m2) Suns Quanta
(einsteins/m 2s)
Sun, D.N. Am1.5 22 1 6xlO- 3

1.4 kW Xe lamp, old 2240 86.6 0.5
1.4 kW Xe lamp, new 5980 230 1.4
1.6 kW HgXe lamp, new 49300 1870 11.2
Solar is a dilute resource: one m 2 of collected solar near- UV flux receives 6'10- 3
einstein/s (Table 2); thus with perfect absorption and a quantum efficiency of unity, it
could process about 22 gram-mols of reactant per hour. A typical photocatalytic
quantum efficiency of I % acting on a very easily oxidizable solute such as
trichloroethylene or perchloroethylene would yield at most 0.22 gm-mol processed per
m 2 per hr. A starting concentration of I ppm of trichloroethylene (TCE) in water could
be processed at a rate of
0.22g-mol 130gKE 1L 28600 L

(17)
g-mol TcE
This is a maximum estimate, as the actual quantum efficiency may decrease with
decreasing TCE concentration.
Several lamps, especially xenon and mercury-xenon, have been used in laboratory
studies to simulate the solar near UV spectrum. As Fig.7 suggests, these lamps may have
a substantial 290-310 nm contribution vs. sea level solar, and the use of such lamps to
594
"simulate" sun must be considered carefully, as not only photocatalysis but also
homogeneous photochemical activation of pollutant (e.g. phenol) or added oxidant (e.g.,
H202) may occur at these shortest wavelengths .
.1.R~R~A=D~IA~N~C~E~(W
__/m_2_-_n_m~)________~______-,
10000..--
1000
100
10
0.1 Solar (ON AM1.S)
0.01
O.OO1~~----~------~------~L-------3~75------~400
275 300 325 350
WAVELENGTH (nm)
Figure 7. Spectral irradiance (W Im 2-nm) of solar source (X) and of several

lamps used as solar simulators. BL = black light. Reproduced from ref.[57].
Experiments with a Solarbox simulator (Xe lamp) and a 340 nm cut-off filter provide
AMI spectral distribution to the photocatalyst. The broad range of contaminant
structures that have been mineralized via this simulated solar illumination include an
extensive list of organics [14].
8.2. INTENSITY: OPTIMAL POWER QUESTION.
The few existing studies of photocatalyzed rate vs. illumination intensity almost all
suggest that at illumination levels appreciably above I sun equivalent, the reaction rate
increases with the square root of intensity, whereas at sufficiently weaker levels (catalyst
dependent), the rate is first order in intensity. As absorption of photons is first order in
intensity, it follows that at low intensity, the photochemical efficiency (number of
molecules transformed per incident photon) is a constant, and at higher levels, it
decreases as 1- 0 .5 , indicating an efficiency penalty for sufficiently intense lamps or
concentrated solar sources. Of course, increased intensity always buys an increase in
595
volumetric reaction rate, until the mass transfer limit (constant rate, Fig.8) plateau is
encountered [13,58].
Thus, the photochemical efficiency, 1[, varies with intensity as follows:
low I rate Q I 1[ = constant

intermediate I rate Q 11/2 1[ Q 1- 1/ 2
high I rate Q 10 1[ Q 1-1
Where reactor costs dominate the process economics, increased intensity increases the
rate per volume (below mass transfer limit) and is worthwhile, whereas if photon
collection or generation is a dominant cost, a lower intensity will provide cheaper
treatment. As the 11.0 to 10.5 transition is catalyst material dependent, and as the 10.5 to
10 .0 transition depends on catalyst configuration (immobilized) and on flow-influenced
mass transfer, the transition points between these regimes will vary with each
application.
Extension of the first order regime to higher intensities may be possible by addition of
better electron acceptors (H202, Cu+, Ag+ all suggested), but there is need for much
additional work in this area so as to maximize the efficiency of the overall process.
OPERATING REGIONS
I
I
mass transfer ,0
In Irate)
In lin tensity)
Figure 8. Theoretical regimes for rate dependence on intensity. Rate varies

with a power law (intensityX), where x=l.O, x=0.5 and x=O.O for surface
reaction dominant, electron-hole recombination dominant and mass transfer
dominant regimes, respectively. Adapted from ref.[13].
596
A similar circumstance exists in photolytic ozonation [104], where lab and field
samples provided
rate a 11.0 (distilled water)
rate a lOA (lake water)
for the dominant photolytic ozonation term in the rate kinetics. Thus, the latter
fractional order dependence of rate on intensity may be found commonly in
environmental applications of photolytic oxidations in general, whether homogeneous or
heterogeneous. Such a circumstance is not surprising, as increased intensity should
increase recombination processes (second order) faster than oxidation processes (first
order in excited oxidant), no matter the photochemistry involved.
9. Photoreactor Design
The photoreactor design literature to date has been largely concerned with homogeneous
systems of quite low optical absorbance. Indeed, many papers have focused on the
design of various reflector systems that could provide a sufficient number of traverses
through the reactant gas or liquid phase to allow achievement of appreciable absorption.
This area has been treated exhaustively by the group of Cassano in Argentina [105,106]
The literature for heterogeneous photoreactor design is much more sparse.
An analysis of slurry photoreactor performance [107] explored photochemical
conversion in a tubular flow reactor with radial dispersion, and found that at a fixed
optical thickness, increased light scattering by increased particle concentration always
diminishes reaction conversion (at any axial position) except one relevant case: that of
negligible radial mixing and high optical thickness. In the latter case, reactant depletion
occurs early in the outer periphery of the reactor and is poorly distributed in the case of
pure absorption. Increased scattering allows conversion of more centrally located
reactant, while retaining complete conversion in the outermost periphery. This effect is
found regardless of reaction order.
The influence of photocatalyst particle size on gas solid photocatalyzed rate has
recently been examined [107,108], using titanium dioxide powder entrained in a flowing
gas transport reactor. Consideration of the complex number form of the particle
extinction coefficient leads to calculated extinction and absorption efficiencies versus
particles size that have maxima at 0.09 J.Lm and become "constant" above 10 J.Lm. Since
particle extinction rises for particles smaller than 10 J.Lm, the calculated reactant
conversion shows a maximum at about 10 J-Lm, falling to the left due to scattering and
the right due to diminished photocatalyst surface area.
Increasing photocatalyst particle concentration is predicted to cause progressively
sharper radial diminution of photon flux; the competing trade-off between increased
catalyst surface and decreased photon distribution gives rise to a predicted and
experimentally observed maximum in the product yield versus catalyst solid fraction.
The maximum predicted at 25xlO- 5 volume fraction or approximately 1.08xlO- 3 g/cm 3
corresponds reasonably to the smallest solid volume fraction (0.1 wt%) [108] found to
give complete absorbance in a reactor of comparable radial dimensions. This study is the
597
first to combine intrinsic photocatalyst kinetics with fundamental photon flux radial
distributions and experiments.
At very low reactant concentrations, as may characterize pollutant removal from water,
an additional effect of solid's loading is expected. Here, increased solid surface area
results in decreased bulk concentration of reactant, and at corresponding diminution of
the rate when strong photon flux gradients exist. In other words, increased catalyst in
the darker region of the reactor removes (by adsorption) reactant availability in the
illuminated zone. Again, a maximum is expected; this influence has not yet been
combined with the predicted scattering phenomena to provide a reactor description for
low concentration systems.
Most photocatalysis studies to date have used ~0.1 wt% slurries of titanium dioxide
particles, of gross size 0.1-30 J.l.m depending on the source. As recovery of micron size
particles from a treated liquid may be awkward in an actual process, a number of papers
have examined means of catalyst immobilization on beads [109,110], inside tubes of
either glass or Teflon [III], on fiberglass [112], woven mesh [113], or ceramic Ti02
membranes supported on glass tube [114]. As with all other areas of heterogeneous
catalysis [115], the convenience of catalyst immobilization on progressively larger
particles is bought at the expense of increased average convective-diffusion distance
from fluid to catalyst surface. This circumstance invites the possibility of reactant mass
transfer influence since, at pseudo-steady state, the mass transfer rate to the surface,
r m , must equal the surface catalyzed rate, rc' Thus
rm = k m (Cb - Cs ) (18)
rc =kc f(C s) (19)
where Cb and Cs are the bulk solution and surface concentrations of reactant, and f(Cs)
represents the concentration dependence of the surface photo catalyzed rate.
Sample
port
Figure 9. Recirculating batch photo reactor for conversion of organic

compounds. Benchtop system. Reproduced from ref.[l18].
598
In 0.1 wt% slurries, the average interparticle distance is so small that the measured rate
of TeE conversion is much less than the potential mass transfer limit [117]. In contrast,
with the catalyst immobilized on walls of tubes of several mm diameter, mass transfer
influence may exist, and has been demonstrated with data for salicylic acid conversion
in a coiled tube [68,116]. A clear variation of reaction rate with flow rate exists, and an
analysis [117] suggested that the data are very strongly mass transfer influenced. A
similar influence of fluid flow rate on the first order rate constant has been noted in
chlorophenol degradation on photocatalyst-coated glass beads [36].
9.1. PILOT PLANT STUDIES
Tests on the potential of photocatalytic process to destroy organic contaminants in water

have been conducted so far at three levels:
- at a laboratory scale (order of liters). Fig.9 represents a slurry photoreactor
[118,119] whereas Fig.l0 a membrane reactor [114].
- at a small outdoor system (ca. 100 liters).
- at a large outdoor scale ( thousands of liters) [118,119], both on slurry (Fig.ll) or
supported catalyst (Fig.12).
Inner
Tube
.-
Ga of
Co oli II I; OutlCf
Ollt!t-I -....
Uquid ",.- Membrane

O"llet
Cooling Chamber Liquid

Elltry
Reaction Chamber
GlaH Cooling
I-j'i/ Elliry
Ga.l"
EIIII ... ·
Figure 10. Schematic diagram of annular photochemical membrane reactor.

