MODELING AND SIMULATION

OF CATALYTIC REACTORS FOR

PETROLEUM REFINING

MODELING AND SIMULATION

OF CATALYTIC REACTORS FOR
PETROLEUM REFINING

JORGE ANCHEYTA

A JOHN WILEY & SONS, INC., PUBLICATION

Copyright 2011 by John Wiley & Sons, Inc. All rights reserved
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Library of Congress Cataloging-in-Publication Data:
Ancheyta, Jorge.
Modeling and simulation of catalytic reactors for petroleum refining / Jorge Ancheyta.
p. cm.
Includes bibliographical references and index.
ISBN 978-0-470-18530-8 (cloth)
1. Catalytic reformingSimulation methods. I. Title.
TP690.45.A534 2011
665.53dc22
2010030993
Printed in the United States of America
oBook ISBN: 9780470933565
ePDF ISBN: 9780470933558
ePub ISBN: 9781118002162
10

CONTENTS

PREFACE

ix

ABOUT THE AUTHOR

xii

PETROLEUM REFINING
1.1
1.2
1.3

1.4

1.5

Properties of Petroleum, 1
Assay of Crude Oils, 4
Separation Processes, 10
1.3.1 Crude Oil Pretreatment: Desalting, 10
1.3.2 Atmospheric Distillation, 12
1.3.3 Vacuum Distillation, 13
1.3.4 Solvent Extraction and Dewaxing, 13
1.3.5 Deasphalting, 14
1.3.6 Other Separation Processes, 15
Upgrading of Distillates, 17
1.4.1 Catalytic Reforming, 18
1.4.2 Isomerization, 18
1.4.3 Alkylation, 21
1.4.4 Polymerization, 23
1.4.5 Catalytic Hydrotreating, 25
1.4.6 Fluid Catalytic Cracking, 27
Upgrading of Heavy Feeds, 29
1.5.1 Properties of Heavy Oils, 29
1.5.2 Process Options for Upgrading Heavy Feeds, 31

REACTOR MODELING IN THE PETROLEUM

REFINING INDUSTRY
2.1

53

Description of Reactors, 53
2.1.1 Fixed-Bed Reactors, 56
2.1.2 Slurry-Bed Reactors, 62
v

vi

CONTENTS

2.2

2.3

2.4

MODELING OF CATALYTIC HYDROTREATING

3.1

3.2

3.3

Deviation from an Ideal Flow Pattern, 63

2.2.1 Ideal Flow Reactors, 63
2.2.2 Intrareactor Temperature Gradients, 66
2.2.3 Intrareactor Mass Gradients, 69
2.2.4 Wetting Effects, 77
2.2.5 Wall Effects, 81
Kinetic Modeling Approaches, 86
2.3.1 Traditional Lumping, 86
2.3.2 Models Based on Continuous Mixtures, 99
2.3.3 Structure-Oriented Lumping and Single-Event
Models, 101
Reactor Modeling, 102
2.4.1 Classification and Selection of Reactor Models, 102
2.4.2 Description of Reactor Models, 106
2.4.3 Generalized Reactor Model, 155
2.4.4 Estimation of Model Parameters, 176
References, 188
Nomenclature, 203

The Hydrotreating Process, 211

3.1.1 Characteristics of HDT Reactors, 213
3.1.2 Process Variables, 220
3.1.3 Other Process Aspects, 229
Fundamentals of Hydrotreating, 241
3.2.1 Chemistry, 241
3.2.2 Thermodynamics, 243
3.2.3 Kinetics, 246
3.2.4 Catalysts, 258
Reactor Modeling, 261
3.3.1 Effect of Catalyst Particle Shape, 261
3.3.2 Steady-State Simulation, 269
3.3.3 Simulation of a Commercial HDT Reactor with
Quenching, 273
3.3.4 Dynamic Simulation, 283
3.3.5 Simulation of Countercurrent Operation, 293
References, 304
Nomenclature, 308

MODELING OF CATALYTIC REFORMING

4.1

211

The Catalytic Reforming Process, 313

4.1.1 Description, 313
4.1.2 Types of Catalytic Reforming Processes, 316
4.1.3 Process Variables, 318

313

vii

CONTENTS

4.2

4.3

Fundamentals of Catalytic Reforming, 319

4.2.1 Chemistry, 319
4.2.2 Thermodynamics, 321
4.2.3 Kinetics, 322
4.2.4 Catalysts, 330
Reactor Modeling, 331
4.3.1 Development of the Kinetic Model, 331
4.3.2 Validation of the Kinetic Model with Bench-Scale Reactor
Experiments, 345
4.3.3 Simulation of Commercial Semiregenerative Reforming
Reactors, 350
4.3.4 Simulation of the Effect of Benzene Precursors in the
Feed, 357
4.3.5 Use of the Model to Predict Other Process Parameters, 361
References, 364
Nomenclature, 366

