Catalytic Reactor Design-Orhan Tarhan

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l\IlcGraw-HilL Book Company

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NOTICE
The information presented in this book has been
compiled from sources considered to be dependable and
is accurate and reliable to the best of the author's
knowledge and belief, but is not o,-uaranteed to be so.
The author assumes no responsibility whatsoever with
respect to any use which may be made of any of :he
data or methods cesc-ibed in this book or any results·
obtained by such t.se. Nothing in this b"ok is lO be
construed as a recommendation of any practice in
violation of any patent. ;aw, or regulation.
Library of Congress Cataloging i1l Publicat;"" Data

Tarhan, M. Orhan.
Catalyti~ reactor design.
Includes bibliographies and index .

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I. Chemical reactors Design and construction.
2. Catalysis. 1. Title.
TP157.T35 1983 660.2'995 82-18015
ISBN 0-07-062871-8
Copyright © 1983 by McGraw-HiII, lnc. All rights resen·ed

Printed in the United States of America. Except as pelIuitted
under the United States Copyright Act of 1976, no pan of this
pUblication may be reproduced or distributed in any form or by
any means, or stored in a data base or retrieval system. wiThout
the prior written permission of the publisher.
1234567890 KGP/KGP 898765-13
ISB l\ 0-07-062871-8
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The edItors for this book were Diane Heiberg and Ceraldine
Fahey, the designer was flliot 'Epstein. and the production
supervisor was Sally Fliess. It was set in Baskerville by Techna
Type.
Printed and bound by The Kingsport Press.
•
CONTENTS
• ••
Preface XIII
CLASSIFICATIC)N OF REACTORS
Chapter AND PHASES (lIF DESIGN . I
1.1 Classification of Reactors I
1.2 Design Definitions 4
1.3 General Methods of Reactor Design 4
1.4 Phases of Reactor Design -
;:,
t>.fodeling of Reactors • 6
"
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•• Collection of Data 7
Use of a Computer 8
Mechanical Design 9
1.5 Operating Considel ations 9
1.6 Who Needs Reactor Design? 10
References 10
OF
Chapler NUMERICAL C()MPUTATION 13
2.1 Types of Differential Equations 13
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Ordinan' Di fferential Equations 13

Partial Diff~rential Equations 14
2.2 Principles of Algorithms 15
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Euler's Algorithm 16
Runge-Kutw Algorithms 20
2.3 nth-Ord·er Ordinary Differential E<J.uations 22
•
vi CQNIENTS
2.4 Simultaneous Ordinary Differential Equations

,
23
2.5 Program for Solving Initial-Value ODEs 24
2.6 Program for Solving Boundary-Value ODEs 28
The Shooting Method 29
The Finite Difference Method 29
The Combined Finite Difference and
Quasilinearization Method 29
Case 1: C, = C;1: = T 31
Case 2: C, # C; T, # T 35
Case 3: C, = C; T, = T; Reaction Is Second Order 37
2.7 Algorithms for Solving Partial Differential
Equations 37
2.8 Handling of Several Parallel Reactions 41
Nomenclature 44
References 46
,
CATALYTIC
Chapter 47
,
3.1 Catalysis 47
Definition of a Catalyst
, 47
Classification of Catal ysts 48
Properties of Hetel'ogeneous Catalysts 49
3.2 Catalytic Reaction Rate Models 55
-,
, Reaction Order 56
-~
Normal and Autocatalvtic , Reactions :>/
3.3 Determination of Reaction Rate :;8
The Differential Flow Reactor 58
The Integral Flow Reactor Integral Analysis 61
The Continuous Stirred Tank Reactor (CSTR) 62
The Recycle Reactor ' 63
3.4 Effects of Pore Structure and Transport Phenomena
on Reaction Kinetics ' 64
The Global Rate of Reaction 64
Yield and Selectivity in Complex Reaction Systems 70
Nomenclature 72
References 74
"
TRANSPORT IN
Chapter 4 GAS REACTORS 77
4.1 Definition 77
4.2 Classification of Fixed-Bed Gas Reactors 78
•
CONTENTS vii
4.3 Interpha~~ Transport in Fixed-Bed Gas Reactors 79

Interphase Flow 'of Gas 79
Pressure Drop across Fixed-Bed Gas Reactor;; 79 .
Radial Dislributitm of Axial Flow Untt' 80
Interphase Mass Transport Phenomena 81
Radial Dispersion of Mass 82
Axial Disj'ersion of M ass 82
J ,. terphas." M ass Tra IIsfer 83
Imerphas.! Heat Transport 85
Radial DI;spersion of Heat 85
Interphasl~ Heat Transfer 86
Radiant lIeal Tramfer 87
Heat Transfer betWi'm Reactor ""(Ill" and Packed fleds 89
4.4 Intraphas,e Transport in Fixed-Bed Gas Reactors 89
lntraphas,e Mass Transfer 89
Imrap'las,~ Heat Transfer 91
intraphas,t Temperature Gradients 91
Interphase Temperature Gradimts 92
ThRnuu BiOi Number., 92
llltraphas.e and Interphrue Heat Trallsfer 93
• N omencl~Lture 94
Referenc(:s 97
PROCESS DESIGN OF
Chapter REACTORS 99
5.1 Isothelllllll Reactors 99
.
• General Design Procedure 99
Example: Design of an Isothermal Reactor 102
5.2 Adiabatic Gas Reactors 106
Definition 106
One-Dimensional Plug-Flow Model 107
Development of Design Equations for Adiabatic Gas
Reactors 107
The Problem of Designing Fixed-Bed Reactors for
Exothermic Reactions 109
Example of Adiabatic Fixed-Bed Gas Reactor
Design: I>esign of a Toluene Hydrodealb;lation
Reactor III
5.3 Nonisotlt,eI'Dlal, Nonadiabatic Fixed-Bed (NINAF)
Gas Reactors ., 129
Existing ~,fodels of the NINAF Gas Reactor 130
Development 01- Design Equations for a NINAF Gas
Reactor for a First-Order Reaction 131
Example of NINAF Reactor Design: Air Oxidation
of Naphthalene to Phthalic Anhydride 136
•
. viii CON I ENTS
Nomenclature 151
References 152
GAS-LlQUID-PHASE REACTORS-
CLASSIFICATION AND TRANSPORT
Chapter OF REACTORS 155
6.1 Definition Classification of Gas-Liquid-Phase
Reactors 155
6.2 Transport Phenomena in Trickle-Bed Reactors 158
Press.lre Drop across Concurrent Trickle-Bed
Reactors 162
Axial Dispersion and Holdup in Trickle-Bed
Reactors 165
Radial Dispersion in Trickle-Bed Reactors 171
Heat Transfer in Trickle-Bed Reactors 172
Mass Transfer in Trickle-Bed Reactors 176
Nomenclature 181
References 184
PROCESS DESIGN OF
Chapter 7 TRICKLE-BED REACTORS 189
7.1 General Procedure 189
Plug-Flow-Trickle-Bed Reactor 192
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Trickle-oed Reactor with Axial Dispersion 197
7.2 Design Examples for Petroleum
H ydrodesulfurization 200
Plug-Flow Industrial Reactor 201
The Computer PTrJl!'am RD.\lOT4 209
Laboratory Reactor with Backmixing 217
The Computer Program RDMOT3 220
7.3 Varieties of Trickle-Bed Reactors 231
Nomenclature 236
References 238
FIXED-BED
Chapter REACTORS 241
8.1 Transport Phenomena in FBBRs 242
Pressure Drop a{TI)S\ FBBRs 242
Gas Dispersion in FBBRs 243
Axial and Radial Dispersion in FBBRs 243
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CONIENTS Ix
Heat Transfer in FBBRs 243

Mass Transrer in FBBRs 244
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8.2 Process Deliign of FBBRs 245
8.3 Gas-Liquid"Phase Fixed-Bed Reactors Which
Operate in the Pulsing or Spray Regimes 245
Transport Phenomena 245
Choice of Fast Reactors and Process Design 247
Nomenclature 247
References 248
SUSPENDED-BED
Chapler
9.1 Definitions Classification
Continuous Stirrel:-T;lI1k Reactors (CSTR)
Slurry Reactors 253
Ebullated-B(>d Reactors 255
Three-Phase Transport Reactor (3<l>TR) 257
• 9.2 Transport Phenomena in Gas-Liquid-Phase
Suspended-Bed Reactors
Pressure Drop across Susnended-Bed Reactors 259
The Dispersion of Gas .3ubbles and Liquid in
Suspended Beds 260
Suspending the Cata!,'st in Suspended Beds 275
Mass Transfer in Suspended-Bed Reactors 276
Heat Transfer in Suspended-Bed Reactors 283
9.3 Advantages and Drawbacks of Suspended-Bed
Reactors 285
9.4 Process Design of Suspended-Bed Reactors 286
Process Design of CSTRs 286
General Procedure 286
Example of CST!? De,litr" 290
Scale-up of Ga.,-Liquid CSTR 293
CSTRs in Series 294
Process Design of Slurry Reactors 295
General Procedure 295
Example of Slurry Reactor Design 296
Other Examples 299
Process Design of Ebullated-Bed Reactors 299
Process Desi'gn of Three-Phase Transport Reactors
(3<l>TR) 301
Nomenclature 304
References 309
•
x CONTENTS
DESIGN OF LABORATORY AND

Chapter 10 PILOT REACTORS 315
10.1 Definitions and Generalities 315
10.2 I ahoratory Reactors 317
General-Purpose Laboratory Reactors 317
The Shaking Autoclave 317
• The Swagelok Reactor 320
Special-Purpose Laboratory Reactors 3?'3
Differential-Flow Reactor 323
Integral-Flow Reactor 323
The Continuous Stirred- Tank Reactor (CSTR) 323
The Re0c1e
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Reactur 324
10.3 Pilot Reactors 325
References 327
REACTOR SAl Ell'

Chapter 11 AND STABILITY 329
11.1 Various Causes of Reactor Mishaps 329
Defects in Mechanical Fabrication 329
Excessive Thermal Excursion during Cataiyst
Regeneration 330
Catalyst Failure during Regeneration 330
Dangerous Reactions 331
Process Control Problems 331
11.2 Parametric Sensitivity 332
\ • 11.3 Reactor Stability 334
Definition and Description of Multiple Steady States 334
Varieties of Steady-State Multiplicity 336
11.4 Discussion and Conclusion 338
References 340
DESIGN
Ch.apter OF COMMERCIAL REACTORS 343
12.1 Designing for Pressure 343
Design Codes 344
The Strength of the Reactor Wall 344
Design' of Thin-Walled R.::actors 348
Design of Thick-Walled Reactors 350
12.2 Various Methods of Reactor Consb uction 353
Low-Severitv Reactors
~
354
High-Severity Reactors 354
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CONTENTS XI
Meeting of Corrosion Resistance Requirements 356