Reproduced from ref.[114].
599
Figure 11. Large outdoor trough system measuring 218 m long by 2.5 m
wide (net area 365 m2 ) with a 38 mm I.D. borosilicate glass pipe. The
sunlight is concentrated 50 times and the flow rate is 100 liters/min. From
ref.[118].
Figure 12. Outline of a plant solar system for treating organic contaminated
groundwater using supported photocatalyst. From ref.[118].
600
9.2. NORMAL VS. CONCENTRATED SOLAR PHOTONS [58]
The near UV spectrum is divided among direct and diffuse sources. The latter cannot be
concentrated to a single point, the former can. Consider a flat plate collector cross
section (Fig.l3, left). Each point at the surface receives a direct contribution of Id
(photons/cm 2-s) and a diffuse contribution of Is (same units). The total intensity of
photons collected by the plate is Ip = Is + Id.
With a tracking concentrator, the perfect concentrator collects a'ld of the direct near
UV ( a = reflectance) and (d/D)'ls of the diffuse. The total intensity It collected is now
a·ld + (d/D)l s . For an aluminum reflector with a = 0.8 and a reactor to reflector radial
ratio of d/D=O.I, the collected photon rate in the Fig.l3 (right) case is 0.8·ld + O.I-Is. If
Is = 0.25·ld is used as the correct order of magnitude for near- UV intensities, then the
convenience of a smaller, simpler tubular reactor using concentrated solar photons is
bought at the price of both the additional reflector equipment and the reduction of
available photons to
It(trough) 0 • 8 + 0.1 ( • 25)

-=~-.:.....;.--
66%
It (1sun) 1.0 + 0.25
of the original solar source availability. Additional small corrections can be made for
tubular reactor reflection and for diurnal variations of intensity ratios.
I FLAT PLATE I ITROUGH REFLECTOR I
......• D.·············
II = I'd + I'.
II=uld O + I. d
l!troughl = u + (JAJ(!..)
D I,
I'PIIII'
Figure 13. Schematic of reactor collection of direct and scattered ( diffuse)

near UV radiation for flat plate (left) and parabolic trough collector
geometries (right). Plate collects Ip=ld+ls' whereas trough reactor collects
It = aId+(d/D)Is' Adapted from ref.[58],
601
10. Comparison with Other Oxidative Degradation Techniques (120)
Table 3 summarizes different techniques used or under development to cope with cases
of severe pollution of the phreatic drinking water reserves, of surface waters used for
the same purpose, as well as for a non-biological treatment of residual waters from
different industries.
It becomes clear that the Ti02 catalyzed degradation method has many technically well
developed and attractive competitors. However, some of their draw-backs should be
mentioned:
TABLE 3. - Present level of technical development of oxidative

degradation techniques based on hydroxyl radical generation [120).
Technique Efficiency Spectral domain Level of

development
H202/ hv h UY-Ca) Production a )

H202/catalyst ha) Production a )
°3/ hv mb) UY-B pilot b )

°3/pH mb) Production b)
H202/03 h C) pilot b )
Ti02/hv sd) UY-A pilot d )
(Electrochemistry) se) Pilot c )

Efficiency related to short residence times: h: high, m: medium, s:
small; a,b,c,d,e) see comments in text.
a) H202 is produced by a small number of manufacturers, and its price is one of the
major constituents of an economic feasibility calculation. The H 202 photolysis is
practically limited to the UY-C domain [121] and its efficiency might be strongly
diminished by inner filter effects due to light absorption by dissolved or dispersed
pollutants, as well as naturally contained humic materials [122].
Many catalysts have been developed for H202 decomposition, however, their use will
be limited in applications where drinking water is involved. Means to maintain a critical
Fe 2+ concentration in a generally oxidative reaction environment are presently
developed.
b) Photochemical and thermal ozone decomposition suffer from the economical draw-
back of very high investment and maintenance (security) costs [123].
As the solubility of 03 in water is rather limited, the absorption cross section of the
dissolved or finally dispersed reactant is of primary concern for reactor design. For the
602
same reason of limited solubility, care must be taken for efficient mixing, relative long
contact or irradiation times and for the recycling of the unreacted oxidant. All these
problems are still topics of new inventions in reactor design and construction.
Alkali addition for thermal 03 decomposition would require pH adjustments after
treatment that could have negative effects on the salinity in drinking water applications.
c) Although, suffering from the different economical draw-backs already mentioned,
the thermal generation of HO· radicals in the combined application of H202 and 03 is
often forgotten, but has found the interest of the water treatment industry.
d) Ti02 has the advantage of an absorption spectrum reaching through the ultraviolet
to the limit of the visible spectral domain and, therefore, may be used for solar
photocatalyzed decontamination processes, whereas competing photochemical processes,
such as H202 or 03 photolysis, as well as the VUV photolysis of water, remain limited
to the use of artificial light sources. Under conditions of solar light excitation, the
absorption efficiency of Ti02 may be further increased when inorganic "sensitizer"
functionalized semiconductor surfaces are used. Furthermore, the concept of Ti02
photocatalysis includes the recycle of the catalyst, hence, no chemical product is
consumed in a first approach toward the technical development of such a process. In
addition, photocatalytic processes operate under mild conditions (temperature, pressure)
and use a safe, cheap and non-toxic catalyst (Ti02).
As mentioned above, all oxidative degradation processes may lead to complete
mineralization of the organic material contained in aqueous reaction systems.
e) This does not seem the case for electrochemical processes [124] which actually do
not belong to the class of oxidation reactions by hydroxyl radicals. In fact, only organic
compounds will be oxidized by this technique that show smaller oxidation potentials
than water. The incomplete mineralization might be due to the decreasing rate of
oxidation of a diminishing concentration of organic material encountered at the
electrodes.
We deduce from the collected information that there are potential domains of
application of Ti02 photo catalyzed degradation processes, e.g. for the detoxification and
TOe diminution in residual waters of industrial activities with a lower operational TOe
limit of 100 ppm and for practically complete mineralization (operational limits: 0.01
ppm < TOe < 100 ppm) for waters mainly used in pharmaceutical and microelectronic
research and manufacturing and for drinking water decontamination, where in both
cases relative low volumes per unit of time are consumed. In most of these applications,
the Ti02 photocatalyzed degradation techniques would be used in combination with
other methods of water treatment. Also, short term drinking water sterilization might be
possible by Ti02 photo catalyzed oxidative water splitting, a process that probably could
compete with the energy consuming ultraviolet irradiation used in many places.
However, no information as to this application has been available.
11. Conclusions
The open literature has by now largely succeeded in establishing the general ability of
photocatalysis to carry out the (usually) complete mineralization of a host of known
603
organic water contaminants. One of the challenges for the next decade for those who
wish to commercialize and to use photocatalysis will be to establish effective reactor
designs for the intermediate and large scale uses that may be envisioned, and for all
involved to demonstrate economic feasibility beyond the initial reports [7,13,24,28,44].
Nomenclature
AMI Air Mass I (i.e. sea level)

bg (subscript) band gap
CB (subscript) conduction band
DOC Dissolved Organic carbon
e- electron (photoexcited)
h+ holes (photoexcited)
PCB polychlorobiphenyls
PCE perchloroethylene
POC Particulate Organic Carbon
ppb part per billion
ppm part per million
TCE trichloroethylene
TCP trichlorophenol
TOC Total Organic Carbon
VB (subscript) valence band
VUV near visible Ultraviolet Light
Acknowledgements
We are indebted to Eniricerche, Regione Piemonte, EEC under Contact EV4V -0068-
C(CD) and CIEMAT for the generous support of the researches. We also thank our past
and present collaborators whose names are extensively cited in the references.
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HETEROGENEOUS PHOTOCATALYTIC DEGRADATION OF mE CATIONIC
SURFACTANTS CETYLDIMETHYLBENZYLAMMONIUM CHLORIDE AND
CETYLPYRIDINIUM CHLORIDE
I.POULIOS AND A.A VRANAS

Laboratory of Physical Chemistry
Department of Chemistry
Aristotle University
54006 ThessalonikilGreece
ABSTRACT. The photodegradation of the cationic surfactants cetyldimethylbenzylammonium chloride