MODELING AND SIMULATION OF FLUIDIZED-BED

CATALYTIC CRACKING CONVERTERS

368

Rafael Maya-Yescas

5.1

5.2

5.3

5.4
5.5
5.6
5.7

5.8

Introduction, 370
5.1.1 Description of the Process, 370
5.1.2 Place of the FCC Unit Inside the Refinery, 371
5.1.3 Fractionation of Products and Gas Recovery, 373
5.1.4 Common Yields and Product Quality, 373
Reaction Mechanism of Catalytic Cracking, 374
5.2.1 Transport Phenomena, Thermodynamic Aspects, and
Reaction Patterns, 374
5.2.2 Lumping of Feedstock and Products, 376
5.2.3 More Detailed Mechanisms, 378
Simulation to Estimate Kinetic Parameters, 378
5.3.1 Data from Laboratory Reactors, 379
5.3.2 Data from Industrial Operation, 384
Simulation to Find Controlling Reaction Steps During Catalytic
Cracking, 385
Simulation of Steady Operation of the Riser Reactor, 387
Simulation to Scale Up Kinetic Factors, 390
Simulation of the Regenerator Reactor, 393
5.7.1 Simulation of the Burning of Nonheterogeneous
Coke, 393
5.7.2 Simulation of Side Reactions During the Burning of
Heterogeneous Coke, 402
5.7.3 Simulation of the Energy Balance in the Regenerator, 409
Modeling the Catalyst Stripper, 410

viii

CONTENTS

5.9

Simulation of a Controlled FCC Unit, 411

5.9.1 Mathematical Background, 412
5.9.2 Controllability of the Regenerator, 415
5.9.3 A Technique to Regulate Tregenerator in Partial Combustion
Mode, 423
5.10 Technological Improvements and Modifications, 438
5.10.1 Effect of Feedstock Pretreatment, 438
5.10.2 Pilot-Plant Emulation, 453
5.10.3 The Sulfur Balance, 459
5.11 Conclusions, 466
References, 468
Nomenclature, 472
INDEX

475

PREFACE

The reactor is the heart of a chemical process, and a thorough understanding

of the phenomena occurring during the transformation of reactants into the
desired products is of vital importance for the development and optimization
of the process. Particularly in the petroleum refining industry, in which apart
from the reactors, other operations (separations, heating, cooling, pumping,
etc.) are carried out in series or in parallel and each plant is connected with
others, improper design and operation of reactors can cause shutdown of a
plant or, even worse, of the entire refinery, with the consequent loss in production and income. It is thus essential to have a thorough knowledge of the
fundamental equations critical to chemical reactor design, such as reactor
sizing and optimal operating conditions.
The reactors used during petroleum refining are among the most complex
and difficult to model and design. The composition and properties of the
various petroleum fractions that are converted in reactors is such that the
reaction system can involve various phases, catalysts, reactor configuration,
continuous catalyst addition, and so on, making the development of a model
a challenging task. In addition, the presence of hundreds of components undergoing different reaction pathways and competing for the active sites of catalysts, contributes to increasing the complexity of the formulation of the kinetics
and reactor models.
Over the years, many excellent textbooks have been published dealing with
various aspects of reactors: chemical reactor design, modeling of chemical
reaction kinetics, reaction mechanisms, chemical reaction engineering, scaleup, and so on. The level of sophistication in each book varies from academic
reactions (e.g., A B), represented by simple kinetic models (e.g., the powerlaw model, rA = kC An ) and using integrated equations for the design of ideal
reactors (e.g., PFR, CSTR), to complex catalytic reaction systems employing
a set of differential equations to solve for mass and energy balances. However,
ix

PREFACE

detailed descriptions of the various reactor models, reaction kinetics, and real
examples of the application of these models for the simulation of experimental
reaction units and commercial plants have not previously been treated in
detail. Moreover, most books do not discuss the modeling of the reactors that
are typically used during the conversion of oil distillates in the petroleum
refining industry, and do not describe reactor models in an uncluttered or
thorough manner.
Modeling and Simulation of Catalytic Reactors for Petroleum Refining is
designed to give an up-to-date treatment of all the important aspects of reactor
modeling, with particular emphasis on reactors employed in the petroleum
refining industry. We explain and analyze approaches to modeling catalytic
reactors for steady-state and dynamic simulations and discuss such aspects as
thermodynamics, reaction kinetics, process variables, process schemes, and
reactor design. To validate the models developed, experimental data obtained
directly from laboratory and commercial plants are used. Our goal is that the
book will become an essential reference for chemical and process engineers,
computational chemists and modelers, catalysis researchers, and professionals
in the petroleum industry, as well for use as a textbook either for full courses
in chemical reaction engineering or as a supplement to related courses.
The book is organized in five chapters, each with individual reference and
nomenclature sections. About 500 references are cited and discussed, covering
most of the published literature regarding the modeling of reactors used in
the petroleum refinery industry. Chapter 1 provides an in-depth introduction
to topics related to petroleum refining, such as petroleum properties, separation processes, upgrading of distillates, and upgrading of heavy feeds. A brief
description of all the conversion and separation processes is given in this
chapter. Detailed experimental data on light, medium, and heavy crude oil
assays are also provided.
General aspects of reactor modeling in the petroleum refining industry are
treated in Chapter 2. The emphasis is on reactors, deviations from ideal flow
patterns, kinetic modeling approaches, estimation of model parameters, and
classification and description of reactor models. The fundamental equations
are given for each reactor model, together with their advantages and disadvantages. A generalized reactor model is proposed from which each previously
reported reactor model can easily be derived.
Chapter 3 is devoted to the modeling of catalytic hydrotreating reactors.
The most important features of this type of reactor are highlighted in the first
sections, such as the characteristics and classification of hydrotreating reactors,
process variables, other process aspects (quench systems, reactor internals),
and fundamentals of hydrotreating (chemistry, thermodynamics, kinetics, and
catalysts). The final section covers hydrotreating reactor modeling, with examples of the modeling and simulation of reactors operating with catalysts of
different particle shapes, steady-state operation, hydrotreating reactors with
quenching, dynamic simulation, and co-current and countercurrent operations
for both laboratory and commercial reactors.