Nomenclature 357
References 358
ITERATION
Appendix A 361
Index 363
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The purpose of this book is to teach the design of catalytic reactors. The
book evolved from notes of summer short courses given between 1969
and 1973 at Lehigh University, Bethlehem. Pennsylvania, in Pocono
Manor, Pennsylvania, and in Istanbul, Turkey. The material has been
subsequently considerably expanded, updated, and of course, com-
pletely reorganized.
Although the title, Catalytic Reactor Design, covers all kinds of catalytic
reactors, the book is limited to heterogeneous catalytic reactors, since
their design presents the greatest challenge today. A particular kind of
,. ,
•
heterogeneous catalytic reactor, the fluidized-bed reactor, has been omit-
-
ted, because an excellent and detailed book by Kunii and Levenspiel
(Fluidization Engineering, John Wiley, 1\ew York, 1969) exists on these
reactors.
Today the reactor designer must be an extremely sophisticated chem-
ical engineer, who is well versed in catalysis, reaction kinetics, transport
phenomena, mechanical engineering, and computer programming. It
would obviously be undesirable to attempt to present adequate infor-
mation in all these fields in a book of this size. Instead, this book con-
centrates on the process engineering aspect of reactor design, including
computer solutions of design problems, in great detail and presents only
a limited amount Gf ~nformatio!1 on catalysis. reaction kinetics, mechan-
ical engineering, and general principles related to computer program-
ming. This limitation is' partially compensated by ample references to
important and informati"e studies.
Separate chapters are devoted to the design of laboratory and pilot
reactors and to the mechanical design of full-scale plant reactors. The
vitally important question of reactor stability and safety is covered in an
~,,,
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xlv PREFACE
overview chapter. This subject was considered too important to be left

out, yet too broad for a thorough coverage.
This book is primarily intended for seniors and graduate students in
chemical engineering and for chemical engineers in the industry. The
question as to who needs cataly(ic reactor design is answered in detail
in Sec. 1.6 of this book.
Here the questi0h arises: How knowledgeable and sophisticated must
a chemical engineer be, in order to re~d and understand this book? An
engineer will be able to read and understand it even with a modest
background in cataly~;!>, reaCtion kinetics, transport phenomena, and
pressure vessel design. Familiarity with Fortran IV programming is also
necessary, although it is not necessary to be a computer analyst.
While these limited bat.kgrounds are adequate for reading and un-
derstanding this book, thIs does not necessarily mean t:lat they are also •
adequate for carrying out a real reactor design assignment. After all, a
person who has just learned to play simple exerci~~s on the piano or the
violin cannot immediately be expected to perfOl III a Beethoven concerto.
This book teaches a great deal of what there is to teach today. How-
ever, de~igners would have to improve on their b"lckgrounds and ca-
pabilities by reading some of the references, and, what is most important
of all, by practicing what they have learned and usipg their own intuition
and ingenuity. In this respect reactor design is still very much of an art
and always will be.
The greatest difficulty in writing this book has been in finding pub-
lished or publishable sets of experimental data on the kinetics of catalytic
processes. Some published data have tu! Bed out to be inaccurate by as
much as an order of magnitude. Others are incomplete sets (e.g., acti-
vation energy values without the corresponding frequency factor~) and
are useless. Some complete sets give obviously wrong reactor sizes. Thus,
most reactor design examples in this book are based on assumed data
that produce results within a reasonable range. The reader is strongly
warned not to use these data in any design, but to procure credible
experimental data before even starting any design work. A:pproximate
results in a book that basically intends to l -IJ general methods and
strategies of reactor design are understandade and even admissible.
However, using anything but accurate and reliable sets of experimental
data in a temperature-sensitive NINAF reactor design would yield com- •
pletely valueless results.

All the computer programs presented in Chap. 2, as well as in design
examples, have been run on a computer and have been fully debugged.
However, with certain highly nonlinear kinetic data, some programs
might become unstable. In such cases, the designer must judiciously
manipulate the parameters and input data to avoid such instability. Also,
•
PREFACE xv
selection of excessively large step sizes (in numerical integration) might

cause program instability, just as selection of excessively small step sizes
might generate erroneous results. The reactor designer must watch for
such pitfalls.
There are a number of books on catalytic reactor design on the mar-
ket. Most of them were written by highly respected university professors,
who have done an admirable job of analyzing the problems of catalytic
reactor process design and setting up the required d~sign differential
equations. However, after tha~, readers are left largely to their own •
••
devices. There is, of course, a lot more to reactor design than setting up
the design equations, and the present bo(,k is attempting to cover these
other factors. Some of these are: a deep concern for the adequacy of
the data that will be used in the design; an explanation of how things
are really done in practice; the numerical solution of the design equa- ,
tions; the incorporation of the reactor design into the overall process
design of the plant; mechanical design considerations; operating con-
cerns; and, of course, the safety and stability of the reactor. Because of
this orientation, this book is probably the first of its kind.
This book could not have been written without the patient tolerance
of my dear wife Biirran, who for: many years allowed me to utilize on
this work the time that I would have otherwise spent with her. There
are nu words to express such gratitude.
I am particularly grateful to Prof. William E. Schiesser of Lehigh
University, my partner in Catalytic Reactor Design Courses of 1971 to
1973, for valuable advice on, and review of, Chap. 2. Actually it was his
lucid lectures during these courses tha:· Illostly inspired me to write
•
Chap. 2. I am also grateful to Prof. Fazil Erdogan of Lehigh University
for his review of Chap. 12, to Dr. NarendraJ. Sheth of Bethlehem Steel
Corporation for patient assistance in debugging computer programs, to
Dr. Bernard S. Mikofsky for years of inspiring teaching and coaching
on technical writing, and to Prof. Leonard A. Wenzel of Lehigh Uni-
versity and the research management of Bethlehem Steel Corporation
for encouragement in the development of the summer courses that even-
tually led to this book.
M. Orhan Tadwn
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•
TION OF REACTORS
Clwpter
PHASES OF DESIGN
Catalytic reactors are vessels or containers in which catalytic chemical re-

actions take place. They may be made of a variety of materials, the choice
of which depends on the temperature and pressur-: at which the reactions
occur and the corrosion resistance qualities required. Catalytic reactors
may also be of many types, depending on the tYFes of catalyst used and
the physical characteristics of the reactants and products.
1.1
CLASSIFICATION OF REACTORS
Catalytic reactors can be classified in a variety of ways. The classification
that appears most logical is that based on the nature of the catalysis.
Catalysis can be homogeneous or heterogeneous. If the catalyst does not
constitute a separate phase from the reactants or the products, the cat-
alysis is said to be homogeneous. In some cases the homogeneous catalyst
is dissolved in a liquid and the reaction ocers in the liquid phase, even
if some of the reactants or products are in the gas phase. An example
of such a reaction is
2 H9S
- + SQ.,
- ) 3 S + 2 H.,O
- (1.1)
which occurs in liquid water of pH I to 6 containing a certain amount •
of ions. The catalvst

•
is the water. In other cases the catalyst
•
and the
reactants are in the gas phase, but the product may be in the gas, liquid,
or solid phase. The reachon occurs in the gas phase, which is again the
phase of the catalyst. An example of such a homogeneously catalyzed
reaction is the Claus reaction [Eq. (1.1 »), which is slowl\' catalyzed by
,
•
2 CATALYTIC REACTOR DESIGN
water vapor at temperatures below 400°C. Above 400°C the reaction

runs noncatalytically. .
If the catalyst constitutes a separate phase from the reactants, we say
that the catalysis is heterogeneous. An example of such catalysis is the
acceleration of the rate of reaction (1.1) in gas phase by solid. bauxite
catalyst.
Thus a first classification of reactors as homogeneous reactors and het-
erogeneous reactors can be made .
Homogeneous catalytic reactors can be classified similarly to noncat-
alytic reactors. One criterion as the number of phases present while
another criterion is the degree of backmixing involved. Thus we may
have homogeneous gas reactors, homogeneous liquid reactors, and ho-
mogeneous gas-liquid reactors. We may also have homogeneous plug-
flow tubular reactors and homogeneous continuous stirred-tank reactors •
(CSTRs). Of course, as mentioned in th~ preface, this book discusses

heterogeneous catalytic reactors only.
A classification criterion for reactors containing heterogeneous solid
catalysts is the movement or the lack of movement of the catalyst particles
in the reactor vessel. On this basis the following types may be defined:
1. If the particles are fixed in their positiom. as a dense fixed bed, we
have a rued-bed reactor.
J
2. If the particles are piled up in a dense bed that moves slowly, losing
some fouled particles and adding fresh ones, we ha\"e a moving-bed
reactor. Reactors of this type are not discussed in this book because
they are in many ways similar to fixed-bed reactors. HO\\"ever, moving
. "
bed reactors differ radically from fixed bed reactors in catalyst fouling
and regeppration behavior.
3. If the catalyst particles are supported by an upflow of gas as a fluid
bed, we have aJZuidized-bed reactor. For reasons mentioned in the pref-
ace, this class of reactors is not discussed in this book.
4. If the catalyst particles are suspended in a liquid, \\'e haye a suspended-
bed reactor.
There are several subclassifications of suspended-bed reactors:
1. If the catalyst is suspended in a flwchanicallv stin cd liquid, we have
a continuous stirred-tank reactor.
2. If the catalyst is maintained in suspension in a liquid by rising gas
bubbles, we have a bulJble reactor or a slun.; reactor,
•
3. If the cat<ilyst is suspended in an upflow of liquid, we ha\e an ebullated-

bed reactor.
•
ClASSIFlCAllON OF REACTORS AND PHASES OF DESIGN 3
4. If the catalyst is suspended in a flow of liquid and gas strong enough

to entrain these particles in the reactor system, we have a three-phase
transport reactor.
Another criter!on for classifying either homogeneous or heteroge-
neous reactors is their mode of operation, i.e., whether they are operated
on a btztch, semicontinuous, or continuous basis. However, most industrially
im~rtant op.!rations are run continuously, and batch reactors are only
desi~ned if there i~ a specific good reason for this mode of operation.
Still apother classification t:riterion for reactors in general is the tem-
perature distribution within the reactor. If the temperature is constant
at all points within the reactor and does not change with time, the reactor
is said to bf' isothermal. If, however, the temperature varies in different
parts of the reactor, the reactor ic called nonisothamal.
Still another dassificauon criterion for reactors is the degree of heat
exchange between the reactor and the outside. If no heat is exchanged,
the reactor is called adiabatic, and if some degree of heat exchange occurs,
the reactor is nonadiabatic.
Still another classification criterion for reactors is the number of phases
involved in the reactions. Of course, in counting the phases the solid
catalyst should not count as a phase. Reactors that handle only ga~es are
called gas-phase reactors, those which nandle liquids only are cal!ed liquid-
phase reactors, and those which handle two-phase reactions are called gas-
liquid-phase reactors. Liquid-phase reactors are not discussed in this book
because they are relatively unimportant and can be considered as a
special case of gas-liquid-phase reactors .
•
We can use several of the above criteria to classify the heterogeneous
catalytic reactors discussed in this book as follows:
Fixed-bed reactors
Fixed-bed gas reactors
Isothermal reactors
Adiabatic reactors
Nonisothermal, nonadiabatic fixed-bed (I\INAF) reactors
Fixed-bed gas-liquid reactors
Trickle-bed reactors
Fixed-bed bubble reactors (FBBR)
Suspended-bed reactors
Continuous stirred-tank reactors (CSTR)
Slurry reactors -
Ebullated-bed reactors
Three-phase transport reactors
•
1.2 -
DESIGN DEFINITIONS
The design of a catalytic reactor involves:
I. Determining the type and shape of the reactor and calculating the
dimensions which will produce a desired quantity of a product or
products from a given feedstock (process design)
•
2. Making certain that the calculated reactor is thermally stable and safe
and will not lead to runaway reactions (stability stud)
3. Selecting the proper materials of construction, wall thickness, and
internals so that the reactor vessel will have the structural strength
to withstand the reaction conditions as well as the corrosive action of
the reaction mixture (meclw.nical design)
•
This book is devoted mostly to the process design and only to a limited
degree to the mechanical design and stability study of reactors. Me-
chanical design and stability are covered in overview in Chaps. 12 and
11, respectively.
1.3
G£NERAL METHODS OF REACTOR DESIGN
The traditional approach to designing chemical reactors in general and
catalytic chemical reactors in particular has been to try the process on a
bench scale, then in pilot plants of increasing size, and finally on a full
industrial scale. This certainly is cautious and safe, but also extremely
•
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time-consuming and expensive I (Fig. 1-1). Of course once this scaie-up
has been made, suffi~:ient information has become available to design
other reactors of about the same size for the same reactions or sets of
reactions. But if another reactor is required for a new reaction, the same
lengthy and costly process has to be repeated. This problem has led
chemical engineers to devise an approach which would make it unnec-
essary to repeat the traditional stepwise scale-up procedure for each new
•
reactIon.
It was thought that: it should be possible to design a catalytic reactor
simply from the knowledge of ~he chemical reaction or reactions which
o >0 -~~ 0 -----.;". . •
Bench
scale
Pilot plants
Full-scale plant
-
FIG. 1-1 Traditional scale-up procedure: (From Vern W. Weekman, Jr., by
per-mission.)
- -
•
ClASSIFICATION OF REACTORS AND PHASE!; OF DESIGN 5
a
Chem. physic.
+ Model Compuler
Plont
dOlO design
FIG. 1-2 Ideal scale-up procedure. J (From Vem W. Weekman,jr., by permission.)
will take place in the reactor. This is called the a priori method of reactor
design and still is an unreached ideal for most reactions. This ideal
approach includes the following steps (Fig. 1-2):
1. All necessary chemical and physical data on the process are gathered,
including information on chemical kinetics and transport phenomena.
2. A chemical reaction rate model is built.
3. The above information is fed to a computer.
4. The design of the full-scale pldnt is prepared.
•
Unfortunately this ideal approach will not materialize for some time
to come because reaction rate measurements are not quite precise J
factors, for example, are imprecise and, most important of all, some
processes have peculiarities and pitfalls which c"nnot be foreseen without
operating a pilot plant for some time.
Today a compromise is made between the traditional and the ideal:
a model is built from collected data and compC1Ted with the behavior of
a pilot plant before progressing to full-scale plant d:..sign. In this way
the number of scale-up stages is reduced and caution and safety are
retained while reJucing costs. The box diagram of Fig. 1-2 is modified
by adding a pilot plant step with data feedback (Fig. 1-3). The additional
, .
,. ..
, data modify the model and we may mo\"e on with increased confidence.
1.4 ..
PHASES OF REACTOR DESIGN
The phases of reactor design vary considerably according to the starting
point. In Fig. 1-3 a completely new process is considered. If some in-
dustrial information is available, this procedure will change. In any case,
each box in Fig. 1-3 represents a phase of reactor design.
Chem. 8 physic. Plont