(CDBACl) and cetylpyridinium chloride (CPCl) in aqueous heterogeneous dispersions of TiOz
semiconductor particles (naked) and Ti02 particles with Pt deposited onto them (TiOiPt) as catalyst is
studied. A photodegradation destroying the aromatic ring is followed by a slower oxidation of the aliphatic
chain. The photo-oxidation is followed phasmatophotometrically together with pH and surface tension
measurements. The degradation rate of CDBACI is faster compared to that of CPCI. TiOiPt is better
catalyst than naked TiOz' Although total mineralization has not been demonstrated, the surface tension
results show a destroying of the surface activity in a few hours using light of lower intensity (40 mW/cmZ)
compared to that used by other authors.
1. Introduction
The elimination of toxic chemicals from waste water is presently of great concern, since their
complete biodegradation is usually very slow and requires several days or weeks (Mittal and
Fendler 1982). These pollutants may originate from industrial applications (petroleum refining,
textile processing etc.) or from household and personal care areas (pesticides and fertilizers,
detergents etc.). In the last few years attention has been directed toward the photocatalytic
degradation of organic and inorganic pollutants in heterogeneous suspensions of semiconductor
particles (Matthews 1987, Kormann et al. 1991, Pelizzetti et al. 1990). A variety of
semiconductor particles (metal oxides, sulfides and others) acting as photo catalysts has been used.
The appropriate illumination of these particles produces excited-state electron and hole pairs that
can migrate to their surface. These pairs are able to initiate a wide range of chemical reactions
that may lead to complete mineralization of the pollutants. The surfactants, whose market for
Western Europe, USA and Japan is now 6.000 Ktonnes continuously increases making a serious
ecological problem (Karsa 1990, Swisher 1963) requiring the development of a waste treatment
technique. Among them, the cationic surfactants (25% of the total surfactant consumption) are
very slowly biodegradable, because of their bactericidal activity (Fenger et aI. 1973), to
substances that may be more toxic or insoluble in water.
In recent literature, some reports have dealt with photodecomposition of surfactants, ionic or
non-ionic, mediated by TiOz as semiconductor particles (Hidaka et aI. 1985, Hidaka et aI. 1986,
Hidaka et al. 1987, Hidaka et aI. 1988, Hidaka et aI. 1990, Pelizzetti et al. 1989) using light of
very high intensity (hex> 330 nm) leading to their total mineralization. It is obvious that the
609
610
photo-oxidation of the substances may be used for detoxification of waste waters and may
sometimes be preferred over the biodegradation method.
This paper contains some preliminary experiments describing the photodecomposition of two
cationic surfactants, cetyldimethylbenzylammonium chloride (CDBAC!) and cetylpyridinium
chloride (CPC!) with naked and with Pt loaded Ti02 as photocatalysts using light of low intensity
(lower than the AMI and the light that has been usually used in the literature).
2. Experimental
2.1. MATERIALS
The cationic surfactants CDBACI and CPCl were Fluka products (cat. no. 13400 and 52349
respectively), of purim quality and were used as received. The catalyst used was Ti~ from
Merck (anatase, cat. no. 808) and it was found to contain trace amounts of carbonaceous and
other surface active materials interfering with measurements of surface activity. In order to
remove these materials Ti02 was treated as follows. A suspension of Ti02 in water was
ultrasonically irradiated using a Kerry Ultrasonics Ltd. for 10 minutes and then centrifugated.
After washing it several times with deionized water it was dried at an oven at temperatures below
90°C. The absence of surface active agents was checked by measuring the surface tension of
water taken from a suspension of Ti02 (72 m-Nm't, the value of surface tension of water at
25°C). TiOiPt was prepared according to the literature (KreutIer and Bard 1978). Water was
obtained from a Millipore ion exchange apparatus; its specific conductance was better than 1'10.8
S·cm·1•
2.2. METHODS
The irradiations were carried out in an quartz reaction vessel (200 ml) using a 150 W
Tungsten-halogen lamp. The distance between the vessel and the lamp was 20 cm. Under these
conditions, the lamp delivered 40 mW/cm 2 which was lower than AMI simulated sun light
(-100 mW/cm2) (Minero et al. 1991). In all cases 150 ml of 2'10.4 M surfactant solutions
(concentration below their critical micellar concentration, CMC) containing the appropriate
quantities of Ti02 or TiOiPt (2g/I), were ultrasonically irradiated for 5 min (in order to increase
the specific surface of TiOJ. The solutions were left for 24 h in the dark. During this time the
maximum of absorbance of surfactants onto the semiconductor surface was achieved. The
suspension was magnetically stirred during the photolysis experiments. Before starting the
experiments and at one hour time intervals, samples of 15 ml were withdrawn. Changes in the
concentration of surfactants present in the supernant solution, obtained by ultracentrifuging the
slurry for at least 30 minutes with a Sorvall RC-5B superspeed centrifuge at 15.000 rev/min,
were observed using a UV-visible spectrophotometer (perkin-Elmer, Lamda 1, UVIVIS).
Changes in the surface tension of surfactant solutions were observed using the Wilhelmy Plate
method with a Kruess KIO tensiometer. Changes in pH were monitored with a Metrohm digital
pH meter. All measurements were carried out at 25°C.
In order to check the reproducibility of the experimental data we had repeated some
experiments and found the measured values of the degradated surfactant concentrations to be
within ± 5%.
611
3. Results and Discussion
The concentration of CDBACI and CPCl were determined spectrophotometrically at 207 nm and
255 nm respectively. Their absorption were ascribed to the phenyl moiety, whose decomposition
can be followed by monitoring the decrease in the 207 and 255 nm band with irradiation time.
These spectral bands are assigned to the absorption band arising from the 11" -+ 11"' transitions of
the aromatic ring.
Initially the following experiments were carried out for both surfactants: (a) Irradiation and
stirring of the surfactant solution without catalyst for 10 hours and (b) stirring of the slurry
containing the surfactant without irradiation (in the dark) for 24 hours. Practically, in both cases,
no decrease in surfactant concentration or increase in the surface tension was observed, indicating
no direct photolysis of the substances. The 2-5% decrease of their concentration was ascribed to
their adsorption onto the catalyst surface, leading to a small decrease in their bulk concentration.
Both light and semiconductor particles are indispensable for the decomposition reactions. It is also
well known (Hidaka et al. 1985, Hidaka et al. 1986) that oxygen is also necessary in aquatic
solutions as no degradation occurs under anaerobic conditions.
The photodecomposition of CDBACI and CPCl as a function of the irradiation time is given
in Fig.l and Fig.2 respectively.
:::!! (a)
.... 1.0
,...
0
(b)
><
0 0.5
0 4 6 8
t ( h)
Figure 1. Photodegradation of CDBACI versus irradiation time in the presence of (a) Ti02 ,(b)
TiOiPt and (c) without catalyst.
Figures la and 2a give the decrease of the concentration of CDBACI and CPCl respectively
with time in the presence of Ti02 as catalyst. The degradation rate of CDBACI is faster compared
to that of CPCI. The decomposition is 33% for CDBACI and 20% for CPCl after 8 hours of
irradiation using naked Ti02 • Ti02 has an amphoteric character with a point of zero charge at pH
6.25, that has been determined by titration (Stumm 1990, Stumm and Morgan 1981). The surface
potential is negative in the neutral or alkaline pH region. The pH of both surfactant solutions is
approximately 5.5. In this pH region zeta-potential of Ti02 , measured microelectrophoretically
612
with an apparatus described in (Avranas et al. 1988) is slightly positive. This slightly positive
charge hinders the adsorption of cationic surfactants onto the surface of Ti02 •
2.0 (c)
1.6 (a)
-....
~
<t
0
1.2
(b)
>< 0.8
0
OA
a 2 4 6 8
t( h)
Figure 2. Photodegradation of CPCl versus irradiation time in the presence of (a) Ti02 ,(b)
Ti02 /Pt and (c) without catalyst.
This is perhaps the reason for the slow degradation of these substances, since they must first be
adsorbed to the surface in order their degradation could begin. These surfactants are adsorbed
with hydrophobic forces between the Ti02 and the hydrocarbon chain. The pH remains practically
constant during irradiation time, ranging between 5 and 5.5 units.
Figures 1b and 2b show the decrease in surfactant concentration when the catalyst used is
Ti02/Pt. It is obvious from both curves that the modified catalyst is more effective. The
respective percentages after 8 hours of irradiation are 55% for CDBACI and 35% for CPCI.
Changes of surface tension with time of CDBACI and CPCI solutions during photolysis are
shown in Fig.3. The results agree with these from the adsorption measurements. An increase in
surface tension of the solution toward that of water (72 mN'm- 1 at 25°C) is obvious after about
5 hours irradiation: a disappearance of the foam during stirring of the slurry is also observed.
It is not possible from the present data to elucidate the mechanism of the decomposition, since
it is very difficult to identify the intermediates. However from published results of similar
systems (Kormann et al. 1991, Harvey and Rudham 1988, Salvador and Decker 1984) it can
be assumed that the mechanism is as follows. Surfactants are adsorbed onto the semiconductor
particles. The adsorption of light by semiconductor,that has a band gap of - 3 eV creates
electron-hole pairs (Fig.4a). The holes, that have a slightly longer life time with respect to
electron transfer are strong oxidizing agents and being in the interface semiconductor/electrolyte,
react with adsorbed water molecules yielding OR- radicals according to
These OR- radicals which are the actual oxidizing agents attack the aromatic ring. The
degradation of the aromatic compounds occurs through hydroxylation of the aromatic ring by
613
means of OH' radicals and further steps that lead to opening of the ring. Finally through various
intermediates, unknown till now, one can at longer irradiation times go to complete mineralization
to CO2 , A possible second type of reactions involve a direct attack of the photogenerated charge
carriers with the surfactant molecules. The presence of nitrogen in the aromatic ring of CPCl may
be the reason for the slower degradation of this surfactant. The photo-catalytic oxidation of
organic compounds containing heteroatoms other than nitrogen generally results in only one type
of inorganic species from each heteroatom in the compound. Usually, more complex results are
obtained with compounds containing nitrogen (Low et al. 1991), especially if it is part of the
ring.
70 (a) ( b)
'ez 60
70
E
~ 50
50
0 1 3 5 0 4 8
t \ h.
Figure 3. Surface tension dependence on the irradiation time for (a) CDBACI and (b) CPcl:
(0) TiOz, (D) TiOzlPt and (~) without catalyst.
red
Figure 4. Schematic illustration of the photogeneration of holes and electrons upon excitation
of a semiconductor particle and the subsequent redox processes in (a) Ti~ and (b) TiOzlPt.
The photocatalytic action of Ti02/Pt can be explained in a similar way (Fig.4b). In this case
a better separation of electronlhole pairs can be achieved that leads to an increase in the number
of holes participating in the reactions (Gerischer 1984). However, a slowing down of the
decomposition rate of sodium benzene sulfonate is reported in the literature (Hidaka et al. 1986),
that perhaps may be due to the different way of preparation of the Ti02 particles with platinum.
614
4. Conclusions
The cationic surfactants CDBACI and CPCI, which are very slow biodegradable, are
photodegraded in aqueous solution using catalytic amounts of semiconducting powder such as
Ti02 and Ti02 modified with Pt. The illumination of such heterogeneous systems with
appropriate irradiation results in the formation of highly oxidizing surface peroxo species as well
as holes and electrons, themselves, strong oxidants and reductants. The primary step in the
photodecomposition of these compounds involves the oxidation of the aromatic moiety followed
by the slower cracking of the alkyl chain. Although total mineralization has not been
demonstrated, the destroying in a few hours of the surface activity together with the toxicity using
light of very low intensity (Aex> 350 nm, 40 mW I cm") is important, making the experimental
results promising.
The photodegradation of such organic compounds in semiconductor systems could find
important applications in the detoxification of waste streams, using artificial or sunlight as a light
source.
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Hidaka, H. Yamada, S. Suenaga, S. Zhao, J. Serpone, N. and Pelizzetti, E. (1990)
'Photodegradation of surfactants Part VI 'Complete photocatalytic degradation of anionic
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Catalysis 59,
279-290.
Karsa, D.R. (1990) 'Innovative approaches to surfactant development' in D.R.Karsa (ed.),
Industrial Applications of Surfactants II, Royal Society of Chemistry, Great Britain, pp.I-21.
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Kormann, C. Bahnemann, D.W. and Hoffmann, M.R. (1991), 'Photolysis of chloroform and
other organic molecules in aqueous Ti02 suspensions', Enviromental Science and Technology
25, 494-500.
Kreutler, B. and Bard, A. (1978) 'Heterogeneous photocatalytic preparation of supported
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Society 100, 4317-4318.
Low, G.K.C. McEvoy, S.R. and Matthews, R.W.(1991) 'Formation of nitrate and ammonium
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nitrogen atoms' Enviromental Science and Technology 25,460-467.
Matthews, R.W. (1987) 'Photo-oxidation of organic impurities in water using thin films of
titanium dioxide' ,I. Physical Chemistry 91,3328-3333.
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PROGRESS IN THE DEVEWPMENT OF CHWROFLUORCARBON (CFC)
ALTERNATIVES
J.J. LEROU & L.E. MANZER

Central Research and Development
Du Pont Company
Experimental Station
Wilmington, Delaware, USA 19880-0262
ABSTRACT. Chlorofluorocarbons (CFCs) are now believed to be major contributors to the seasonal
orone depletion over the Antarctic continent. They are so important for society that substitutes must be
rapidly found and commercialized. Several substitutes have been selected by the industry and significant
research and development programs are underway to commercialize them. Unlike the simple, fully-
halogenated CFCs which can be made in a single step, there are many potentially viable routes to the
alternatives, requiring significant improvements in catalysis. Many other important issues such as materials
compatibility, energy efficiency, developing country needs and product life cycle of the alternatives need
to be resolved before a timely transition to substitutes can be accomplished.
1. Introduction
Early refrigeration systems were developed with cooling fluids such as CH 3CI, S~, NH 3 ,
C2H2 C12 , CH2CI2 and hydrocarbons. From a thermodynamic standpoint, they gave good
refrigerating performance but were flammable and toxic. In 1928, two scientists, Thomas
Midgely and Albert Henne, at the Frigidaire Division of General Motors were asked to develop
non-flammable, non-toxic replacements for these hazardous cooling fluids in home refrigerators.
Albert Henne used the chemistry pioneered by Swarts [Swarts,F., (1892), Swarts,F., (1893)] at
the University of Gent, Belgium during the late 1890s for the synthesis of chlorofluorocarbons.
Within two days, Midgley and Henne had selected CFC-12 (CCI2F2) as an ideal refrigerant. The
initial stoichiometric reaction between SbCI 2F 3 and CCI4 was developed into a continuous process
in a joint venture between Du Pont and General Motors during the 1930s. The carbon
tetrachloride and HF were continuously fed to a reactor containing pentavalent antimony, and by
adjusting process conditions the degree of fluorination on the carbon could be controlled. This
synthetic route was further developed and formed the basis for modern-day commercial
chlorofluorocarbon processes to make the important refrigerants, cleaning agents, and blowing
agents: CFCs-ll (CFCI 3), CFC-12 (CF2 CI2), HCFC-22 (CHF2 CI), CFC-I13 (CF 2 CICFCI2),
CFC-1l4 (CF2 CICF2 CI) and CFC-1l5 (CF 3CF2 CI).
By 1988, total CFC world consumption had grown to over 10<' tons. In the U.S. some 5000
businesses at nearly 375,000 locations produced CFC-related goods and services worth more than
$28 billion a year [Glas,J.P., (1989)]. CFC-related jobs totalled more than 700,000. Within the
United States, the three major uses are as refrigerants (30%), as foam-blowing agents for
polystyrene and polyurethane (28%), and as industrial solvents and cleaning agents (19%).
617
618
Outside North America, a significant amount (> l.5x108kg) of CFCs have continued to be used
as aerosol propellants, even though that application was essentially banned in the U.S. in 1978.
Information contained in the International Ozone Trends Panel Report [WMO, (1988)] and
supported by more recent information including the ozone trend results from analysis of the Total
Ozone Mapping Spectrometer (TOMS) data [Stolarski, (1991)] provides compelling evidence that
production and use of CFCs should be phased out to reduce risk of ozone depletion. In 1990 the
Montreal Protocol, an international agreement regarding CFC production and use, was
strengthened to require a phaseout of production in developed countries by 2000 and by 2010 in
developing countries.
2. Selection of Suitable Alternatives
A recent market projection by Du Pont [Du Pont, (August 1989), Du Pont, (January 1989)] has
attempted to determine how the current markets that use CFCs will be satisfied in the year 2000.
Increased awareness to environmental issues and costs will result in about a 30% reduction in the
market through improved conservation measures. These include better maintenance systems and
product recovery, recycle, and reclamation. Another 30% of the market will switch to less
expensive, not-in-kind replacements. For example, organic/H2 0-based systems may be used for
certain cleaning applications and mixtures of CO2 , hydrocarbons and water could be used as foam
blowing agents. Du Pont, however, predicts that the remaining 40% of the projected market will
still require fluorocarbon-based products because of the unique properties associated with these
molecules, particularly in the refrigeration industry. The unique vapour phase thermal
conductivity of CFCs contributes to the efficiency of plastic insulating foams for refrigerators,
freezers, buildings, refrigerated railway cars and trucks. Even if the foams could be expanded
with air or carbon dioxide, the thermal efficiency would be reduced by about a factor of two.
The energy penalty associated with the elimination of hydrochlorofluorocarbons from insulating
foams could be equivalent to several billion gallons of additional fuel consumed in the United
States annually. Hydrofluorocarbons and hydro chlorofluorocarbons have emerged as alternative
fluorocarbon products for the remaining market segment and will form the basis for the
remainder of this discussion.
Selecting appropriate substitutes for an industry that has developed over 50 years is no trivial
task. Many factors must be considered and thoroughly evaluated. Foremost is environmental
acceptability for the ozone and other environmental concerns such as global warming and acid
rain, but economic factors are important as well. There is an estimated $135 billion worth of
equipment in the U.S. which depends on CFCs, with an expected lifetime of 20-40 years.
Therefore, it is very important that the physical properties of the alternatives closely match those
of the CFCs they are replacing.
The ozone depletion potential (ODP) of a compound can be calculated by dividing the
cumulative calculated ozone depletion caused by the release of a compound by the calculated
ozone depletion of an equal emission (by weight) of CFC-l1. In a similar manner, relative
halocarbon global warming potential (GWP) can be calculated. Thus, ODP is an estimate of
relative effects and should, therefore, be used to determine the relative long-term environmental
benefits of alternative compounds. Since the HFCs do not contain chlorine and therefore have
an ozone depletion potential (ODP) of zero, they are very attractive alternatives. The absence
of chlorine in HFCs, however, often results in a higher vapour pressure and lower solubility than
CFCs. These two characteristics limit their use for some applications. Significantly-reduced
ODPs can be obtained by introducing H atoms into the molecule, even if it contains chlorine.
619
This causes the molecule to decompose in the troposphere so that very little reaches the ozone
in the stratosphere.
The most likely substitutes for the three major CFCs are shown in Table 1. It should be
pointed out that CF2HCI (HCFC-22) has been produced for many years and is currently used in
certain foam-blowing and refrigeration applications. Additional growth in the use of this
compound will likely continue. The projected costs for these molecules are approximately 2-5
times that of the CFC they are replacing as a result of the complexity of new manufacturing
processes and higher ingredients' costs because of the higher molecular weights of the substitutes.
Table 1. Potential CFC Substitutes
Market Current CFC CFC-Alternative
Refrigerants HFC-134a (CF3CFH2)