PREFACE

xi

The modeling of catalytic reforming reactors is the subject of Chapter 4.

The description and types of processes, process variables, and fundamentals of
catalytic reforming are described at the beginning of the chapter, followed by
a section on reactor modeling in which the development of a kinetic reforming
model is reported. Validation of the model developed, with bench-scale isothermal reactor experiments and simulation of commercial semiregenerative
reforming reactors, is discussed. The effect of benzene precursors in the feed
in both laboratory and commercial reactors is also simulated, and use of the
reactor model to predict other process parameters is highlighted.
In Chapter 5, Dr. Maya-Yescas describes the modeling and simulation of
the fluid catalytic cracking reactor. Descriptions of the process, reaction mechanism, transport phenomena, thermodynamics, and kinetics are provided in
the initial sections. Simulations used to estimate kinetic parameters from laboratory and commercial reactors, to determine the controlling reaction steps, of
steady-state operation, of scale-up kinetic factors, of the regenerator reactor,
of burning nonheterogeneous coke, of side reactions during the burning of
heterogeneous coke, and of the energy balance in the regenerator are discussed in detail. Other sections deal with modeling a catalyst stripper, simulation of the controlled unit, pilot-plant emulation, and industrial plant
emulation.
Detailed experimental data and comparisons with reactor model predictions are provided in each chapter. Also, all data and parameters required to
build up each reactor and kinetic model are detailed, so that readers can adapt
their own computer programs for use in reactor simulation, optimization, and
design purposes.
It is our intention that Modeling and Simulation of Catalytic Reactors for
Petroleum Refining will quickly become a leading book in this field through
its emphasis on detailed descriptions of catalytic reactor modeling used in the
petroleum refining industry, its use of laboratory and commercial data for
model validations, the details provided of results of simulations in steady-state
and dynamic operations, and in general its focus on more practical issues
regarding reactor modeling than have been available in previous textbooks on
chemical reactor engineering.

ACKNOWLEDGMENTS
I would like especially to acknowledge Dr. Rafael Maya-Yescas, Professor of
Chemical Reaction Engineering. Universidad Michoacana de Nicols de
Hidalgo, Morelia, Michoacn, Mxico, who kindly agreed to write Chapter 5.
I also thank all the M.Sc., Ph.D., and postdoctoral students who over a period
of many years have contributed enormously to the preparation of this book.
JORGE ANCHEYTA

ABOUT THE AUTHOR

Jorge Ancheyta, holds a bachelors degree in petrochemical engineering

(1989), a masters degree in chemical engineering (1993), and a masters degree
in administration, planning, and economics of hydrocarbons (1997) from the
National Polytechnic Institute of Mexico. He split his Ph.D. between the
Metropolitan Autonomous University of Mexico and the Imperial College
London (1998), and was awarded a postdoctoral fellowship in the Laboratory
of Catalytic Process Engineering of the CPE-CNRS in Lyon, France (1999).
He has also been a visiting professor at the Laboratoire de Catalyse et
Spectrochimie, Universit de Caen, France (2008, 2009, 2010), and Imperial
College London (2009).
Dr. Ancheyta has worked for the Mexican Institute of Petroleum (IMP) since
1989, where his present position is project leader of research and development.
He has also worked as a professor on the undergraduate and postgraduate
levels at the School of Chemical Engineering and Extractive Industries at the
National Polytechnic Institute of Mexico since 1992 and for the IMP postgraduate program since 2003. He has supervised about 100 B.Sc., M.Sc., and Ph.D.
theses as well as a number of postdoctoral and sabbatical-year professors.
Dr. Ancheyta has worked on the development and application of petroleum
refining catalysts, kinetic and reactor models, and process technologies, primarily in catalytic cracking, catalytic reforming, middle distillate hydrotreating,
and heavy oils upgrading. He is the author or co-author of a number of patents,
books, and about 200 scientific papers, and has been awarded the highest distinction (level III) as a national researcher by the Mexican government and
is a member of the Mexican Academy of Science. He has also been guest editor
of various international journals: Catalysis Today, Petroleum Science and
Technology, Industrial Engineering Chemistry Research, Energy and Fuels,
Chemical Engineering Communications, and Fuel. Dr. Ancheyta has also
chaired numerous international conferences and is a member of the scientific
boards of various prestigious journals.
xii