dolo Model Computer design
I
L ______ ,
---------------" I
I
- •
Pi 101 :.1echonicol
plont #
design
FIG. 1-3 Improved scale-up procedure for a new process. I (From Venr W. Week-
man,Jr., by pelmission.)
•
full-scole Chem. a ph ysic. Computer

plont doto Mo!le I
------' J.
Improved,
optimum
plont design
FIG. 1-4 Modeling of a commercial process.' (From Vent W. Weehman,jr., by

permission.)
We want to study each of th,ese phases. We will begin with the modeling
phase, because the kind of modeling used determines the relationship
between the various phases.
Modeling of Reactors
To model a reactor is to write a set of mathematical equations which
express the behavior of the reacting system in this reactor under various
operating conditions. In a way, modeling is a simulation. The purpose
of modeling is to develop thorough and detailed information on a proc-
ess, which then can be used for optimizing the process both technically
and economically. A thorough· study of even an old and well-known
process usually reveals so many unknown or even unsuspected aspects
that the proces~ can Qe improved by the modeling.
Let us now consider the modeling of such an old commercial process.
The procedural diagram is shown in Fig. 1-4. Such a commercial process
should have yielded a considerable amount of data over the years. These
data are very helpful in building a mathematical ~odel, which usually
. . uncovers a considerable number of so far unsuspected facts. However,
the process data are not enough. The kinetics and transport phenomena
of the process must be studied in addition and must be included in the
model. When such a model is finally completed, it is run on the computer
to find the best operating conditions. If these conditions differ from
those actually used in the full-scale plant, the operation of the plant is
modified on the basis of the computer results to the extent that economic
and other conditions allow such change. The new plant data are fed to
the model and to the computer to test the model. If the new data do
not exactly verify the model, or- using the model expert's \'ernacular~
if the fit is not perfect, the model may have to be "fudged" a little, so
that the new data fit. The procedure is repeated a few times until the
designer is convinced that the model thus obtained reall)' simulates and
represents the process. Besides improving the operation of the modeled
plant, such a study also provides an optimized design for the next plant.
There are two different approaches to mode ling new processes. The
first is to start the model development about the same time as the process
development and to keep working along with the research and devel-
•
aASStFICATION OF REACTORS AND PHASES OF DESIGN 7
opment (R & D) group until a fitting model is obtained. The steps of

this approach and the interactions along the various steps are shown in
Fig. 1-5. Here kinetic and transport experiments have to be performed
simultaneously with process development work. Information is ex-
changed back and forth between the groups conducting the model study
(the second line in Fig. 1-5) and the process study (the top line in Fig.
1-5). An economic model of the plant is also developed alon~ with these
studies and this model is optimized. When the plant is started up, the
economic model is used for on-line optimization. After this first plant
is operating successfully, data obtained from it are fed to the model until
they fit it perfectly. When a second plant is built for this process, its
design can be technically and economically a "buIrs-eye hit."
The second approach to modeling new processes utilizes the most
modern concept of modeling: . no preliminary laboratOl] experiments •
are made. Instead, all kinds of data are collected and assembled ;n order
to define the model. Only those data which are lacking in the literature
are experimentaHy determined. Once all the needed information is on
hand, the model is constructed and if it looks good, i.e., if the data used
fit the model well, then an experimental model (a bench-scale or pilot-
scalp plant) is first built to check the fitting. This procedure is shown in
Fig. 1-3. This approach, called developing a process around a m,)dei rep-
resents a recent trend in the V.S. petroleum industry.:!
Modeling and optimization of reactors are outside the scope of this
book although both are necessary for reactor design. Two excellent books
by Luyben3 and Franks,4 are recommended for this phase of reactor
design. A STowing Jit{:rature on the subject is also available.
Collection of Data
A reactor designer to whom a new design job is assigned must imme-
diately define the reacting system and then collect all the data needed
Exploratory
a process a
Chem. physic. Plant Mechanical Construction Operation
development dota design design
t t t t + t
Kinetics and
transport Model Model Model
•
experiments extended updated
•
. + t
Plont Develop
••
economiC
• Optimize I- - - - - - - - i on-line
model plont opt im izotion
FIG. 1-5 Simultaneous process and model study for new process.' (From Ven,
W Weekman,jr., by pe/mission.)
•
for writing the set of design reactions or the model, depending upon
the approach to be used. Although the definition of the reacting system
may sound obvious, it is anythinl5 but obvious when the feedstock is a
complex mixture and when the reaction involves more than one of the
feed components. An exact analysis of the feedstock must be available,
with the possible ranges of variation of each component. If the reacting
mixture is anything such as a coal hydrogenation product or a petroleum
stream, then the numerous (possibly hundreds or thousands) of chemical
compounds must be grouped in classes of compounds that behave sim-
ilarly. It must be established whether the reacting system includes a single
reaction, simultaneous r6actions, consecutive reactions, or complex re-
•
action systems.
The chemical rroperties of all reactants and products must be known
so that their likely behaviur in the defined reacting system can be fore- •
seen and calculated. Similarly. various physical and therlIlodynamic

properties of all reactants and products must be known so that the design
equations or the model can be written.
Normally the reactor designer must be given all these data plus a
reaction kinetic model of the reacting system. This information may be
available either from the process development work or from the mod-
eling work, depending upon the dlesign approach used. In any case, the
reactor designer must have this information. In most of the problems
treated in this book a relatively simple kinetic model has been selected,
in order not to overcomplicate the problems and in order not to deflect
the reader's attention from the su~ject being taught. However, the reader
\ is cautioned at this point that in most real-life design problems the kinetic
model can be infinitely more complicated. It may include all kinds of
complexities, such as simultaneous and c:msecutive reactions, reversible
reactions, chain reactions, catalyst surface effects, and catalyst fouling
and aging effects. It may happen that the reactor designer receives' less
kinetic information than is necessary and is compelled to personally
obtain more information and thus, become involved in discussion of the
kinetics and the kinetic model of the reacting system, which subjects are
outside the scope of this book. A number of very good books on reaction
kinetics are available.5-9 The literature on reaction kinetics is very extensive .
•
When designing a reactor aJrOund a model, the collection of data is

the starting activity of the designer. In practice this is a large 'enough
job for a group of che"!ists and chemical engineers, depending upon
the complexity of the reaaing system. Thus the designer can concentrate
more on designing. -
Use of a Computer
The set of simultaneous equations describing catalytic reactors of certain
types can be solved only by means of a computer. In the 1960s analog
•
CLASSIRCATlON OF REACTORS AND PlIASES OF DESIGN 9
computers were used for this purpose; however the job is now perfOl med
much better by digital compu·ters. This book devotes considerable at-
tention to the practkal use of computers for the solution of reactor design
problems. Chapter 2 is devoted to the discussion of general methods of
numerical computation that are needed in reactor design. Also several
of the design problems in other chapters are treated completely, with
their computer programs and, if necessary, computer solutions.
Mechanical Design
The mechanical desilgn of a catalytic reactor includes the selection of the
proper materials of construction to hold up for an economically long
period under the reaction conditions, the calculation of the correct wall
thickness of the reactor vessel, and the design of internals and externals.
•
Chapter 12 is devoted to this subject.
The mechanical design phase usually begins at the same time as the
process design. Although the results of the process design are needed
to jize the reactor, the selection and testing of materials of construction
has to start immediately. In most cases the process designer and the
mechanical designer are different persons, but each must well under-
staTJd the other's problems. It is not unusuai for the process design of
a reactor to be determined by the limitations imposed by mechanical
design ~see broken tie lines in Fig. 1-3).
1.5
.
" t OPERATING CONSIDERATIONS
The design("rs, both process and mechanical, must constantly keep in
mind the way the reactor will be operated. Although the design is always
aimed at the optimum steady-state operating"'conditions, it must also be
able to meet start-up and shutdown conditions, especially the unexpected
kinds. If a fixed-bed reactor has to be designed for in situ catalyst re-
generation, the mechanical designer must meet not only one but t,,·o
sets of temperature-pressure conditions. For example, a light aromatic
pretreater reactor, filled with cobalt molybdate-on-alumina catalyst, may
be operated at 200 to 250°C and say, 40 to 60 bars when on steadY-Slate
stream. However if the catalyst has.v be r("generated in situ, the regen-
eration gases (Nz containing 0.5% Oz) may go as high as 550°C after
combustion of the coke when under strict controL If the oxygen content
is permitted to exceed 0.5-% in nitrogen, the combustion gases may be-
come dangt'rous\y hot and weaken the reactor. Thus the pretreater is
designed to withstand {WO sets of conditions:
1. 300°C at 70 bars for operation
2. 550°C at 5 bars for regeneration
•
10 cATAlYTIC REACTOR DESIGN
1.6 •
WHO NEEDS REACTOR DESIGN?

Reactor design is not used only by certain professionals who practice it
as their major occupation. There are quite a few other types of chemical
engineers who need! reactor design know-how, even if their designs may
never be translated into chemical hardware. For example:
· Many catalyst manufacturers in this country have been offering to size
the reactors of clients who purchase their catalysts. Some have devel-
oped specific computer programs to size certain types of reactors.
· R & D engineers must design, specify, assemble, and operate experi-
mental reactors they will use.
· R & D engineers who have completed a prvcess study must design full-
•
scale reactors and estimate their costs in order tn sell their new process
to the management.
· Project evaluation engineers must often si7e reactors for processes they
evaluate.
· Engineers who desire to check the design of reactors that may be
purchased by their company may have to carry out independent design
calculations.
The various types of chemical engineers mentioned in the above ex-
amples definitely need reactor design know-how. If they work for a
corporation which employs an experienced reactor designer, they should
\. ' . ~ry to obtain the services of this designer or of a good consultant in the
field. If such services are not available or are needed too often, engineers
may decide to learn to design their own reactors. It cannot 1:..:: emphasized
too strongly at this point that amateurish reactor design is both expensive
and very dangerous. Anyone who wants to tackle the design of catalytic
reactors must learn it properly and thoroughly, with all the mathematics
and the computer work involved. The purpose of this book is actually
to teach chemical engineers all the basic know-how and all the "tools of
the trade" and to guide them along the road of experience gathering.
REFERENCES
1. Vern W. Weekman, "Reactor Modeling," unpublished lecture at the Catalytic
Reactor Design Course at Pocono Manor, Pa., June 25-29, 1973.
.. 2. Vern W. Weekman, Private communication .
3. William L. Luyben, Process Modeling, Simulation, and Control for Chemical En-
gineers, McGraw-Hill, New York, 1973.
4. Roger G. E. Franks, Modeling and Simulation in Chemical Engineering, John
Wiley, New York, 1972.
•
ClASSIFICATION OF REACTORS AND PHASES OF DESIGN 11
5. Rutherford Aris, Elementary Chemical Reaction Analysis, Prentice-Hall, Engle-

wood Cliffs. N.]., 1969. .
6. Michel Boudart. Kinetics a/Chemical Processes, Prentice-Hall, Englewood Cliffs,
NJ., 1968.
7. A. R. Cooper and G. V. ]effreys, Chemical Kinetics and Reactor Design, Prentice-
Hall, Englewood Cliffs, N.J., 1971.
8. Octave Levenspiel, Chemical Reaction Engineering. 2C: ed., J"hn Wiley, New
York, 1972.
9. J.M. Smith, Chemical Engineeting Kinetics, 2d ed., McGraw-HiH, New York,
1970.
•
•
METHODS OF ERICAL
Chapter •
CO ATION
The design of fixed-bed reactors depends upon the simultaneous so-

lution of sets of differential equations, as will be seen in the following
chapters. Also, any type of reactor designed for the handling of complex
reaction systems often requires the simultaneous solution of sets of dif-
ferential rate equations. In the 1950s and 1960s such sets of ordinar:1'
differential equations (ODE) were usually solved by analog computers. In
the late 60s and the 70s digital computer methods were developed to
the point where they now can solve any kind of differential equations
encountered in reactor design work, including sets of partial differential
equations (PDE) occurring in the design of nonisothennal nonadiabatic
"' fixed-bed (Nlr\AF) reactors.
Therefore, the purpose of this chapter is to prepare the reader fo,
setting up and solving reactor design problems by means of digital com-
l
puters. The reader should be fully familiar with the Fortran IV language
and have sufficient mathematical background to manipulate differential
equations. However, it is not necessary to be a mathematician or " nu-
merical analyst.
2.1
TYPES OF DIFFERENTIAL EQUATIONS
Dirferentiul eq tlations encountered in reactor design can be broad Iv,
classified into two categories, as described below.
Ordinary Differential Equations