HCFC-22 (CHF2CI)
Blends!Azeotropes
Blowing Agents CFC-ll (CFCI3) HCFC-141b (CH3CFCI2)

HCFC-123 (CF3CHCI2)
HCFC-22 (CHF2Cl)
Blends!Azeotropes
Cleaning Agents CFC-l13 (CF2CICFCI2) Blends,!Azeotropes

New Compounds
In many cases, enhanced performance over single compounds may be obtained by combining
two or more compounds as blends and/or azeotropes. For example, Du Pont has announced
[Du Pont, (January 1989)] a ternary blend that may prove to be a near "drop-in" replacement for
refrigerant CFC-12. The blend consists of HCFC-22 (CF2HCI), HFC-152a (CHF2CH 3) and
HCFC-124 (CF 3CHFCl) and has an ODP of only 3% of CFC-12. These blends do not appear
to have the problems with oil compatibility in automotive air conditioners as does HFC-134a and
may be very attractive, drop-in substitutes for systems equipped to use CFC-12. It is estimated
that 60 million vehicles designed for CFC-12 will still be operating in the United States in the
year 2000. An important molecule that has unique properties as a solvent and cleaning agent is
CF2CICFCI2 (CFC-l13). Although much research has focused on the identification of an
acceptable single substitute, no widely accepted candidate has emerged.
3. Potential Routes to CFC-AIternatives
The only viable chemical route to the simple CFCs involves the reaction of a chlorocarbon with
HF, either in the gas phase over heterogeneous catalysts or in a liquid phase. For the two-carbon
CFC-alternatives, the chemistry becomes much more complicated since there are now at least 4
chlorocarbons that could be produced on a large scale commercially, and a wide variety of
620
reaction pathways exists to convert each of these feedstocks to HFC-134a (Fig 1).
Fig. 1. Potential Routes to HFC-134a
Of the many routes to HFC-134, two have received the most attention in the literature; those
based on HCFC-133a (CF 3CH2 CI) and CFC-114a (CF 3CCI 2F).
HCFC-133a (CF 3CH2Cl) is a small volume commercial product today, although it is
carcinogenic and embryotoxic. Its preparation is well documented either in gas phase [ICI U.S.
Patent 3,755,477 (1973)] or liquid phase [Du Pont U.S. Patent 2,230,925 (1941); Du Pont U.S.
Patent 3,003,003 (1961)], by the reaction of HF with trichloroethylene (fCE):
CHCl=CC12 + HF --.. CF3CH2Cl + CF3CH2F

(1)
TCE HCFC-!33a HFC-l34a
It appears unlikely that a single-step, high yield route to HFC-134a, analogous to that for the
preparation ofCFC-12, exists. Early work by Dow [Dow U.S. Patent 2,885,427 (1959)] showed
that the direct reaction of TCE with HF gave only 3 % HFC-134a and 78 % HCFC-133a, using
an "oxygenated-chromium fluoride" catalyst at 300-400°C. By increasing the temperature to
500°C over a modified Cr+ 6/AI2 0 3 catalyst, Kaiser [Kaiser U.S. Patent 4,782,643 (1988)]
claimed a 20% single pass yield to HFC-134a. The main products were HCFC-133a (50%) and
20% "other". Conversion of a -CH2Cl group such as that in HCFC-133a, to -CH2F is known
to be a very difficult transformation, often requiring expensive fluorinating agents [Hudlicky,
(1963)]. The reaction of HF with HCFC-133a requires a large excess of HF to drive it to a
reasonable organic conversion. For example, a 30% single pass yield of HFC-134a is obtained
at 350-400°C with 6-10 moles of HF per mole of HCFC-133a fed [ICI U.S. Patent 4,129,603
(1978)]. This requires a large recycle of organic and HF. Catalyst lifetime is a major problem
with this process. Daikin [Daikin Great Britain Patent 2,030,981 (1978)] indicated that with
Cr-based catalysts, the conversion decreased 15% in only 40 hours of operation. However, by
co-feeding small amounts of air, a constant conversion was maintained for 80 hours of operation.
621
Recent Du Pont work [Du Pont U.S. Patent 4,922,037 (1990)] suggests that a variety of metals
on an aluminum fluoride support provides extended catalyst life.
Another two-step route that has received considerable attention in the patent literature involves
CFC-114A as an intermediate (2-3):
CC12=CC12 + Clz + HF --- CF3CFCl2 + CF2ClCF2CI (2)

PCE CFC·114a CFC·114
CF3CFCl2 + H2 --- CF3CFH2 + HCl (3)

CFC-114a HFC.l34a
Since only the asymmetric isomer, CFC-114a, is readily hydrodechlorinated to HFC-134a, a

high isomer yield is important. Montedison has reported [Vecchio, (1974)] that the
chlorofluorination of ethylene or tetrachloroethylene over promoted-aluminum fluoride catalysts
gives 75 % CFC-114a. The second step involves the selective hydrodechlorination of CFC-114a
from the mixture to give HFC-134a and unreacted CFC-1l4 [ICI Great Britain Patent 1,578,933
(1980)]. Over a Pd on activated carbon catalyst, the yield to HFC-134a is >90%. A recent
patent has claimed that CFC-1l4 can then be isomerized to CFC-1l4a, potentially giving a high
overall yield in a 3-step process [Montedison U.S. Patent 4,748,284 (1988)]. Numerous patent
applications [Asahi Glass Japanese Patent Applications 1-128942, 1-132537, 1-132538 (1989)]
have claimed a wide variety of metals for the hydrodechlorination chemistry (3), addressing
problems associated with catalyst life.
4. Process Development
The recent patent literature has suggested that many of the routes indicated in Fig. 1 have
received attention and improvements can be expected. However, it is clear that the processes to
manufacture alternatives will be far more complicated than existing CFC processes. In pilot
plants around the world, chemists and engineers are aggressively working to develop critical data
which will allow them to design and build world-scale commercial facilities in record time to
meet the needs of society as CFCs are phased out. Obviously, for a development program of this
magnitude and environmental significance, the normal time lines cannot be followed. In less than
4 years, Du Pont has designed, constructed and started up 10 pilot and interim commercial
facilities to simultaneously develop process technology for many CFC alternatives and provide
initial quantities for customer evaluations, as well as toxicity testing. Commercial plants are
being designed based on a minimal amount of data, with the potential risk that a problem could
occur during the pilot plant work requiring very significant and costly changes. Physical property
data on many of the new compounds and their intermediates is not available, so extensive
experimental work is required to make these measurements. Since many fluorocarbons form
unpredictable azeotropes with each other and with HF, the purification operations of new plants
can be expected to be complicated and require extensive development.
622
5. International Cooperative Programs
Extensive toxicity studies are required before large volumes of these new products will be
released for general use. Since these studies are costly and timely, several CFC producers have
formed consortia to share costs and expedite the testing process. To date, four consortia, PAFTs
I, II, III and IV (programs for Alternative Fluorocarbon Testing) have been established to
evaluate the toxicity of HFCs-134a, 125, and HCFCs-124, 123, 225ca, 225cb and 141b. A
preliminary report from PAFT's I and II indicated that no problems have been encountered, so
far, for HFC-134a and HCFC-141b. HCFC-123 recently was found to cause benign tumours in
male rats.
Another group, AFEAS, (Alternative Fluorocarbon Environmental Acceptability Study) was
formed to survey the effect of the alternatives and their degradation products on the environment.
Their first report [Scientific Assessment of Stratospheric Ozone, (1989)] summarized existing data
and proposed a program to collect the necessary data to complete the evaluation. A $6 million/3-
year program has been funded by 12 CFC producers and is underway to attempt to fill the gaps
where data is missing. The five categories under study are: (1) their potential to affect
tropospheric ozone; (2) how the compounds degrade in the atmosphere; (3) the potential
environmental effects of the degradation products in air, water and soil; (4) their potential to
affect stratospheric ozone; and (5) their potential to contribute to future global warming.
6. Some Remaining Key Issues
Action by the CFC producers and users around the world has been very positive. Many of the
key programs are in place to provide a safe and timely transition away from CFCs to
environmentally acceptable alternatives. The scientific community has reached a consensus that
the rapid and successful introduction of HFCs and HCFCs will result in lower stratospheric
chlorine levels. Government cooperation is required to ensure a rapid transition away from
CFCs. Uncertainty about availability of HCFC and HFC alternatives delays commitments by
producers of goods currently dependent on CFCs. Companies must know what alternatives will
be available before committing major investments to the research and development necessary to
use the new compounds in their products. Policy makers need to provide clear and prompt
signals to industry and the consumer. If HCFCs and HFCs are deemed acceptable alternatives,
a strong statement to that effect will speed their development and the transition from CFCs. If
they are deemed unacceptable, industry may focus its resources elsewhere which will likely mean
continued use of CFCs until other viable technologies are identified.
The compatibility of CFC-alternatives with the internal plastic parts of many pieces of
equipment is a concern. In many applications, parts such as the O-rings, gaskets and seals will
need to be changed to other polymer materials that are not affected by the new materials. This
can only occur after large quantities of CFC-alternatives are available for extensive customer
testing.
Energy efficiency is also a factor that must be considered. In some refrigeration applications,
the alternatives are less efficient than the CFCs they are replacing, which could result in higher
energy consumption or require a significant redesign of the equipment.
Although many of the CFC-producing nations are likely to agree to a phaseout by the year
2000, they account for only about 30% of the world population. Developing countries must be
encouraged to restrict their growth of CFCs and implement new technology based on HFCs and
HCFCs, to ensure a rapid and complete phaseout of CFCs.
623
References
Asahi Glass Japanese Patent Applications 1-128942, 1-132537, 1-132538 (1989).