Ordinary differential equations (ODEs) each have one independent \"ar-
iable x (e.g., reactor length or reactor volume) and one or more de-
•
14 CATAlYTIC I(EACTOR DESIGN
pendent variables y (e.g., reaction temperature, fractional conversion,

or concentration) and may be written in the general form
(dyldx) = f(x,y) (2-1)
where, y and f are vectors, if there is more than one dependent variable.
Such ODEs will be used in the following chapters in the design of adi-
abatic fIxed-bed reactors and of some types of trickle-bed reactors. An
ODE is said to be initial-value if all its auxiliary conditions are written
for the same value of the independent variable. ODEs used in the design
of adiabatic fixed-bed reactors are typical examples of initial-value ODEs.
ODEs used in the design of certain kinds of trickle-bed reactors ha\"e
auxiliary conditions written for at least two values of the independent
variable and are said to have boundary- conditions. The methods used in
the solution of iniLial-value and boundan"-condition
•
ODEs are substan-
tially different.
Partial Diffelential Equations

Partial differential equations (PDEs) each have two or more independent
variables x (e.g., reactor length) and T (e.g., radial coordinate) and one
or more dependent variables y (e.g., fractional conversion, concentlation,
or temperature) and can be written in the general form for cylindrical
coordinates as
(2-2)
where A is a constant but B usually is a highly nonlinear quantity. More
generally, for any coordinate system, Eq. (2-2) can be written as
2
(dy/dX) -= AV J + B (2-3)
2
where V is the so-called laplacian operator.
/'True solution y( x)
o Xo xf x. b x
o
FIG. 2-1 Approximate numerical solution of a differential equation.
•
METHODS OF NUMERICAL COMPUTAllON 15
This may be of interest for spherical coordinates, i.e.,

•
(2-4)
because of their application to reactions in catalyst pellets. Such PDEs
will be used in the design of NINAF reactors.
Detailed digital computer programs to solve reactor design problems
involving differential equations of both categories wi!! \)(" described in
the following pages. However, before going into tile details of each
program the principles of the algorithms on which these computer pro-
grams are based will be reviewed.
2.2
PRINCIPLES OF ALGORITHMS
An algorithm is a rule or calculational procedure for solving a mathe-
matical problem that frequently involves extensive numerical operations.
A number of such algorithms are used in compmer programs for the
solution of simultaneous ODEs or PDEs. These algorithms have a com-
mon underlying principle that the user of computer programs should
know and understand.
How can one solve first-order ODEs (equations with only first-order
derivatives)? Let us assume a first-order ODE, which by definition would
be of the form
(dy/dx) = !(x,y) (2-5)
\., ,
Solving this ODE means finding a solution y(x) which satisfies both Eq.
(2-5) and one specified initial condition. In general, y(x) cannot be de-
termined analytically. Instead, the interval of interest (a,b) in the inde-
pendent variable x is subdivided into sub intervals or discrete steps. The
value of the true solution y(x) is approximated for each evenly spaced
value of x, so that an approximate numerical solution is obtained. This
approximate solution consists of discrete values corresponding to the
evenly spaced values of x, as shown in Fig. 2-1. If there are n + 1 evenly
spaced values of x, which may be called Xo, XI> X2, ... x,,, the step size h
would be
(2-6)
•
and x, = Xf) + ih where i'= 0, I, ... n.

How can the true solution )'(x) be approximated? Suppose the value
)0' corresponding to the initial value Xo of x, is known and the next value
)'1' corresponding to XI' is to be computed (see Fig. 2-2). One way of
•
•
y
•
~Known initiol volue of y
..---y(x,l True value of XI
..---y(X)
Et Error
- - _1
y, ( - Numerical value af y,
-b.x--
--h--
FIG. 2-2 Method of approximating a differential e«Juation.
getting from )'0 to )'1 is to compute the tangent at the initial point ),0,
which is given by the derivative at Yo or the slope of the tangent at )'0:
dy
)'1
- = 'Yo
- + Ax = -1'(xd
dx ."=l
.u
Referring to Fig_ 2-2, what we are looking for is the true value Y(XI) on
the true y(x) curve, but all we have from constructing the tangent at
point )'0 is the numerical value YI' Now, according to Eq. (2-5),
(dJldx)\:,,, = !(x;J, )'0) and we can write:
(2-7)
-
which is the approximate value of )'1_ Here an ermr El is made. If one
continues to approximate further values of)' by this method and is not
careful, the error may accumulate excessively. The essential feature of
all numerical calculations of differential equations is the estimation of
this error El> since the true value Y(XI) is not known. The error E can be
reduced if a smaller step h is selected. This can be seen from Fig. 2-2
and can be demonstrated by calculation. A simple method to estimate E
is that of Euler.
•
Euler's Algorithm
Euler's integration algorithm is
),,, + 1 = Y" + !()'n, xu) h + En (2-8)

•
METHODS OF NUMERICAL COMPUTATION 17
This expression looks like a Taylor series, since f(y", x,,) is the derivative
dy,/dx. Thus, a few more ternlS can be added by Taylor expansion:
2 3 3
=
- y + dy" . h + cly" . h + d y" . 1t +.. . . (2 9)
Y t/+ J t/ dx dx 2 21 3 dx 31 -
The added terms in the brackets may be called truncation error. If we

want to be really.accurate, we should use a large number of these terms.
Ho~:ever, that would be too time-consuming and expensive, and we can
compromise by using only the first term as a truncation error estimate,
\\< hich is what Euler did. Such a procedure is called a one-term en-OT estimate.
The derivative dy/dx can itself be expanded in a Taylor series:

dYn+J h
(2-10)
dx
2 2
From this expression d y/dx can be calculated:
cly" _ (dYn+ J/dx) - (dYn/dx)
q - (2-11) ,
dx- h
Equation (2-1 I) IS substituted into the first term in the brackets of Eq.
(2-9) and one can write: -
d..,.h
to
""
= - , "
dx 21
(2-12)
where subscript e denotes "estimated."

-
Equation (2-9) can then be written as ,
•, -
dy"
y. + I =1'. + dx . h + E (2-13)
which is the essence of the Euler algorithm.

Now, how can we convert this algorithm into a computer program?
Let us asst.::ne that we have to integrate a single ODE:
d~'
.
-([x
=x+J' (2-14)
with the initial value of y(xo) = y(O) = O. This initial value ODE has a
known analytic solution:
• y=e'-x-I (2-15)
In order to apply the Euler method to this ODE, we can start in Fig. _
2-2 from the known point)o and decide up to what maximum x value,
or XMAX, we will integrate. We can diagrammatically represent in Fig.
•
CATALYTIC REACTOR DESIGN
c C U L E R E T HOD
to!
C •••• ~EAO 04TA ANO tNtTtALIZ~ x. v. TRUEy ••••
•
~E4D CS.I00' XM4X. H
.~ITE (6. 2001 X~AX.H
x = o.
y = o•
•
TqUEY = O.
WRITE (6. 201) X. v. TRUEv
c
C •••• EUL~R·S ~=TH~O INTEGqATI~~ ••••
NSTEO : (X~AX + H/Z.)/H
00 3 N=l. NSTEP
V = V • H .ex + YI
X = FLOATlN) • H
TRUEY = EXP(X) - X - I .
WRITE (6. 201) x. Y. TRUEY
3 CO'HINU:;
c
C •••• FOR~AT FO~ J~PUT AND OUTPUT STATE~E~S ••••
100 FO~MAT (10X.~10.~.10X.FIO.6)

ZOO FOq~AT (7HIXMAX = .FIZ.6. sx. 5H H ~ • F12.5)
201 FOq~.T (IH • 4HX = • FIO.b. 5X • • HY = • F16.6. 5X. 8HTRU~v ~ •
1 Fl~.61
c
X.t.4Ax = 1.000000 H - (I.olcoeo

-,- ~ X - 0.0 Y = 0.0 TRUEY -- 0.0
X -
- 0.010000 y = 0.0 TRUEY = 0.OOO:J50
X = 0.020000 y -- 0.000100 TQUEY - a.~00201
X - - 0.030aoo Y - 0.000301 T~UEY -
X - 0.0"0000 Y = O.OC0604 TQUEY -
O.OO;)4CO"4
0.000811
X - -- 0.050000 Y -- 0.001010 TI;:UEY - 0.001271
X 0.060000 \' -- 0.001520 TQUEY - O.OO193-b
X - 0.07000~ Y --- 0.00:21"35 ""AUEY : 0.002507
X ;
o .oeoo ov Y
-
0.002857 TQUEV -- 0.00 '2:86
X ;
o.OQOOOJ Y 0.0036A5 TRUEY - 0.00&174
X -- 0.100000 Y - 0.00"622 '!J(UEY - 0.005171
X - a.110000 y --- 0.005668 TRUEY - o .a06277
X = 0.120000 Y - O.OO~~25 TRUEY -- 0.007496
X ;
0.130000: Y -- 0.0")8093 TRUFV = 0.006525
•
" •
•
•
•
•
•
•
•
X -- -
O.92000~ O.57794~ TQUEY -
y 0.5'39290
X -- O .. ~ :':0000 Y - O.-S;282f- TC:UEY - O.~04S\)9
"x --
; y -
O.~40~O') o .60S0C:;S Tc:;;utY : 0.619951
O.43~:>OOv -
y - O.62~S35 TRUEY - - 0.635 7 09
X --O.9~OOO:l Y - O.t' 3Q270 TPUEY - 0.~51696
X -- O.97~OOO Y - 0.6<;5263 TRUEY -- 0.667945
X ; o.ce0300 y - 0.61'1516 -- O.6S4456 T~UF.Y
X --
().990~OO y -- 0.H'6031 TOUE\' - - 0. 7 01234
x - -
1.4100000 Y - :).7()"Al1 - 0.71'3282 T~UE·Y
FIG. 2-3 Computer program for Euler algorithm and printout of computer
ruJ1.
•
•
MffiIODS OF NUMERICAL COMPUTATION 19
2-3 the various computer operations that we will perform. We must first
supply, or "read in," some information such as the chosen value of
XMAX (we choose XMAX = 1.0) and the step size H. We should have a
sufficient number of steps between the start and the end to achieve an
accurate mtegration. Of course, the more steps, the more accurate the
integration. We also conveniently print the input.
Next, we initialize the starting values of x, the computed yalue of )',
and the true value of y, which we call TRUEY. Initin.lizinK means setting
the initial values before the computations. We set x = 0.,), = 0., and
)0 = TkUEY = O. Again we ask the computer to print these initial data.
Now we calculate the number of steps I\"STEP we want the Euler
algorithm to use. Then we can construct the DO loop for the repeated
execution of the algorithm.
DO 3 N = 1,1\rSTEP
Y=Y+H*(X+Y)
X=FLOAT(N)*H
TRUEY = EXP(X) - X - 1.
WRITE(6,201)X,Y,TRUEY
3 CONTINUE
where N is the counter for the number of applications of the algorithm.
Here the most important statement is
Y=Y +H*(X+ Y)
It is derived from Eq. (2-13) by replacing dJldx with its value in Eq. (2-14).
.. ,
An actual computer run is presented in Fig. 2-3. This is an abbreviated
run. Normally, the programmer may want to ask the computer to cal-
culate and print the errors and considerac!y more information of in-
terest. But the basic idea is shown in the diagram of Fig. 2-4 and in the
program of Fig. 2:-3. It should be noted that an apparent discrepancy
exists between the y yalues and the TRUEY values in the computer
printout. The difference corresponds to the error El illustrated in Fig.
2-2. This inaccuracy can be decreased by selecting a smaller step size h.
While smaller step sizes make computer calculations more accurate, they
also make them more expensive, and the programmer must aJ\\"ays com-
promise between the degree of accuracy needed and the price which
must be paid for it. .
There is, of course, .another way of achieving better accuracy. One
can use a better algorithm than the old Euler method. A.ctuall\'. besides
being somewhat inaccurate, 'the Euler method has limited 5tabilil)'. A
-
solution is said to be unstable if errors introduced at some stage of the
calculations are propagated without bound throughout subsequent cal-
•
"
START
•
READ
XMAX,H
/ WRITf 7
" , XMAX,H
/INITIALlZE 7
X=O. Y=O. TRUEY=O
i 7
WRITE
X,Y, TRUEY
•
NSTEP=(XMAX +H/Z)/H
"
00 3 N=l, NSTEP
N =1
NO
K:SNSTEP E!\J
N=N"l
YES
Y·Y1-H.(X .. Y)
X =FLOAT(r;).H
TRUEY' EXP(X)-X-l
WRITE
X ,Y, TRUEY./
L
•
FIG. 2-4 Flow diagl am of Euler algorithm.
culations. There have been numerous improvements in the Euler method.

Perhaps the best known of these are the Runge-Kutta algorithms.
Runge-Kutta Algorithms
The main reason for developing improvements oyer the Euler algorithm
has been the need for more accuracy. The Runge-Kutta algorithms sat-
2
isfy this need. They exist in several variations.
The improved Euler method or Heun's method consists of using the
Euler algorithm twice in sF.'quence. First, a preliminary estimate of Yn+l
is obtained from
•
- y" + I = J" It f (x", Y,,) (2-16)
Referring to Fig. 2-5. y,,+ I is the ordinate at x = X,,+ I of the straight line
•
METHODS OF NUMERICAL
A passing from point (x", y,,) with slope f(x", y,,) = kl Furthermore, an
improved estimate Y.+I is obtained from Eq. (2-17):
h
Y.+I = Yn + 2 [f(xm Yn) + f(x,,+l> Yn+l)] (2-17)
The slope of the straight line used for this purpose is the weighted
a\-erage of approximations to the derivative at the two ends of the in-
tenal. Equation (2-16) may be considered as a predicting equation for
y,,_. -.vhereas Eq_ (:2-17) may be considered as a correcting equation to
yield the improved estimate OfYn+I' Equation (2-17) can be used itera-
ti\-e!v to give a stl-ies of COl lected Yn+ 1 values until convergence is achieved.
Thus this method is called a predictor-correct{}r method.-
The Improved polygon or m<Jdifi~d Euler method also us~s Euler's method
twice in sequence. Referring to Fig. 2-6, an approximation il> first ob-
tained for Y at the halfway point Xn + h/2. This value, called Yn+ -" is
obtained from Eq. (2-18):
(2-18)
The see:md step uses the equation:
)'n~1 = y" + hf (2-19)
Equation (2-19) is used to evaluate f(x,y) for x = Xn + hl2,y = Y"+'h and

uses this value as the average derivative over the whole interval h .
•
•
Slope flx""Yn.,)
d·j
•
,i
,,
•
JO'1
,
•
,
•
•
I, Yn.,
•
I,,
,•
· Yn
,I,
,
,
••
: h-·-~
•
Xn Xn.. x
FIG. 2-5 Second-order Rubge-Kutta procedule: Heun's predictor-corrector
method. (From Camahan et al.,. by pel'lnission from John Wiley.)
•
h
Slope I(x'+"2 .1.+i)
y ./
./
y •••
./
./ B
A
Yn
.h.. l!..-;
2 2
FIG. 2-6 Second-order Runge-Kutta procedure: improved polygon method.

(From Carnahan et al.,z by pe,.mission from John Wiley.)
The terms second-order and third-order Runge-Kutta algorithm mean

th,t approximations with accuracies equivale'1t to Taylor expansions of
2 3
y(x) retaining terms in h , and h , respectively, have been used. The order
of the terms has nothing to do with the number of terms used in the
• •
eITnr estImatIon.
2.3
nth-ORDER ORDINARY DIFFERENTIAL EQUATIONS
Up to this point only first-order ODEs, i.e., ODEs which contain only
first derivatives, have been considered for integration. How can one
-- , integrate an nth-order ODE? The form of such an equation is '
~ • d"yldx
2 3 3 n
F(x,;' dyldx, J2yldx , d yldx • • ) = 0 (2-'20)
Equation (2-20) is an ODE because it contains no partial derivatives, i.e.,
it has only one independent variable x. It is of nth order because the
highest-order derivative is of nth order. An nth-order ODE can be \\"[1t-
ten as a system of n first-order ODEs by defining n - 1 new variables.
For example, consider the second-order equation:
2
dy
9 . dy 9
x- 9 +X + X-)' = 0 (2-21)
dx- dx -
•
A new variable z: = dyl4x can be defined, and with it Eq. (2-21) can be
rewritten as a system of two first-order ODEs:
- -,
dy
-"--z:=O (2-22)
dx
•
ME1HODS OF NUMERICAl COMPUTATION 23
2 dz .,
X
dx'
+ XZ + x-"-' = 0 (2-23)
Any nth-order ODE can be converted to a system of n first-order ODEs,

which then can be solved simultaneously.
2.4
SIMULTANEOUS ORDINARY DIFFERENTIAL EQUATIONS
Consider a system of 11 simultaneous first-order ODEs in the dependent
variables -,'b -)'2, . . • -I,.:
•
(2-24)
•
d"-'"
= f,,(x, YI. Y2 • ... )',,)
dx
with initial conditions given at a common point xo, i.e.,
= )'1.0
,
,
,
•
•
(2-25)
•
The simultaneous solution of such a system of equations is, in general,

as easy as that of a single first-order equation. The algorithm selected
is applied to each of the simultaneous equations in parallel at each step.
VarioW'. computer programs have been developed to solve systems of
simultaneous ODEs. ~lost computer centers have these programs, either
in their program libraries or on tapes, which may simply be called. Some
programs, such as the DSS/2 program 0+ Lehigh University,3 are pro-
prietary and can be used either by purchasing them or by using the host
computer or one of its terminals for a fee. The use of such proprietary
•
•
•
programs is warranted only if they offer ad vantages not found in openly

available programs or if the user happens to have easy access to them.
2.5 .
PROGRAM FOR SOLVING INITIAL-VALUE ODEs
A particular fourth-order Runge-Kutta algorithm will now be discussed
and used in the solution of initial-value ODE systems encountered in
fixed-bed adiabatic reactor problems.
All fourth-order formulas conform to the equation
(2-26)
in which kl' k2' ks, and k4 are derivative ·.'alues calculated on the interval
Xn ~ x ~ Xn+I' Kutta has developed a particular algorithm in which •
a = 116 b = 2/6 c = 2/6 d = l!6

Then Eg. (2-26) becomes for a single equation dyldx = f(x,):
h
Yn+ I = Yn + 6" (hi + 2kz + 2k3 + k4 ) (2-27)
where kl = f(x", Yn)

kz = f(x + lf2h, Yn + lf2hk l )
71
k3 = f(x" + lf2h, Yn + 1/2kk2 )

k4 = f(x" + h, Yn + hk3)
1 ~t us apply this algorithm to the solution of n first-order ODEs.
. .
dYI
dx = fl(X, Y1> Y2, ... Yn)
•
(2-28)
•
•
with n initial conditions
"
j = 1, 2, 3, ... n (2-29)
Subscript i denotes "initiaL"
The development of this algorithm becomes rather lengthy and co m-
•
METHODS OF NUMERICAL
plicated. We willl discuss it only briefly and will try to at I ive quickly at
the result, which is the FUNCTION RUNGE, the calling program that
we will use without change.
We said above that Eq. (2-27) is written for a single ODE. For sets of
ODEs, y, x, Yn+" Y... hl' k2' k3' and k4' can be converted to vectors with one
component for ea~h ODE, e.g.,
(2-30)
h
Y"+\ = y. + 6(k\ + 2k2 + 2k~ + ~) (2-31 )
where k\ = f(x., Yft) (2-32)

k2 = f(xn + h12, Yft + V2hk\) (2-33)
•
k3 = f(xn + h12, Yft + V2h~) (2-34)

~ = f(x" + h, Y" + hks) (2-35)
Equations (2-30) to (2-35) are applied in parallel at each point in the
algorithm for alii component ODEs. This leads to a rather lengthy and
complicated development which we should avoid. The interested reader
can find the enti.re d~velopment in the book by Carnahan et al.,2 pages
361-375.
2
The block diagram of Fig. 2-7 has been designed to make it easy to
understand how the algorithm operates and how it communicates with
the main program. The main program contains the ODEs that the Runge-
Kutta algorithm is supposed to integrate and solve. We did not set up
any main program in this chapter. However, Chaps. 5 and 7 contain a
total of three such main prob":-ams that communicate with the Runge-
Kutta algorithm. Let us simply assume here that our main program
would contain n 'ODEs that must be solved simultaneously, and that each
-
of these ODEs contains the variables listed in Table 2-1.
The main program sets up the number 11 of the ODEs, initializes Y
for each component ODE, and initializes the independent variable x
(usually the reactor length) for all the ODEs. Then the Runge-Kutta
algorithm is implemented in the form of a five-step procedure that is
diagrammatically explained in Fig. 2-7 and presented as a computer
program entitled FUNCTION RUNGE in Fig. 2-8: The worki!1g of
FUNCTION RUNGE will be explained in the following by referring to
these two figures: Figs. 2-7 and 2-8.
First four variables me dimensioned. Then, the pass counter M is set
to 0 and then to 1 and the .frst pass is executed. This first pass simply
sets RUNGE = I and returns to the main program. At this signal, the
main program computes the derivative values f and returns to FUNC-
•
. CAlliNG
PROGRAM
INITIALIZE m& m+ 1
;-
/'
/'
;-
/'
PASS 1 PASS
m
K' RUNGE (n, Y, F,., h)
Yj • Y
'" • f
h
Y • Y;+Zf
1 : 1'" h/2
•
E
4
PRINT • ' .... 2f
SOLUTIONS
Y , Vi'" h f
x =J +
PASS 5
CHANGE
h IF ~- Y'Yi ... ~", ... fl m'O
DESIRED
,
! -, , YES
END
FIG. 2-7 Diagtam of communications between FUNCTION RUNGE and the

main calling prognm. Camahan et al./ by fromJohn Wiley.}
TION RUNGE. This time the second pass is executed for all the ODEs
by means of a DO loop which calculates
y=¥ I
•
cl> = f
• ¥=Y+lhhf I
..
and sets RUNGE = 1. Agaiu we go to the main program and update

derivative values at an advanced X value and come back to the FUNC-
TION RUNGE.
•
2-1
Nomenclature Used i"1 FUNCTION RUNGE and Conesponding Sym-
bols Used in the Text
•
Symbol
name • text
In Definition
N n Number of ODEs
y y Vector of dependent variable (solution)
F f Vector of derivative approximations
X x Independent variable (in Chaps. 5 and 7 Z is
used instead as reactor length)
H h Step size
M m Pass counter for Runge-Kutta algorithm
PHI Vector. values
SAVEY y Vector of initial conditions
Fl'!'CTIOl' Rl'l\:GE (!'. Y. F. X. H) .