Bivens, D.B., Gorski, R.A., Wells, W.D., Yokoseki, A., Lindstrom, R.A., and Shimon, R.L.
(1989) 'Evaluation of Fluorocarbon Blends as Automotive Air Conditioning Refrigerants', SAE
Paper No. 890306; Bateman, D.J., Bivens, D.B., Gorski, R.A., Wells, W.D., Lindstrom,
R.A., Morse, R.L. and Shimon, R.L., (1990) 'Refrigerant Blends for the Automotive Air
Conditioning Aftermarket', SAE 900216.
Daikin Great Britain Patent 2,030,981 (1978).
Dow U.S. Patent 2,885,427 (1959).
Du Pont U.S. Patent 2,230,925 (1941); Du Pont U.S. Patent 3,003,003 (1961).
Du Pont, (January 1989), Alternatives Circular, #HI2524.
Du Pont, (August 1989), Alternatives Circular #H-07421.
Du Pont U.S. Patent 4,922,037 (1990).
Glas,LP., (1989), 'The Global Impact of CFCs', Printed Circuit Assembly, Sept. 1989, 10-19.
Hudlicky, Adv. Fluorine Chern., 185 (1963).
Kaiser U.S. Patent 4,782,643 (1988).
ICI U.S. Patent 3,755,477 (1973).
ICI U.S. Patent 4,129,603 (1978).
ICI Great Britain Patent 1,578,933 (1980).
Montedison U.S. Patent 4,748,284 (1988).
Scientific Assessment of Stratospheric Ozone, (1989), Volume II; Appendix: AFEAS Report.
World Meteorological Organization Global Ozone Research and Monitoring Project - Report
No.20.
Stolarski, Richard S., Bloomfield, Peter, McPeters, Richard D., and Herman, Jay R. (1991)
'Total ozone trends deduced from Nimbus 7 TOMS data', Geophys. Res. Lett. 18, 1015-1018.
Swarts,F., (1892), 'Note sur un nouveau derive fluore du carbone', Bull. Acad. Roy. Belg. 24,
309.
Swarts,F., (1893), 'Sur Ie fluorchlorbrommethane', Bull. Acad. Roy, Belg. 26, 102.
Vecchio, M., Groppelli, G., and Tatlow LC. (1974) 'Vapour-phase process for the Manufacture
of chloroethanes', J. Fluorine Chern., 18, 1; Montedison Italian Patent 680,700 (1965)
WMO (World Meteorological Organization) (1988), Report of the International Ozone Trends
Panel, Report No.18.
INDEX
abrupt exit 516 alkylate 40,65, 147, 153

accidental spills 577 alkylation 19,21, 166
acid-base properties 291 alkylation agents 209
acid rain 379 alkylation with unsaturated hydrocar-
acid-site density 76 bons 206
acid strength 61,76,86 ALKYMAX 159
acidic catalysts 73 Alternative Fluorocarbon Environmen-
acidic sites 294, 427 tal Acceptability Study 622
acidity 57, 290 alternatives to steam reforming 274
activated soda 467 alumina calciners 537
activation energies 111 aluminium chloride 17
activation energy for the n-hexadecane aluminum 53
ultrapyrolysis 336 aluminum acid sites 54
active sites 86 aluminum sites 52
active zeolite 51 ammonia 268
additives 2 ammonia injection 389
additives in FCC 40 ammonia production 252
adiabatic fixed bed 169 ammonium ion 51,53
adiabatic pre-reforming 249, 264 anatase 578
adiabatic reformer 251 andalusite 56
adiponitrile synthesis 353 Anderson-Flory-Schulz 230
Adler and Enig criterion 446 anionic vacancies 295
advanced cracking reactor 341 annulus 538
advanced energy transfer systems 252 Antarctic continent 617
advanced reforming 273 anthracite coal 397
advanced riser separators 39 antimony 72
aeration 23, 28, 46 apparent densities 29
Ahlstrom license systems 515 apparent effective hydrogen dif-
Ahlstrom Pyroflow CFB combus- fusivity 238
tor 396 approach to equilibrium at reformer
air 2,7 outlet 251
air compressors 382 aquatic environment contamina-
air-lift fermentors 359 tion 577
air pollutant emissions 404 arc 329
air pollution 13 ARCa 305
Al28 538 ARCa process 228, 311
alcohol 2,9 aromatic 9
alcohols and ethers 7 aromatics 2,40, 148
alkyl aromatics 74 aromatization selectivities 156
alkyl phenols 585 Asahi Glass Japanese 621
625
626
ash 380 Berty-type reactors 262

ash agglomeration 386 bifunctional mechanism of hydrocrack-
asphalt residual treating process 341 ing 427
ASVAHL 432 bifurcation point 449
asymptotic Sherwood and Nusselt binder 51
numbers 562 Bintula 284
atmospheric distillation 18 Bintulu project 245
atmospheric fluidized bed boiler 382 biological waste water treatment 353
atmospheric gas oil 328 bismuth 72
atomization 500 bituminous coal 397
atomizing nozzles 32 blowing agents 619
atrazine 587 boiling range of gasoline (T90) 151
attrition 66, 80, 385 bond 427
Auto/Oil Air Improvement Research bond angle 56
Program 147 Boolean matrix 415
automobile emission control 547 Boolean relation matrices 409
automotive catalysts 547 Boudouard reaction 262
automotive pollution control 547 bromination 189
autothermal reformer 251,267 Bronsted acid sites 75,418
autothermal reforming 249,267 Brown coal 403
Average Bulk Density 52 bubble assemblage model 308
averaged suspended solids den- bubble coaslescence 356
sity 511 bubble column 233
axial dispersion 355 bubble column modeling 354
axial dispersion coefficient 355 bubble column reactors 353
axial normal stresses 368 bubble wake 360
azimuthal velocity 367 bubbles 27,353
bubbling 28
backmixing of the liquid phase 353 bubbling bed combustor 399
baffles 33,354 bubbling bed combustors 383
ballistic separator 21 bubbling fluidized bed combus-
BASF process 201 tors 507
batch reactors 328 bublbing regime 27
bed density 33 bullet shaped bubbles 357
bed dynamics 143 burning coal 379
bed pressure drop 141 burning coal particles 511
Benesi method 290 burning natural gas 379
Benson process 190 butane 2, 15, 147
bentazon 586 butanes 77
benzene 2,148,582 butenes 75
benzene alkylation 159 butylenes 19
benzene concentration 147
Bernoulli equation 137 c/o 77
Berty reactors 93 C-efficiencies 212
627
C-efficiency 203 catalysts for hydrotreating 428

C-H bond rupture 301 catalytic cracking 71
C2H4 oligomerization 196 catalytic fluidized-bed reactor 306
C2H4 selectivities 197 catalytic hydrocracking 409,417
C3H6 formation 207 catalytic OCM reaction 300
C2+ selectivity 306, 317 catalytic oxidative coupling of
Cl-chemistry 249 methane 286
calcination 58 cationic surfactants 609
calcium limestone (CaC0 3) 386 catlytic cracking 409
calcium oxide 292, 467 CATOFIN process 173
calcium sulfite 380, 467 catstill process 160
CANMET hydrocracking 436 CBr4 188
CaO-Ce02 mixed oxides 294 CCl4 188
CaO lattice 297 CCR (conradson carbon) 42
capacitance probes 358,512 CCR moving bed 173
capillary condensation 233 CDBACl 609
capture of S02 468 CDTECH 159
capture polluting gases 380 Ce02 556
carbenium ion mechanisms 409,418 ceramic monoliths 548
carbenium ions 74 cetane index 147
carbocations 74 cetane number 431
carbon 262 cetyldimethylbenzy lammonium
carbon dioxide 379,582 chloride 609
carbon dioxide emissions 380 cetylpyridinium cloride 609
carbon formation 201, 262 CF3CHFCI 619
carbon forming reactions 251 CFB 537
carbon left on regenerated catalyst CFBC 507
(CORC) 33 CFC-1l3 617,619
carbon limit diagram 265 CFC-1l4 617
carbonium ions 74, 75 CFC-1l5 617
CARPT 360 CFC-12 617,619
CaS0 3 500 CFC substitutes 619
CaSO/CaS04 500 CFCs-ll 617
CaS04 400, 500 CHzBrz 188
cat-to-oil coke 76 CHzClz 188
catalyst activity decay functions 85 CH3Br 188
catalyst coolers 46, 72 CH3CI 188
catalyst flux 23 CHpH 184
catalyst immobilization 597 CHpH synthesis 220
catalyst preparation 51 CH3 species 300
catalyst residence time 34 CH4 alkylation 209
catalyst steaming 79 CH4 pyrolysis 205
catalyst time-on-stream 85 chain-length-independent growth
catalysts 51,237 process 240
628
chain transfer 75 coal combustion 379

changes of surface tension 612 coal combustion technologies 380
channel Reynolds number 551 coal combustors 537
channelling 134 coal-fired utility plants 379
char 403 coal particle fragmentation 385
char combustion 384, 385 coal reserves 227,228
charge distribution 56 coalescence-redispersion 356
CHBr3 188 cobalt 428
CHCL3 188 cofeed method 290
chemical feedstocks 283 cofeed mode 305
chemisorption of methane on coke 21,33,59,75,325,430
nickel 258 coking reactions 327
chlorination 353 collection efficiency 36
chlorofluorcarbon (CFC) 617 column compartments 368
chum turbulent bubble columns 355 combustion 4, 7
chum-turbulent flow 356 combustion efficiencies 381,508
circulating fluidized bed 537 combustion efficiency 386
circulating fluidized bed boilers 379 combustion of a bituminous high
circulating fluidized bed combustors sulphur Eastern Canadian coal 532
(CFBC) 379,507 combustion of high sulfur fossil
circulation flux of solids 513 fuels 467
Cl2 188 combustion of single carbon par-
clay 51 ticles 385
clean air act 380 combustion pilot plant 510
clean fuels 147 combustion process 379
Clean Air Act Amendments 147 combustion promoters 72
cleaning agents 619 commercial risers 84
closed cyclones 164 commercial unit 77
cluster analysis 84 compressed natural gas 227
clustering 519 computer aided tracking of a single
clusters 27, 529 radioactive particle (CARPT) 353
clusters of particles 519 computer-generation of reaction
Co 430 schemes 415
Co-Mo on alumina 438 concentration measurements 144
Co-Mo-S phase 176 configurational diffusion 79
CO 2,11,44,63,64, 118, 147, 151, configurations of reformer fur-
549 nace 253
CO/C02 ratios 45 conradson coke 76
CO nonattainment areas 149 contaminant coke 76
CO oxidation 564 convection 357
CO-rich gases 271 convective dispersion 359
CO2 44, 118,249,549 conventional fluidized bed
CO 2-reforming 249,265 boilers 381
coal 4, 185,210,381 conversion of petroleum residues 353
629
copper-based 270 dense fluidized beds 72