11'TEGER RU:,GE
DIMEl\SIOl\ I'HI(50). SAVEY(50), YeN). F(l\)
DATA MIOI
M=M+I
GO TO (1,2,3,4,5). M
C .... PASS I ....
I RV:\GE - I
RETURl'
C .... PASS 2 ....
2 D022J - 1.1'
SAVEYU) - Y(jl
• PHl( J) = Ft J)
\., , 22 Y(j) = SA\TI'U) + 0.5 * H * Ft J)
x - X + 0.5 * H
RCl'\GE = 1 •
RETURl'
C .... PASS 3 ....
3 DO 33 J - I. X
PH!(J) = PH!(J) + 2.0 * F(j)
33 Y(j) = SA\'EYU) + 0.5 * H * F(j)
RL'XGE = 1
RETCRX
C .... PASS 4 ....
4 DO-t4J=I.X
PHI(j) - PHI( J) .. 2.0 * F(j)
44 (Y JI = SA\'EY(j) + H * FU)
x = X + 0.5 * H
RCXGE - 1
RETL'RX
C .... PASS5 ....
5 Dv 55 J = I. X •
55 Y(j) = SA\'EY(j1 + (PHI(j) + FU)) * H16.0
M = 0 ..
Rl'XGE = 0
RETURl'
El\D
FIG. 2-6 FUNCTION RUNGE (From Camahan et al.,. by penllissioll from John
Wiley.)
27
•
In the third pass the following computations are made for all nODEs
•
cfl = cfl + 2f
Y = Yi + Il2hf
RUNGE = I then sends us back to the main program to revise and
update derivatives f; X is not advanced.
In the fourth pass the following computations are made for alln ODEs
cfl = cfl + 2f
Y = Y i + hf
X=X+hI2
Here RUNGE = I sends us back to the main program to revise and
upgrade f at an advanced X. •
In the fifth pass only one equation is computed:

Y = Yi + ( cfl + f)hl6
This time RUNGE = 0 skips the calculations of derivatives in the main
program and thus completes the integration and solution of the ODEs.
From there on, the main program proceeds in doing whatever else it is
supposed to do with the integration results, such as calculating further
dependent variables and printing the results.
The operation of FUNCTION RUNGE will be better understood
when it is used in Chaps. 5 and 7 in connection with reactor design
problems.
2.6 "
PROGRAM FOR SOLVING BOUND'ARY-VALUE ODEs
Initial-value ODEs are really special cases in which all auxiliary conditions
are written for the same value of the independent variable. In the general
case, auxiliary conditions are written for different values of the inde-
pendent variable. Such ODEs are called boundary-value ODEs. For ex-
ample, a second-order differential equation of the form
9
dy d-y
F x~. y, dx' dx2 = 0 (2-36)
is the subject to thf' follo>ving boundary conditions:

y(a) = a -v(b)
•
= ~ (2-37)
as ca;~ be visualized in Fig. 2-9. The numerical solution of boundary-
value ODEs is considerably more complicated than that of initial-value
ODEs. Three types of algorithms are available, as described below.
•
Y 10: a 1 ft . , : b
•
y..,'/3
•
Yo .Q
{3
a
o a b I
FIG. 2-9 Trial-and-error solution of a boundary-value problem. (From Car.

nahan et al./ by pellnission from John WiIey.)
The Shooting Method

•
The shooting method consists of a trial-and-error procedure in which

a boundary point having the best-known conditions is selerted as the
initial point. Any other missing initial conditions are assumed. The
initial-value probl,em is then solved by one of the step-by-step proce-
dures, such as the fourth-order Runge-Kutta algorithm (see Sec. 2.5).
The initial conditions are adjusted and the problem is solved again. This
process is repeated until the computed solution agrees with the known
boundary conditions within specified tolerances.
The Finite Difference Method

The finite difference method consists of approximating the derivatives
. in the ODEs by finite difference quotients. This results in a system of
difference, or algebraic, equations that require considerable computer
memory. However, present-day computers can easily handle such systems.
Some ODEs can successfully be handled by means of the finite dif-
ference method, while others are too nonlinear and require the use of
the method described below.
The Combined Finite Difference and Quasilinearization Method

The combined use of the finite difference method and quasilinearization
4
as described by E. Stanley Lee is recommended only in cases of com-
rlicat;:d and nonlinear ODEs that cannot be handled by the finite dif-
ference method alone.
In most cases reactor designers do not have to use boundary-value
ODEs, but there are cases when they are necessary, for example, when
significant axial dispersion exists within the reactor. For integrating these
equations, this book recommends either of the two methods or the com-
bined method, as explained below.
•
30 CATAlYTIC REACTOR DESIGN
The types of boundary-value ODEs encountered in reactor design

are of the general form: . .
(2-38)
(2-39)
where Z = dimensionless axial coordinate and independent

variable
CT
= reduced molar concentration (= CICo), dimensionless
dependent variable
TT = reduced absolute temperature (= TITo), dimensionless
dependent variable
fh f2 = functions of C and TT
T
P~ = Peelet number for axial dispersion, gas-liquid phase
Subscripts: mal denotes liquid-phase mass transfer

ha2 denotes two-phase heat transfer
o denotes reactor inlet condition
The functions fl and i2 are highly nonlinear functions of catalyst
surface temperatureTs and may also be non linear functions of catalyst
surface concentration C.. depending on reaction order. In turn, in the
,
• case of first-order reactions Ts and Cs are related to bulk fluid temper-
ature TT and concentration Cn respectively, through the relationships:
Cs = C Co/(l + Dam)
T (2-39a)
Da,. = T1k1kca (2-40)
Ts = To(TT + Dah) (2-41 )
Dah = (- AH)ffiJa h To (2-42)
where Da,. and Dah are Damkohler numbers for mass and heat, respec-
tively. The reader is referred to Chap. 4 for more information on these
surface-bulk relationships. ..
It is believed today that catalyst surface concentrations and temper-
atures are practically identical to corresponding bulk fluid properties In
industrial-scale trickle-bed reactors. Of course, the design equations are
then considerably simplified. But there certainly are also cases in which
this simplification does not apply.
•
MElHODS OF NUMERICAL COMPUTATION 31
The boundary conditions are:

.
at bed inlet Z=O CT(O) = T,(O) = 1 (2-43)

dC,(Zr) dT,(ZR)
at bed outlet Z = ZT = =0 (2-44)
dZ dZ
In the following se\"eral cases, boundary-value ODEs of varying degreLS
of nonlinearity will be considered.
Case I: C, = C; T, = T
In a first-order rea((ion. by assuming that C, = C and T, = T Eqs. (2-38)
and (2-39) can be written as:
I dZC,
. dZ 2 -
dC, I
dZ = hi exp (- E R(;T)C,C, =
13(C,. T,) (2-45) .
Pern.1
I ~T, dT,
. 'dZ 2 - dZ = - b',! exp (- EIRcT)C,Co = 14(Cp TT) (2-46)
Peh.2
where b l and b2 are products of constants

E = activation energy, kJlkmol
Rc = gas constant = 8.314 kJ/{kmol . K)
f3,14 = funaions of C and T, T
The combined finite difference and quasilinearization method must

be used in this case because of the nonlinearitv• of the ODEs. In order
to apply the finite differena approximation metlwd the catalyst bed length
ZT is subdivided into M equal increments of length az as diagrammat-
ically shown in Fig. 2-10. Since ZT is not really known yet, it must be
guessed; it is preferable to overestimate so that we do not run the risk
of underestimating and repeating the whole calculation. Let C(l) and
T,(l) denote the values of er and Tn respective\:", at positions I!1Z; i.hf"n
the derivatives of Egs. (2-45) and (2-46) can be replaced by the following
difference quotients:
2
d C, I
-7? = ? [Ca + 1) - 2 C,(l) + C,(l - I») (2-47)
dZ- .lZ-
-
,
~tlZ"l .
1 2 3 4 5• 6 ; M
I: 1 2 3 4 5 9' 7 M-2 M-l M M+l
M increments
FIG. 2-10 Diagram of reactor length increments.
•
(2-48)
(2-49)
dZ
dT TX
= I [T (I + 1\ - T (I)] (2-50)
dZ tlZ TX )TX
in whic!; I = 1,2,3,. ., (M - 1). The subscript x denotes an unknown

value in a forthcoming iteration, while nonsubscripted TT values are
known eililer from the initial value or from the previous iteration.
Equations (2-49) and (2-50) are an old version of the finite difference
approximation of the first denvative. It was used in this section because
4
E. Stanley Lee used it in his work. H,)wever. it is more accurate to write:
•
dC,
=-- (2-51 )
dZ
dT,x
=-- (2-52)
dZ
This is done in the development of partial differential equations in Sec.
2.7. The difference in accuracy would probably be insignificant in reactor
design.
Let us now replace the derivatives in Eqs. (2-45) and (2-46) by the
proper difference quotients:
\. 1
Pe tlZ2 [C,(I + 1) - 2C,(I) + CT(I - 1)]
mal
I
- tlZ [C,(l + 1) - C,(l)]
= bl exp (- EIRcT,(l)T,,) . C(l) . Co = f3(C n TT) (2-53)

1
Peha2 t1Z2 [Til + 1) 2T,(l) + TT(l - 1)]
1
- tlZ [TT(l + 1) - TT(/)]
= - b2 exp (- EIRcTT(I)To)CT(l) . Co = f4(C" n (2-54)

•
•
Equation (2-53) is perfectly linear in C and does not need to be T
quasilinearized. However, Eq. (2-54) is not fully linear in TT; it contains

a TT term in the exponential. Thus only Eq. (2-54) has to be quasilin-
•
METHODS OF NUMERICAl COMPUTATION 33
earized. The function f4(C" TT) can be quasilinearized by using the fol-
lowing equation for TT only: .
dJ(TT)
J(T,x) = J(T,) + dT (Tn: - TT) (2-55)
r
TLus, Eq. (2-54) can be quasilinearized as follows:

•
J(T,x) = - b2 exp (E/RcToT,(/»C,(I)Co

+ l(df(T,)/dTr)1 . [Trx(I) - Ir(/)] (2-56)
Here the derivative df(Tr)ldT, can be calculated by using well-kno.m

formulas:
dJ4/dT, = b2 C,(I) Co [d exp (- E/RcToTr(/»/dT,]
•
Let u = exp [E/RcToRT{l)]. Then

du-l/dT, = u-'\duldTr) = (l/exp (2E/RcToT,»(duldTTI
Substitution of the above derivatives into Eq. (2-56) gives

E(T",(I) - T,(l))
J(T.,) = - b2CoC.(I) exp ( - E/RcToTl 1) T oRc(T,(/»2 - I (2-57)
Equation (2-53) is rearranged and Eq. (2-54) is combined with Eq. (2-57)
and rearranged to give
•
2
CT(I + 1)[(l/Pema lllZ ) - (l/LlZ)]
+ +
9
Cr (..')£( - 2/Pemal~Z-) (l/LlZ) - blCo exp (- EIRcToT,fJ))] (2-58)
+ Cll - 1)(lIPema1 LlZ 2
) = 0
2
Trx(l + 1)[(lIPemaI LlZ ) - (lIAZ)]
-l Trx(/)[( -2/Peha2tlZ2) + (I1LlZ) - (b2COC (/»E exp (-EIRcToT,{l)
T _
2 2 (2-09)
/ToRcTT(I)] + TTiI - 1)( I1Pe ha2 Z )
= b2COCT(l) exp [.- E/RcToT,(/)] [( - EIRcToT,(l)2) - I]
It should be noted that in Eq. (2-58) the C, terms have no subscript
x because that equation is already linear in C and all C terms in it are T T
considered "known" or . 'calculable bv the method of Thomas. which is .
explained below. The C term in the right-hand side of Eq. (2-53) is

T
assumed to be in the "main" increment I and not in incremem.5 I + 1

or I - 1 and is so subscripted. All the C, and TT terms in Eq. (2-58) and
•
-
Eq. (2-59), which do not originate from Eqs. (2-47) to (2-50), are sub-
scripted I. .
Equations (2-58) and (2-59) can be simplified and rearranged by de-
fining the following coefficients:
2 l
Cll = (Pemal • I1Z r
CI2 = -2' Cll + (1/I1Z) -b l C o CCl
,
Cl3 = Cl! - (1/I1Z)

Cl4 = 0
l
C21 = (Peha2' I1Zr
C22 = -2' C21 + (lII1Z) + CC~ . CCI
C23 = C21 - (lh~Z) (2-60)
C24 = CCI . CC3
where CC 1 = e -EIRGTOT,(l)
-----;; - 1
Substituting these coefficients in Eqs. (2-58) and (2-59)

Cl I . C,(I - 1) + CI2 . C,(I) + C13 . CT(1 + 1) = Cl4 (2-61)
C21 . T",(I - 1) + C22 . T",(I) + C23 . T,/I + 1) = C24 (2-62)
-
Note that the terms are ordered from left to right in the order of I - 1,
I, I + l. For I = I, the term containing (I - 1) would be zero. Because
a subscript is not pennitted to be zero in Fortran IV, instead of setting
I = 1,2, 3, ... , M, the values of I will be set I = 2,3,4 .... , (M + I),
as shown in Fig. 2-10. Then,
at the reactor inlet Z = 0 I = I
I C,(i\t + 1) = C,(M)
at reactor outlet Z = ZT I = M +
T,{M + 1) = TT(M)
(2-63)
When the value of I is varied, the following types of equations are
obtained: •
•
C1I . C T(I) + CI2 . CT(2) + Cl3 . CT(3) = Cl4 (2-64)
CII . C,(l - 1) + CI2 . Cll) + Cl3 . ClI + I) = Cl4 (2-65)
•
C 11 . Cr(M - 1) + Cl2 . C,(M) + C13 . Cr(M + 1) = CH (2-66)

C21 . T",(l) + C22 . T;x(2) + C23 . Tr.•(3) = C24 (2-67)
C21 . T.)/ - 1) + C22 . Trx(l) + C23 . TTX(l + 1) = C24 (2-68)
C21 . Tn:(M - 1) + C22 . TrAA1) + C23 . Tn;(M + 1) = C24 (2-69)
Since C. ~ 1) = 1, and Trx(l) = i., the terms C ll'Cr(l) and C21· T,x(l)
become known quantities and can be transferred to the right-hand side
of Eqs. l2-64) and (2-67). Also, because of the boundary conditions of
Eq. (2-63), Eqs. (2-66) and (2-69) can be simplified and the following
system of six equations is obtained:
C12 . Cr(2) + C13 . C,(3) = C14 - Cll
(2-70)
ell· er(I - 1) + CI2 . cm + CI3 . e,(I + 1) = C14 (2-71)
Cll . e,(M - I) + (C12 + C13)C,(M) = C14 (2-72)
C22 Trx(2) + C23 . T ,,(3) = C21 - C21
(2-73)
C21 . T,x(I - 1) + C22 . Trx(I) + C23 . Trx{I + 1) = e24 (2-74)
•
C21 . T",(M - 1) + (C22 + C23)Trx (M) = C24 (2-75)

It can be seen that the first and last equations of each set of M-I
equations contain only two unknowns, and all other equations in the two
sets contain three unknowns. These equations have a tridiagonal coefficient
56
matrix and may be solved by using Thomas' melhod. • This method and a
2 •
subroutine TRIDAG to implement it are presented by Carnahan et al.
,- 1
This procedure is applied alternately to the mass and heat equations

until Cr and 1~ values for any Z do not change any more than a desired
amount from one iteration to the next.
There are some problems here: the bl and b2 "constants" are not really
constant. Also, these quantities cannot be calculated from increment !:J.Z
to increment AZ because all increments are calculated simultaneously by
the Thomas method and not in steps beginning with the reactor inlet.
The only time new coefficient values are calculated is between iterative
steps and then they can be picked up by the computer program for each
A2 or each I value.
•
2: Cr ;I!: C; Tr ;I!: T
In case of a first-order'reaction, Eqs. (2-38) and (2-39) can be written as
•
-
(2-76)
•
(2-77)
where Cs is replaced by its value from Eq. (2-39a), while Ts is left as is.
The following equations result:
(2-78)
(2-79)
Equation (2-78) is linear in Cr and Eq. (2-79) is linear in T r. The Ts in

Eq. (2-79) can be related to Tr during local iterations. Both equations
can be treated 0~11y by finite difference approximation. No quasilinear-
ization is needed.
•
The simplifying coefficients are defined as follows:
C 11 = r (Pe ma l.6.Z 2 l
Cl2 = -2' CII + (1/.6.Z) - bl CC

•
Cl3 = CII - (1I.6.Z)

Cl4 = 0
C21 = (Peha2.6.Z2rl
(2-80)
C22 = -2' C21 + (1/.6.Z)
.
'. C23 = C21 - (1/.6.Z) .
C24 = - b2Cr(f) . CC
Co e-EIRcT,
where CC = D
I + am
In Case 2, the overall iteration is not adequate to calculate new coef-

ficient values. The values of TlJ), Cif) and functions of other parameters
related to reaction kinetics must be calculated for each I value before
integrating each ODE. This must be done by an efficient local iteration.
It is best to recalculate the temperature Ts(f) by this local iteration and
to compute other parameters from that recalculated temperature value.
A Newton-Raphson iteration procedure required only three steps to
arrive within ±O.OOI of the true figure, while a Picard iteration needed
four steps for the same ·purpose. Iteration
.. tpchniques are discussed in
App. A.
•
MElHODS OF NUMERICAL COMPUTATION 37
Case 3: Cs =C; Ts =
T; Reaction Is Second-Order
Equations (2-38) and (2-39) c~m be written as:
•
(2-81 )
(2-82)
Again, both finite difference approximation and quasilinearization are

applied to both equations in the same way they were used in Case 1.
The simplifying coefficients are defined as:
CII = (Pemal.::lZ2rl
C12 = -2' Cll + (lI.::lZ) - 2 - blCCl
CI3 = CII - (1/.::lZ)
. Cl4 = -bl - CT(I) . CCI
(2-83)
C21 = (Peha2 .::lZ
2 l
r
C22 = -2' C21 + (lI.::lZ) - CC2 - C,(l) . CCI . b2IT,(l)
C23 = C21 - (If.::lZ)
C24 = -b~· C'(l) . CCI(CC2 + I)
where CCI = C~ C,(I) e-E1Rr,ToT.(/)
CC2 = ElRcToT,(l)
•
The rest of the plrOcedure is again quite similar to that of Case 1.

A word of caution is absolutely necessary before leaving. the subject
of boundary-value ODEs: the foregoing algorithms do work with reac-
tion kinetics of reasonable nonlinearity. However, if the nonlinearity
exceeds certain limits, the computer program might not work. The only
possible remedy I know of in such cases is to try to decrease the nonlin-
earity of the kinetic equations by juggling parameters.
2.7
ALGORITHMS FOR SOLVING
PARTIAL DIFFERENTIAL EQUATIONS
PDEs describing NI]'.;~.F reactors are of the parabolic type, i.e.,
d'f
- = A
. a r.,
2
I aY
+ - + C (2-84)
dZ iJR- R aR
•
where Z is the axial coordinate, R the radial coordinate, and Y a de-

pendent variable such as concentration or temperature.
A conventional approach to the numerical solution of PDEs is to
replace the spatial derivatives in both the axial and radial coordinates
with finite difference approximations. The resulting system of nonlinear
algebraic equations is then solved by an iterative procedure such as the
Newton-Raphson algorithm. Typically, the equations are coupled tri-
diagonal systems, which can be solved in a circular iterative fashion by
Thomas' method. A generalized program for PDEs based on this ap-
i
proach has been reported by M. G. Zellner et. al.
Alternatively, the radial derivatives of the PDEs can be replaced with
finite difference approximations, while the axial derivatives are retained.
This approach leads to a system of coupled non linear ODEs consisting
of subsets of ODEs for each PDE. The ODEs are initial-value in the axial
position if only first-order axial flm" terms appear in the original PDEs.
The entire system of oeEs is then integrated numerically with respect
to axial position, starting at initial conditions corresponding to those at
the inlet to the reactor. The dependent variables Y, i.e., the reactor
temperature and concentrations, can be visualized as evolving along lines
of constant radial position. Therefore this approach is often termed the
method of lilles, since the ODEs contain difference terms. The method
has also been termed the state-7)G1iable algorithm.
The method of lines will now be illustrated in detail as applied to
the solution of the PDEs that model the XINAF reactor. As we will see
later in Chap. 5, mese PDEs are of the form:
q •
aCT 1 _a-_c-,;., + I aCT

=-- (2-85)
az aR
2
R aR
aT 1 1 aT
T
=- + ---'- T
(2-86)
az R aR
and have the following auxiliary conditions:
Bed inlet CT(R, 0) = T,(R, 0) = I (2-87)
Bed centerIine aCr(O, Z)/aR = aT,(O, Z)/aR = ° (2-88)
Bed wall aC,(RT,Z)/aR = 0 (2-89)
. aTr(RnZ)/aR = (BiUT, - T(RT,Z» (2-90)
The radial derivatives in Eqs. (2-85) and (2-86) are replaced bv standard
second-order central difference approximations:
-
1 ac,
+-.-....:
+
C..tri+l - 9C·
C ri-l
- ~~----~----~ + .... 1"/
(2-91 )
R aR I1R~ il1R 211R
•
METHODS OF NUMERICAl. COMPUTATION 39
- 2Tri + T ri - I 1 T ri +1 - T ri - I
(2-92)
aR 2 + iaR . 2aR
These approximations are written for the ith radial grid point, where r
= iaR, i = 0, 1,2, ... , N" and aR is the radial increment and is assumed
constant in the subsequent development. If Eqs. (2-91) and (2-92) are
substituted in Eqs. (2-85) and (2-86), two ODEs result for each radial
grid point:
dC ri
- -2Cri + Cri - 1 1 . Cri + 1 - Cri - 1 _ f R
(2-93)
dZ aR 2 + iAR 2aR I I
dT" - 1 . Tn+1 - 2Tri + T ri _ , + ri

1 . T + - T -
1 ri , +f R
- iaR 2/lR
(2-94)
dZ Peh 2 I
where i = 0, I, 2, ... , N r
Similarly Eqs. (2-87) to (2-90) are approximated as:
(2-95)
(2-96)
(2-97)
(2-98)
Equations (2-95) to (2-98) are used to eliminate the fictitious L-0undary

points Cr_1> Tr_ h CrNr + I, and TrNr+ 1 from Eqs. (2-93) and (2-94).
\ The initial conditions for Eqs. (2-93) and (2-94)
CTl = I
T rz = 1
correspond to the inlet conditions for the reactor, Eq. (2-87).

Equations (2-91) to (2-100) constitute an initial-value problem in ODEs
with, in this case, a total of 2(Nr + 1) ODEs (two equations for each of
the radial grid points i = 0, 1, 2, ... , N r). In other words, the compu-
tational problem is now to integrate the two derivative vectors dCri(Z)1
dZ and dT ri(Z)/dZ that define the concentration and temperature distri-
butions within the reactor. Any numerical integration algorithm can in
principle be used to solve this initial-value problem. This book will use
the fourth-order Rung~-Kutta integration algorithm, which was devel-
op~d in Sec. ~.3 for initial-value ODEs.
The implementation of this method presents two problems: .first, at
the centerline the expression (lIiAR)(C ri + I - C'i- d/2t1R becomes 010, or
•
indeterminate; second, some of the subscripts become zero, something

that the computer does not accept. Consequently, measures must be
taken to solve these two problems.
In order to avoid the first problem, the PDEs for i = 0 must be
modified. The terms (lIR)(iJC/iJR) and (lIR)(iJTjiJR) in Eqs. (2-85) and
(2-86) can be modified by applying l'Hospital's rule to them (i.e., dif-
ferentiation of the numerator and denominator with respect to R).
1 ac, -
lim (2-101)
R~O R aR
1 iJT, "
a-T,
R iJR = -aR~2 (2-102)
Substituti'ln of the rt:lationships in Eqs. (2-85) and (2-86) gives:
ac, = 1 . "
2 a-c, - f,(R,) (2-103)
•
az Pem 2
aR
aT, = "
1 . 2 a-T, f
az Pe" aR 2 + 2(R I )
(2-104)
The finite difference analog for these new equations are:

oCr = 2 . C'i+1 - 2C ri + C,i-I _ f'R ) (2-105)
az Pem !1R2 1\ I
iJTr _ 2 . T'i+' -2T'i + T,i-, f

az - Pe" . !1R2 + 2(Rd (2-106)
.. Equations (2-95) and (2-96) can be substituted into Eqs. (2-lO5) and
(2-106), respectively, to obtain:
..
ac, = 4 . C,i+ I - CT ; _ f· (R ) (for i = 0) (2-107)

az Pem !1R2 I I
aT, = 4 . T'i+l - TTi + f (R ) (for i = 0) (2-108)

az Peh !1R2 2 I
Thus the first problem is resolved. The second problem can also be
resolved by setting i = 1, 2, 3,4, 5,6 instead of i = 0, 1, 2, 3,4, 5. Then
NT = 6. In this way i will never become zero or negative. In order to
modify Eqs. (2-93) and (2-94) for this change, the fJra~tions lIi!1R will
be replaced by l/(i - 1)!1R. The set of equations to be integrated by
FUNCTION RUNGE 'can then be set up as shown in Fig. 2-11.
Under certain conditions computer programs that integrate partial
differential equations by the foregoing method can develop serious in-
stability problems. In its mild form, instability becomes evident when
temperature or concentration profiles begin to swing. Of course, in its
•
METHODS OF NUMERICAl 41
C •••• CALL ON ThE FOURTH-ORDER RUNGE-KUTTA FUNCTION ••••