copper-promoted shift catalysts 270 design procedures 354
core-annular flow patterns 519 desulfurization 426
core-annular solids transfer 530 desulfurization chemistry 177
core region 538 desulfurization processes 499
counter-current backmixing desulphurization 252
model 307 detergent additives 148
COx 187,300 detoxification of waste water 610
CPCl 609 devolatilization 383
cracking 4 devolatilization process 403
cracking catalysts 77 dibenzothiophenes 178
cracking of pure compounds 108 diesel fuels 147, 184
creep rupture strength 253 diesel oil 425
crude lumped reaction schemes 418 diffusion 78
crude oil 7, 17,227,283 diffusion limitations 238, 565
cryovortactor 341 diffusion mechanism 239
crystalline pore structure 393 diffusion through the product
CSIROIBHP process 310 layer 480
CuCIKC1/LaCI3 catalyst 188 diolefins 168
CuO catalyst supported on "(- direct conversion 274
alumina 454 direct conversion to CzHz 199
Curie Point Pyrolyser 330 direct methane conversion 183
Curie Point temperature 333 direct partial oxidation to
cyclohexene 61 methanol 183
cyclone efficiency 36 disengagement zone 356
cyclone performance 36 disengaging height 23
cyclones 24,33,36,52,381,508,538 disposal 430
cyclopropane 61 distillate hydrotreating 439
cyclopropene 61 distribution 230
cylindrical monoliths 552 distributor plate 431
distributor region 355, 364
Davison Circulating Riser (DCR) 91 DME 170
DDT 586 dolomite (CaC03 MgC03) 386
de-alkylation 74 dolomite 380, 508
deactivation constant ~ 477 doping reducible metal oxides 290
deactivation models 476 downward flux 542
dealuminated zeolites 54 DPOM processes 218
dealumination 52 DPOM reactor 214
DEALY 51 drinking water 577
decay functions 82, 97 dry flue gas desulphurization
defluidization 233 processes 500
dehydrogenation 14,171 dry processes 467
dehydrogenation of ethane 304 dry processes for SOz removal 492
denitrogenation 426 Du Pont 621
630
dust collectors 388 emissions 151

DyP3 318 energy efficiency 622
dysprosium oxide for oxidative energy resources 325
coupling of methane 317 enhancing effect on reactor
runaway 451
ebullating fluid 435 ensemble averaged velocity 360
ebullating reactors 435 ensemble control 266
ecosystem 1 entrainment 359
eddy viscosity 363 entrainment region 342
effcts of coal composition 397 entrance 32
effect of oxygen-ion conductivity 294 entrance and exit effect 329
effect of oxygen on the yield environmental 1
of C2+ 321 EPA regulations 147
effect of temperature on C2+ selec- equivalent reaction time 329
tivity 299 equivalent reactor volume con-
effect of temperature on selectivity cept 329
of C2+ 321 Equivalent Reaction Time 337
effect of Zn 2+ cations 296 erosion of the tube surfaces 507
effective pore diffusion coefficient of ethanol 7,8, 13, 150
S02 478 etherification chemistry 168
effective residence times 338 ethers 2, 8, 13
Effective Residence Time 337 ethyl tertiary butyl ether (ETBE) 7,
effectiveness factor 259,562 14, 150
effects 32 ethylene 159
effects of exit geometry 515 Eulerian fluctuating velocities 368
effects of sorbent type 392 evaporation of solid pellets 133
elastomers 9 excited-state electron 609
electric arc 185 exit 32
electricity 4, 379 exit effects 514
electrochemical processes 602 expanded beds 169
electroconductivity 359 expansion turbines 382
electron/hole recombination 581 explosion limits for a hydrogen-
electrons 613 oxygen mixture 456
electrostatic precipitator 21 explosive systems 443
electrostatic precipitators 388 exponential decay function 85
Eley-Rideal-mechanism 303 exponential decay model 110
elliptical monoliths 552 extra particle mass-transfer limita-
embrittlement 9 tions 239
emission 7 Exxon Donor Solvent coalliquefac-
emission 11 tion process 354
emission 537
emission control strategies 379 fabric filters 388
emission standards 547 fast pyrolytic processes 326
emissions 1 faujasite 51,53, 162
631
FCC 51,133,147,217 fluidized bed 278, 367

FCC catalyst 71 fluidized bed combustors 467
FCC cycle oils 175 fluidized-bed operation 196
FCC hardware 164 fluidized bed reactors 87
FCC Naphtha 176 fluidized-bed reactors 305
FCCU additives 63 fluidized beds 353,360
Fe 430 fluidized regime 143,234
Fe-Ni-Cr alloys 264 Fluidized Catalytic Cracking
feed injection 31 (FCC) 17
feed nozzles 31 fluorophenols 584
feed point location 384 2-fluorophenol 583
feed riser 31 fly ash 388
feedstock crackability 82 fly ash addition 500
fennentation 353 folded riser reactors 91
ferric fonnation of big bubbles 239
ariacety lacetonate/triethylaluminum fossil fuels 507
catalyst 208 framework 54
FeS04 503 free nickel site 258
fibre (whisker) 262 free radical 74
fibre optic 134 free-radical mechanism 327
fibre optic probe 139 freeboard 34
fibre optic sensors 518 freeboard region 364,511
fibre optic techniques 133 fuel blending 150
field ionization mass spectrometry fuel cells 252, 270
(FIMS) 179 fuels 1, 17
filament pyrolyzers 329
fines 52 gamma rays 538
Fischer-Tropsch (FT) 218,283,353 gas and liquid velocity distribu-
Fischer Tropsch ARGE process 277 tion 356
Fischer-Tropsch synthesis 227,441 gas backmixing 515
Fischer-Tropsch waxes 227 gas bubble fonnation 356
fixed bed 14,305 gas compression duty 212
fixed inventory system 512 gas distributor 353
flow instabilities 346 gas expansion duty 212
flow reactors 329 gas-filled pores 238
flow sheeting 305 gas holdup 356
flue gas desulfurization 353, 467 gas-liquid mass transfer 356
flue gas desulphurization 499 gas mixing 133
fluid bed 233 gas oil 71, 82,327
fluid bed boilers 380 gas-solid reaction kinetics 133
fluid-bed MTG process 221 gas sparged bubble columns 353
fluid-bed processes 233 gas velocity measurements 136
fluidizability of various catalysts 306 gaseous fuels 227
fluidization 17,27,52, 133 gasoline 1,7, 12, 13, 17,20,42,52,
632
72,75,147,184 HDS 428

gasoline octane 178 heat conduction 556
gasoline yields 102 heat conductivity 552
GC-MS 107,421 heat exchange reformer 249,255,269
GC-RON 104 heat of reaction parameter 447
general dispersion model 355 heat pulse-probe 359
generalized criterion for parametric heat transfer 380
sensitivity 446 heat-transfer duty 212
generalized sensitivity criterion 444 heat transfer in circulating fluidised
generating heat 379 bed 524
geothermal 379 heat transfer surfaces 515
global warming 379 heat transfer surfaces in industrial
Graetz-Nusselt model 554 circulating fluidised bed 524
grain models 474 heat transfer to immersed tubes 357
grain models neglecting pore diffu- heating of the coal particles 383
sion 470 heating rates 326
greenhouse 4 heavy (resid) 17
greenhouse effect 47 heavy hydrocarbon pyrolysis 348
grid pressure drop 24 heavy metals 148
groundwater 577 heavy metals content 325
group A particles 521 heavy oil pyrolysis mechanisms 326
group B particles 521 heavy oil ultrapyrolysis 338
gulf streaming 357 heavy paraffin conversion 229
GX-30 109,117 heavy paraffin synthesis 229,233
GX-30 catlysts 100 heavy polynuclear aromatics 438
gypsum 380 heptene 60
herbicides 582
H-Oil 354, 435 herbicides and pesticides 585
H2 549 heterogeneous photocatalysis 578
HiCO ratio 249 heterogeneous photocatalyst 579
Hp 549 heterogeneous photocatalytic degrada-
HP2 503,601 tion 609
H2S 431 HFC-152a 619
halocarbon global warming potential high alloy tubes 252
(GWP) 618 high performance chromatographic
halogens 188 separations 178
HBr 189 high performance liquid chromatog-
HCFC-22 617,619 raphy (HPLC) 179
HCHO 186 highest steady state 556
HCl 191 highway diesel fuel 149
HCO 107 holdup 355
HCON process 432 hole pairs 609
HDA 428 holes (h+) 279
HDN 428 homogeneous bubble flow 356
633
honey-comb catalysts 260 impeller speed 143

hoppers 23, 29, 538 impinging horizontal jets of
hot film sensor 135 solids 347
hot spots 260, 262, 386, 444 in-situ velocity 144
hot wire anemometry 133, 358 incipient wetness 233
Houdry's CATADIENE 172 incremental energy of vaporiza-
HPLC 421 tion 234
Huels Arc Process 199 indirect conversion process 221
HY 78 indirect liquefaction of coal 228
hydro-dehydrogenating sites 427 indirect processes 227
hydrocarbon formation 301 industrial pyrolysis reactors for
hydrocarbon recombination reac- olefins 340
tions 327 inhibitors 4
hydrocol 234 instantaneous suspension density 518
hydrocracking 242, 426, 427 intensity of turbulence 363
hydrocracking process 240, 425 inter-cell interaction 358
hydrocraking 252 intermediate geometry exit 517
hydrodesulfurization 425 intermittency index 519
hydrodesulphurization 268 internal recycle reactors 92
hydroelectric sources 379 internally circulating fluidized
hydrogen 1,8,270 bed 346
hydrogen-deficient feedstocks 341 International Ozone Trends Panel
hydrogen on coke 44 Report 618
hydrogen peroxide 579 intraparticle diffusion 429
hydrogen transfer 51,54,59,71,75 intrapartic1e diffusion limitations 235,
hydrogenation 426 239
hydrogenation of coal 227 intrenal recycle reactors 134
hydrogenation on Pt 419 inviscid models 357
hydroisomerization of n-paraffins 241 iron 426
hydroprocessing 175, 270 irradiation time 611
hydrotreating 4, 353,426 iso-amylene 14
hydrotreating processes 425 iso-butane 14
hydroxyl radicals 579 iso-butylene 14,38
Hyvahl-F process 433 iso-o1efins 13
HYVAHL 432 isobutane 19, 66
HZSM-556 isobutylene 169
isomerate 153
ICFB 346 isomerization 14,61, 74, 158
ICI process 220 isooctane 9
IFP process for the oxypyro1ysis of isoolefins 62
natural gas 311 3-isopropy1-2,1 ,3-benzo-thiadiazin-4-
ignited zone 552 one-2,2-dioxide 586
ignition 449 isotropic turbulence assumption 356
impeller rotational speed 134
634
jet fuel 425 liquid fuels 283

liquid holdup 362
k-e turbulence model 356 liquid hydrodynamics in bubble
Kellogg orthoflow F 22 colums 356
kinetic energy of turbulence 363 liquid recirculation 357,364
kinetic modeling 71, 4lO, 417 liquid transportation fuels 228
kinetic modeling of catalytic crack- liquified petroleum gas 227
ing 81 local ignition process 552
kinetic parameters for pure hydrocar- local instantaneous velocities 360
bons 112 local mixing 355, 356
kinetic parameters for the 8-lump local sensitivity 449
model 115 low sulfur/high quality distillate 174
kinetic parameters in the riser low uniform combustion tempera-
simulator 109 tures 507
kinetic reaction scheme 308 low volatile fuels 399
Knudsen diffusion 239,563 Lowenstein's Rule 58
LPG 249
L~03-CaO 293 lumped models 4lO
Lagrangian fluctuating velocity 364 3-lump model 98
Lagrangian integral time scale 364, 8-lump model 98, 117
368 lO-lump model 98
landfill hazardous waste sites 577 lumped schemes 417
Langmuir adsorption isotherm 589 lumping strategy 81
Langmuir-Hinshel-wood-type Lurgi process 220
adsorption 301
laser 329 M-forming 157, 160
Laser Doppler Velocimetry 358,537 macroscale hydrodynamics of
lateral mixing of solids 508 circulating fluidised beds 511
LC-Fining process 354,435 manganese 148
LCO 27,47,66, lO7, 162, 176 27Al MASNMR 55
lead 2,7,72, 148 MAT 88,93
Lewis acid fluorides 195 matrix 51
Lewis acid sites 74 maximum allowable tube
Lewis number 570 diameter 277
Li/MgO 318 maximum basicity 294
light-off 549,566 maximum conversion of calcium
light-off temperature 549 oxide 484
light olefin condensation reactor 216 maximum spoutable height 345
light olefins 38 mechanism of the photocatalytic
lime slurry in a spray dryer 499 process 579
limestone 380,389,395,508 mechanistic modelling of CFB 530
limestone attrition 402 MeOH synthesis 275
limestone retention time 40 I mesopores 52, 55
liquid additives 63 mesoporosity 51, 54
635
metal complexes 185,209 model of Kunii and Levenspiel 307

metal deposit 432 modeling 255, 553
metal dusting corrosion 263 modeling catalytic monoliths 547
metal oxide 289 modeling of the OCM fluidized-
metal oxides 185,196,209 bed 307
metallic monolith 553 modelling and kinetic equations in the
metallic monoliths 548 riser simulator 95
methane activation 209 models considering pore diffu-
methane reforming reaction 250 sion 473
methanol 4,8, 14,38,252 modification of basic catalytic
methanol fuels 150 solids 294
methanol/gasoline mixtures 150 MOG 171
methanol plant 271 MOGD (Mobil Olefin to Gasoline
methanol/synfuels 270 Plus Distillate) 154, 174
methanol synthesis 277,353 molecular models 410
methyl radical formation 300 molecular sieves 158
methyl radicals 286, 289 molten-salt reactor 196
methyl species 300 molybdenum 428
methyl tertiary butyl ether (MTBE) 7, MON 77
147 monolith boundary 553
micro-catalytic-fixed-bed reactor 300 monolith ignition 552
micro-selectivity test 89 monolithic catalytic converter 553
microactivity test reactor 87 Monte Carlo method 537
micromixing 368 Monte-Carlo simulation 537
microstructure of circulating fluidised Montedison 621
bed 517 Mo0 3-Crp/Si0 2 catalyst 186
mid-distillate 20, 27 Motor Octane Number 9
mild hydrocracking 438 moving bed processes 432
mineralization of the pollutants 609 moving bed reactors 87
minimization of maximum vor- MTBE (Methyl Tertiary Butyl
ticity 357 Ether) 12, 14, 15,38,52,62,66,
minimum fluidization 142 150, 169
minimum fluidization velocity 367 MTBEffAME 153
minimum particle size 235 MTG (Methanol-To-Gasoline) 283
mixing 359 MTO (Methanol-To-Olefins) 283
mixing cells-slug exchange muffler geometry 552
model 355 multi-ring polyaromatic com-
mixing patterns 133 ponents 327
mixing time 137 multi-tube furnaces 340
Mn-Mg oxide 196 multicylones 386
Mo 430 multiple beds 159
Mobil MTG 271 multiple circulation cells 364
Mobil MTG-process 275 multiple nozzle feed injection 72
model of Davidson and Hanison 307 multiple recirculation cells 358
636
multitubular fixed bed 233 reactors 443

nonframework alumina 52, 54
n-butane 40, 75 nonframework tetrahedral alumina
n-d-M method 83 (NFTA) 57
n-decane disappearance 412 nonporous draft tube 342
N-butane 14 normalized objective sensitivity 460
N-hexadecane ultrapyrolysis 333 normalized Thiele modulus 448
N z 549 novel riser simulator 133
NzO 187,395 NOx 2, 11, 19,21,42,47, 118, 151,
NaI scintillator detectors 538 244,253,391,404,507,532,549,
naphtha 40,147,264,327 570
naphtha cracking 409 nozzle pressure drop 34
naphtha pyrolysis 328 nozzles 34
naphtha reforming 409 nuclear plants 379
naphthalene 133 number of lumps 84
naphthenes 74 Nykoping Sweden 400
narrow-pore catalysts 237
natural gas 4, 228, 283 03IHzOZ 579
natural gas reserves 325 OCE reactor 217
natural gas to methanol via steam OCM 284
reforming 220 OCR (onstream catalyst replacement)
natural gas-to-methanol via steam process 434
reforming process 183 octacat 100, 109, 117
needle capacitance probe 518 octane 8,52,59, 147
NH3 431 octane additives 65
NH4N0 3 187 octane-enhancers 2
Ni 430 octane number 2, 76, 77
NiIHzS-chemisorption 262 octanes 162
nickel 43, 72, 78, 426, 428 OH radical desorption 589
nickel-molybdenum 429 oil refractoriness 82
nickel-tungsten 429 oil reserves 227
NiMo-Alz03 175 olefin 59
nitrogen 168 olefin 66
nitrogen oxides emissions 387,380 olefin polymerization 74
nitrogen removal 426 olefin production plants 325
nitrous oxide 187 olefins 40, 62, 73, 264
noble metals 64, 429 a-olefins 75
Nomex (nylon) 388 oligomerization 207
non-catalytic homogeneous gas-phase one dimensional turbulence inten-
reaction 286 sities 369
non-conventional reactor technol- optical fibre probes 537
ogy 341 optical probes 359
non-explosive behavior 458 overall thermal efficiency 252
nonadiabatic nonisothermal tubular Oxco process 277
637
oxidative coupling 195 particulate emissions 388

oxidative coupling of methane 133, PbO/yAIP3 catalyst 302
228,275,283 PCBs 590
oxidative coupling to ethylene 183 PCE 590
oxidative degradation techniques 601 pentacoordinated species 57
oxides of nitrogen 379 perchloroethylene (PCE) 582
oxidizable contaminants 579 percolation mechanism 386
oxidized intermediates 582 percolation of gas 342
oxidizing converter 569 perforated plates 354
oxidizing inorganic species 591 peroxycompounds 591
oxo-alcoho1s 252 petroleum 379
oxychlorination 192 petroleum coke 403
oxygen atoms 53 Phillips ' STAR process 173
oxygen bridges 53 photo-oxidation processes 579
oxygen content 11,38, 148 photocatalytic processes 577
oxygen plant 270 photocatalyzed degradations 582
oxygenate 2, 7 photoexcited electrons (e-) 579
oxygenates 1,13,61,147, 149 photogenerated charge carriers 613
ozone 38,148,149,579 photogeneration of holes 613
ozone decomposition 601 photomineralization process 581
ozone depletion 617 photooxidation 577
ozone depletion potential (ODP) 618 photoreactor design 596
ozone-forming constituents 149 pilot plant 77, 84
pilot plants units 90
paired sites 60 PIONA-analysis 410
palladium 547 plant solar system 599
paraffin ring closure 154 plasma jet pyrolyzers 329
paraffins 73 platinum 64,72,547
parametric sensitivity 456 platinum-rhodium 550
parametric sensitivity criteria 444 pneumatic conveying 28
parametric sensitivity of a CSTR 454 pneumatic transport 73
parametric sensitivity of catalytic pneumatic transport reactor 521
tubular reactors 448 poisoning 556
parametric sensitivity region boun- poisoning mechanism 556
daries 445 pollutant profiles 532
partial oxidation 273 pollutants 569
partial oxidation processes 251 pollutants emissions 379,384
particle agglomeration 233 pollutants released in the atmos-
particle cloud 360 phere 548
particle fluidization experiments 139 pollution abatement 381
particle mixing 381 polycyclic aromatic rings 76
particle-particle collision polyester urethane 10
mechanism 530 polymerization 353
particles transfer 537 polymethylene 240
638
pore diffusion resistence 468 race-track monoliths 552

pore models 475 radial density distribution 542
pore mouth closure 468 radial gas holdup profile 358
pore-mouth plugging 79 radical mechanisms 410
post riser cracking 32 radicals 409
power law function 111 ~-radicals 411
power recovery 21 ~-radicals 414
pressure drop 143 radioactive particle 360
pressure swing adsorption 270 radioactive stand 538
pressurized fluid bed combustors rare earth 51
(PCFBs) 404 rare earth exchange 54
pressurized fluidized bed boiler 382 rare earth exchanged zeolite 74
primary and secondary reforming 268 reaction network 409
primary photochemical act 580 reactivity of n-paraffins 243
probability of chain growth 232 reactor design 305
process of decrepitation 387 reactor performance 354
process scheme 309 reactors for FCC studies 87
processes 234 reactors for kinetic studies 325,328
production of ethylene 309 recirculating fluidised bed combus-
production of polyolefins 353 tion 507
Programs for Alternative Fluorocar- recycle fluidized batch reactor 133
bon Testing 622 recycle ratio on NOx 395
promoters 556 recycle reactors 92
propane ultrapyrolysis 333 redox potential 581
propylenes 19, 75, 159 reduced metal oxide 289
pseudo-adiabatic region 462 reduction in nitrous oxide emis-
pseudo-pure compound 328 sions 403
pseudo-steady-state approxima- reduction of the number of
tion 414 parameters 412
Pt on chlorinated alumina 159 refinery 19
Pt on mordenite 159 refinery configuration 155
pulse-microcatalytic reactor 89 refining 1, 5
pulse-mode units 329 refining industry 425
pyrolysis of heavy hydrocarbon reflection factor 530
mixtures 327 reformate 40
pyrolysis of hydrocarbons 325 reformer optimization 254
pyrolysis of mixtures 325 reformer outlet temperature 272
pyrolysis of recycled ethane 278 reformer pressure 272
pyrolysis of volatile matter 383 reformers 154,225
pyrolysis processes 326 reforming 4
pyrolytic reaction pathway 326 reforming of higher hydrocarbons 264
reforming process 154
quick contact 47 reformulated gasolines 38,53,147,
quick contact reaction system 341 153
639
refonnulation of gasoline 38 scission of a C-C-bond 419

refrigerants 619 scission of a carbon-carbon 427
regeneration 430 ~ scission 75,241,421
regenerator 21,24,28 scrubbing processes 380
regenerator pipe grid 35 seals 9
regenerator temperature 45 secondary cells 372
regenerators 45 selective hydrocracking 243
regions of multiplicity 456 selective oxidation of methane to
regulations 5 synthesis gas 267
REHY 76 selective production of hydrocarbons
Reid Vapor Pressure 2,8,11,147 of a specific carbon number
removal of S02 499 range 240
research octane 174 selectivity 52
Research Octane Number 9 self-condensation reaction 209
reserves of oil and gas 284 Semenov number 447
resid 43 Semenov problem 443
resid catalytic cracking 72 shale 185
resid cracking 42, 55 shale 210
residFCC 19 shape of catalyst particles 429
residence time distribution (RTD) 552 shedding of the liquid in the
residue hydrotreating 432, 440 wakes 359
REY 76,78,117 Shell gasification process 232
rhodium 547 Shell Middle Distillate Synthesis
riser 21,28,39,72,162,508,543 (SMDS) 227
riser catalytic crackers 537 shock-tube reactors 329
riser diameter 346 short circuiting 134
riser fluidizing velocity 346 SijAI ratio 59
riser simulator for catalyst testing 99 Si-O-Al-bonds 58
riser velocities 31 Si28 358
Riser Simulator 92 side-by-side FCC 22
rising gas bubbles 353 side-chain scission 74
road octane 150 signal frequency 141
RON 65,77 silica-alumina 429
RON 77 silica-alumina matrix 71
RTDs 537 silica-oxygen-alumina bonds 80
runaway 443 silicon hexafluoride 54
runaway phenomenon 449 simulated RTD curves 543
runaway region boundaries 444 single event rate coefficients 420
RVP 38,150 single liquid recirculation 353
single pellet dynamic technique 467
s-triazine herbicides 586 single pellet moment method 491
saturation of fatty acids 353 single step hydrocracking 437
scale-down 354 sintering 468
scale-up 354 site isolation 54, 60
640
sites 54 stable operation 354

six-lump model 84 staged combustion 391,399
size of catalyst particles 429 standpipes 28, 52
slide valves 21 steady state multiplicity 566
slip velocities in a CFB 519 steam reformer 220
slip velocity 73,381 steam reforming 249
slotted pipes 34 steam reforming catalyst 258, 260
slug-cell exchange coefficient 355 steam reforming of methane 231
slug flow 357 Stratospheric Ozone 622
slurry phase operation 437 strippers 24, 28, 33, 46
slurry process 239 structural parameters 486
slurry reactors 235,353 structure 51
Smp3 318 Studsvik Energy 515
SMDS process 227 sulfate ions 467
smooth exit 516 sulfided Co-Mo-AIP3 175
SOi 389,401,467,508 sulfonated acidic resin catalysts 169
S02-activated soda reaction 468 sulfur 40, 150, 168
S02-limestone reaction sulfur capture 401
mechanism 468 sulfur capturing capabilities 392
S02 remoal efficiency 499 sulfur content 147
S02 scrubbing 500 sulfur dioxide 379,467
S03 508 sulfur dioxide-activated soda reac-
sodium 51,53,292 tion 489
sodium dispersed on CaO 292 sulfur dioxide emissions 380
solar energy 252 sulfur dioxide-limestone reaction
solar photochemical reactors 591 kinetics 468
Solarbox simulator 594 sulfur dioxide scrubbing 499
solid catalytic additives 63 sulfur emissions 386
solid flow pattern visualization 537 sulfur retention 401
solids circulation rate 343 sulfuric acid 467
solids velocity profiles in circulating sulfuric acid alkylation 167
fluidised beds 523 sulphor passivated reforming 266
solubility limit 294 sulphur 325
sorbent injection 389 sulphur oxides 507
SOx 19,21,42,47,63,65,118,244 sulphur poisoning 262
SPARG-process 265, 272 super-acid catalyst 195
spectrophotometry 359 super-acids 184
spectroscopic techniques 178 superficial velocity 33
spout-fluid bed with draft tube 345 supported lead oxide 290
spout gas bypassing 345 surface area 80
spout nozzle velocity 343 surface basicity 291
spouted bed with draft tube 342 surface lattice oxygen 295
spray drier absorption 499 surface Na content 292
spray drier scrubbers 499, 500 suspension density 512
641
swelling 9 three-phase fluidized 233

swing reactor 432 three phase fluidized bed 354
swirl-tube separator 72 three-way converters 550, 570
synfuels 228 time averaging 356
syngas chemistry 227 Ti02 577, 609
syngas manufacturing 229 Ti02 particles with Pt 609
synthol 234 TiO/Pt 609
systematic reduction of the number of toluene 582
species 413 toluene/xylene 40
topping/reforming 18
t-plot 55 Topsoe Monotube Steam Reformer
tailpipe 11 Pilot 259
TAME 14,40,62,162,169 Topsoe process 267
Tammann temperature 258 Topsoe R-67-7HR 260
TDH 511 Topsoe reformer furnace 254
Teflon coated fiberglass 388 Topsoe TIGAS process 271,275
temperatur rise time 333 tortuosity 238
temperature-conversion phase total aromatic 147
plane 444 total organic carbon (TOC) 582
temperature profiles 443 total reaction time 339
Temperature Rise Time 337 Total Ozone Mapping
ten-lump model 83 Spectrometer 618
terrace wall fired reformers 261 toxic chemicals 609
tertiary amyl methyl ether (TAME) 7 trace emissions 388
tertiary butyl alcohol 7 tracer simulations 542
tetrahedral coordination 56 tracer studies 358
tetrahedral silicon 53 transient response techniques l34
thermal boundary layers 525, 529 transportation fuels 147,227
thermal coal conversion 383 trichloroethylene (TeE) 582
thermal cracking 77,165,409 2,4,5-trichlorophenoxy-acetic
thermal efficiency 184,212,382,404 acid 585
thermal efficiency of the bed 381 2,2,4 trimethylpentane 9
thermal energy losses 214 trickle-bed reactor 431
thermal explosion 443 trickle flow hydrocracking
thermal runaway 443 process 244
thermal sensitivity 443 trona (natural soda) 500
thermal steam cracking 328 tube lifetime 254
thermalpyrolysis 185 tubular fixed bed reactors 87
thermodynamic-equilibrium yields of tubular reformer 249,251
ethane and ethylene 285 tungsten oxides on alumina 428
thermolytic pyrolysis processes 326 turbulence models 358
thermovortactor 341 turbulence parameters 367
Thiele modulus 238,477,563 turbulent eddies 359
three lump model 81, 109 turndown 508
642
two direct conversion processes 211 vis breaking 409

two step reforming 271 VOC 149
voidage profile 514
U.S. gasoline pool 147 volatile combustion 384
ultrapyrolysis of heavy oils 325 volatile organic compounds 149
ultrapyrolysis of steam atomized volatility 1, 2
Alberta heavy oil 344
ultrapyrolysis reaction kinetic W 430
studies 333 wall-layer disturbance factor 530
ultrasonic Doppler technique 358 wall-to-core flux coefficient 530
under co-feed mode 317 wash-coat 564
unit cell 53, 60 waste waters 244,609,577
unit cell size 55, 80, 104 water 9
University of Calgary microreactor water gas shift reaction 250
system 330 wet gas compressor limit 165
unleaded 7 wet processes 467
unreacted core model 469 whisker carbon 265
UOP high efficiency 22 whisker mechanism 264
UOP's OLEFLEX 172 wide pore 237
upward flux 542 x-ray absorption fine structure 176
USY 41,51,56,78 XRD 55
USY/ZSM-5 41 xylenes 582
V 430 Y-type 78
VPs 503 Y zeolites 17,429
vacuum gas oils (VGO) 17, 19,327
vanadium 43, 72, 78, 426, 428 zeolite lattice 55
vapor pressure 61 zeolite particle size 55
variable inventory system 512 zeolite surface area 54
VEBA combi-cracking process- zeolites 17, 71
ing 436 ZMS-5 159
VGO 42,45 ZnO 591
vinyl acetate synthesis reaction 452 ZSM-5 40,52,59, 79, 163, 174,429

Chemical Reactor Technology For Environmentally Safe Reactors and Products

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Chemical Reactor Technology For Environmentally Safe Reactors and Products

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Chemical Reactor Technology

for Environmentally Safe Reactors and Products

The Series is published by an international board of publishers in conjunction with the

A Life Sciences Plenum Publishing Corporation

C Mathematical Kluwer Academic Publishers

F Computer and Systems Sciences Springer-Verlag

Series E: Applied Sciences - Vol. 225

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

Printed on acid-free paper

All Rights Reserved

I. Fuels of the Future and Changing Fuel Needs

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

A. Pekediz, D. W. Kraemer, J. Chabot, H.!. de Lasa

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

II. Alternative Sources

M.M. G. Senden, S. T. Sie, M.F.M. Post, J. Ansorge

J. Rostrup-Nielsen, I. Dybkjaer, L.J. Christiansen

O. Altin, I. anal, T. Dogu, J.B. Butt

F. Berruti, L.A. Behie

M.P. Dudukovic, N. Devanathan

III. Emission Control, Chemical Reactor Safety and Engineering

G. Dogu, G. Olmez, T. Dogu

C. Brereton, J.R. Grace, C.J. Lim, J. Zhu

J.P. Leclerc, D. Schweich

J.J. Lerou, L.E. Manzer

With this general background, a NATO-Advanced Study Institute on Chemical Reactor

I would like to express here my gratitude to the co-directors of the NATO-ASI,

London, Ontario, Canada

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

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

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

O. Marroquin, Instituto Mexicano del Petroleo, Direccion Investigacion Aplicada, Processes.

Organizing Advisory Committee

ABSTRACT. This contribution, presented as an introduction to a Panel Discussion of the NATO-Asi

2. Product Quality and its impact on emissions

Table 1. Reactivity and Vapor Pressure of Gasoline Blending

COMPOUND Atmospheric Reactivity (2) Blending RVP (3)

(l)Gas-phase reaction rate with the hydroxyl radical (Unzelman, 1990)

Table 2. Octane Rating of Aromatics and Oxygenates.

Compound RON MON (RON + MONl/2

4. Need for Processing changes

G.L. HARTING, HUGH SHANNON

2. Oxygenates for Fuel Blending

Volume "10 Oxygenate In Indolene

Data Source: (API, 1988).

Figure 1. Effect of Oxygenates on Blend Vapor Pressure

Gasoline (premium Unleaded) 91-94

Water tolerance is another important parameter to be measured for gasoline/oxygenate blends.

2.75 Volume % Methanol

Data Source: (API, 1988).

Figure 2. Water Tolerance of Gasoline-Alcohol Blends

Table 3. Elastomer Swelling Due to Oxygenates.

Elastomer Gasoline Methanol(l) Ethanol(l) MTBE(I)

3. Emission Impact Of Oxygenates

Figure 3. Effect Of Air/Fuel Ratio On Emissions.

Table 4. MTBE Effect On Tailpipe Emissions.

Emissions Effect. %(1)

Current Fleet -5.1 -11.2 Not Significant

Oxygen COOlent, "

Data Source: (Most,W.J., 1989).

Figure 4. CO Emissions vs. Fuel Oxygen.

Figure 5. Ethanol Production Process - Simplified Diagram

N-Butane Iso-Butane Iso-Butylene

.-_Bu_'_an_e_s_an_d_L..."IQ,-h_,e_r_ _ _ _ _ _ _ _ _ _ _ _ _ _~:c~ Gas

Cooled 1:1-+J1k'rioS-- ~:~;~~~~dPiPe