2 K=RUNGE (12,Y,F,Z,H) .
C IF Kc1 COMPUTE DERIVATIVE VALUES
IF{K.NE.1) GO TO J
DO 10 I= 1, NR
IF{I.NE.1)GO TO 11
P (1.1 ) .. (4./PEM)· (CR (1+1 )-CR Cl) )/(DEL'l'AR**2)- (DP*R1(1 )/(CO"U»
J:o'CI .2 )&(4 ./PEH)· (TR (1+1) -'l'R (I) )/(DELTAR"2)+",HR(I )"uf
1 /( CP"U.RHOC*'l·O)
GO TO 10
11 1F(I.EQ.NR) GO TO 12
WALL=(TR(I+1}-TR(I-l»/(2.·D~LTAR)
F (I .1 )=( l./FEM)" ( (CR(I+1) -2. "CR (I )+CR( 1-1) )/(DE.L'l"R"2)
1 ... (1. I{ (I-1) "DBL'l'AR) ). (CR(I+1 )-CR( 1-1) )/( 2. "ufU.'l'AR) )
2 -(DP*Rl(I)/(co*u»
F(I.2)=(1./PEH)·«TR{1+1)-2."TR(I}+TR{I-l»/{DELTAR**~J
1 + ( 1. 1« 1-1 ) "DELl'AR )) *WALL)
2 +(DHR(I)*DF/(CP*U*RriOC*TO»
GO TO 10
12 WALL=BIW*(TW-TR(NR»
F(1.1)=(2./PE~)*(CR(I-1)-CR(I»/(DBLTAR*·2)
1 -(DP*Rl(I)/{Co·u»
F(1,2)=(2.IPEH)*(TR(I-l)-TR(I»/(DELTAR··2)
1 +(l./{{I-l)*DELTAR)*WALL)
2 +(DHR(I)*DF/{CP*U*RhOC.TO»
10 CONTINUE
GO TO 2
C •.•• IF TR EXCEEDS TR";AX, TERb:INATE INTl:.GRAHOh ••••
) IF(TR{l).LE.TR~~X) GO TO 4
GO TO 5 (5 is a WRITE s'tatement)
FIG. 2-11 The essentials of the computer progr am to solve partial differential
•
equations.
more serious form, it makes the program unworkable. Instability is usu-

ally caused by too large a I:!.ZII:!.R2 ratio. For linear PDEs there is a classical
stability condition that requires (I:!.ZII:!.R2)(l/Pe) to be <112. For strongly
\. nonlinear PDEs, such as Eqs. (2-85) and (2-86), that term must be much
smaller stilL There is apparently no universal rule for nonlinear PDEs.
Since for NINAF reactors the Peclet number is constant, we can simplify
the condition to I:!.ZII:!.R2. In the RDMOT2 computer program developed
in Sec. 5.3 for the naphthalene oxidation process, a I:!.ZII:!.R2 ratio of (0.11
52) = 0.004 was chosen. It was observed that e,"en a ratio as low as (0.11
2
2.5 ) = 0.016 caused mild instability. The designer must plan for a stable
2
computer program by judiciously preselecting the proper l1ZIl1R ratio.
Both the increase of l1R and the decrease of l1Z should result in a greater
number of computer calculations, hence in greater computing costs.
However, increasing I:!.R might get us to a given ratio more cheaply,
since I:!.R is squared.
•
2.8 .
HANDLING OF SEVERAL PARALLEL REACTIONS
Up to this point we have considered algorithms that would handle a
single cheIllical reaction. Processes that include several pal alld reactions
•
CATALYTIC -REACTOR DESIGN
are quite common in coal hydrogenation and in petroleum refining. In

Sec. 7.2 we will discuss in detail the design of an industrial-size trickle-
bed reactor for petroleum oil hydrodesulfurization and that of a labo-
ratory trickle-bed reactor for the same process. Both designs will handle
four parallel reactions. The first one will be designed as a plug-flow
reactor in a manner quite similar to that used for an adiabatic fixed-bed
gas reactor and will use the same algorithm. The second one, however,
will be designed as a backmixed trickle-bed reactor and will require a
more complex algorithm than was discussed in Sec. 2.6.
We want to extend the Case 2 boundary condition algorithm of Sec.
2.6 to a process with n parallel first-order reactions. The mass equations
can be collectively expressed as:
dC.(])
(2-109)
dZ
where] = 1,2,3, ... n ] = 1 will denote sulfur concentration

j = 2 will denote oxygen concentration
] = 3 will denote nitrogen conce~tration
] = 4 hydrocrackables concentration
] = 5 unsaturates concentration
The heat equation can be written:
(2-110)
The simplifying coefficients are definf'ri as follows:

CII = (Pemal ~Z2rl for all reactions
C121 = - 2 . Cl1 + (1I6.Z) - bll Co exp (- E/RcT,}/(l + Daml)
C122 = - 2 . Cll + (1I6.Z) - b12 Curl) exp (- E2IRGT,)/(1 + Da,d
C123 = -2 . Cll + (1/6.Z) - bl3 CNO exp (-E3IRGT,)/(l + Da",s)
C124 = -2' Cll + (1I.1Z) - b[4 CHyO exp (-EJRGT,)/(l + Da",4)
C125 = -2 . Cll + (1/6.Z) - b[s C HCO exp (-EsiRGT,)/(l + Da",s)
C 13 = C 11 - (1I.:lZ) same for all reactions
C14 = 0 • same for all reactions
2 !![
C21 = (Peha2 .:lZ )
C22 = -2 . C21 + (l/.:lZ)
C23 = C21 - (lI.:lZ)
•
METHODS OF NUMERICAL COMPUTA1ION
dpEL L (ilHj R/Damj)

C24 = - - - - - - - -
To(EpCpU + ELPL CpLUL)
where R j = 1'1 Aj exp (- E/Rc T ,) CO} CT(j,l)

In case of several parallel first-order reactions, the calculation of the
heat transfer becomes somewhat complicated. Equation (4-23) becomes:
ha(T, - T) = L (- M-l,)~R;
or L (-dH,hR;
T=T+---- (2·111)
, h .a
Here, fR; occurs on the catalyst surface, where conditions are different
from those in the bulk gas phase in the case of small-scale trickle-bed
reactors.
Thus fR; = 1'1; Aj exp ( - E,lRcT,) C" (2-112)
•
Since Cs; = C Ti Co/(l + Dam,} (2-113)
Dam; = 1'Ik;lk( a (2-114)
1'I;A; exp (- E;lRcTs) CT ; Co, _ 1'Iik, C r; Co;
~= - (2-115)
1 + (1'I j A/kc a) exp (-E;lRGT,) 1 + (1'I,k;lk(a)
T, = T + "Z /(h a) (2-116)
This information is needed in the Ne~ton-Raphson iteration in the lab-

, , , oratory-size trickle-bed algorithm in Sec. 7.2.
The iterative calculation of T, according to I\ewton-Raphson can be
made by means of the fOl mula:
T - f(Ts;) - r,d' (T,J (2-117)
s.i+ 1 - I - f' (T,;)
where Tsj = the T, value calculated at any increment i
Ts•i + I = the T, value calculated for the next increment i + I
f(T,j) = the T,j function or the expression giving the T" value [in
this case, Eq. (2-116)]
f' (T,;) = df(T,;)ldT'i
•
Since we already have f(Tsi) [Eq. (2-116)], let us calculate j'(T,;). In
these calculations we can eliminate the subscript i from T,. The only
term in Eq. (2-116) that contains Ts is kj , which we can expand into
ki = Aj exp (- E/RcTJ
•
Then
exp ( - E/RcT,)
1 + (TJiA;lk(a) exp (- E;lRcT,)
(2-118)
In order to obtain the derivative of the expression in the brackets let
us set:
u = exp ( - E;fRcT,) and
The well-known formula fCl d(u/v)/dT, is of course
d(ulv)
- (2-119)
dT,
Let us calculate each term of Eg. (2-119): •
du/dT, = exp ( - E;lRcT,)E;fRcT; (2-120)

dv/dT, = (TJiAiE/k(aRcT;) exp (- E/RcT,) (2-121)
Substituting Eqs. (2-120) and (2-121) into Eq. (2-119) ahd simplifying
•
gIves:
d(u/v)/dT, = exp (-E/RcTJ(E;lRcT;)/[1 + TJik;lk(a) exp (-E;lRcT,)f
(2-122)
and substituting Eq. (2-122) into the brackets of Eq. (2-118) gives:
(l/ha) 2:TJi( - tlHi)C,iCOiAi E ; exp (- E/RcTJ
f' (T,) = ----;;------:-:-------:-____.-;;-- (2-123)
RcT;[l + (TJ;A;lkca) exp (- E;lRcT,)f
With these results the internal Newton-Raphson iteration can be per-

formed. The use of the full program is illustrated in Chap. 7.
The number of overall iterations (not the intemnf Newton-Raphson
iterations) is usually 3 for a single-reaction process. For the four-parallel-
reaction process described in Sec. 7.2 the number of overall iterations
is 11.
NOMENCLATURE
a Ratio of external surface area to catalyst particle volume,
-I
m
A Frequency factor
3
C Molar concentration, kmollm
Da Damkohler number, dimensionless
•
METHODS OF NUMERICAl COMPUTATION 45
Activation energy, kJlkmol

Derivative value in the Runge-Kutta algorithm
Functions of eT and TT
Step size
Longitudinal increment in finite difference approxima-
tion method;. integer
- .
k KeactJon rate constant
Coefficients of the Runge-Kutta algorithm
Liquid-catalyst mass-transfer
,
coefficient, mls
Nur,.ber of longitudinal reactor increments
n Total numJer of terms in a series, or the number of a
-
typical member of a series
Pedet numter for heat, two-phase (gas and liquid) axial
dispersion
Peelet Dumber for mass, axial dispersion, liquid-phase (see
Chap. 7)
R Reduced radial coordinate, dimensionless
Rc Gas constant = 8.314 kJl(kmol . K)
3
9?. Rate of global reaction, kmoV(m • s)
T Absolute temperature, K
\.
x Independent variable
y Dependent variable
z Variable = dvldx
-
Z Reduced longitudinal coordinate, dimensionless
ZT Reduced total reactor length, dimensionless
Heat of reaction, kJ/kmol (positive if endothermic, neg-
ative if exothermic)
E • Error
Void fraction
,
Intraphase effecti\'eness factor, dimensionless

•
Subscripts
e Estimated
h Heat
• •
46 CATALVTlC REACTOR DESIGN
Nr Label of the outermost radial increment near the reactor

wall .
o Initial or inlet
r Reduced
s Catalyst surface
x Unknown value
REFERENCES
1. Daniel D. McCracken, A Guide to Fortran IV Programming. 2d ed. John Wiley.
New York, 1972.
2. B. Carnahan, H. A. Luther, and J. O. Wilkes, Applid Numerical Methods, John
Wiley, New York, 1969.
3. William E. Schiesser, "DSS/2 (Differential Systems Simulator. Version 2),"
Lehigh University, 1982.
4. E. Stanley Lee, "Quasilinearization, Difference Approximation, and Non-
linear Boundary Value Problems," AlChE j., 14:490-496 (1968).
5. Leon Lapidus, Digital Computation for Chemical Ellgzneers, McGraw-HiIl, New
York, 1962, p. 254-255.
6. Matthew G. Zellner, "DSS Distributed Systems Simulator," Ph.D. thesis, Le-
high University, 1970.
7. Matthew G. Zellner, Fred P. Stein, Robert W. Coughlin, and WiIliam E. Schies-
ser, "A DSS Study of the Kinetics of Adsorption and Chemical Reaction,"
Proceedings of the 1970 Summer Computer Simlllaiivll Canfernue, Denvn, June
10-12, 1970, pp. 284-294 .
•
•
Chapter CA'rALYTIC MODELS
This chapter briefly reviews the general area of heterogeneous catalytic

kinetics and the modeling of catalytic reactions. Such a review is necessary
because reactor designers may have to pass judgment on the value and
completeness of kinetic information they receive. for this, they must
fully understand the entire subject. This chapter provides a bird's-eye
view of the field and an introduction to further stUl.!ies. Reaction mod-
eling is actually the initial phase of reactor design.
The task of reaction modeling is usually a difficult one, because of
complex kinetic mechanisms involving parallel and consecutive reac-
tions, chain reactions, catalytic surface inhibition and poisoning, and
, catalyst aging. If heat and mass transfer relations both inside the catalyst
pores and outside the catalyst pellets are added to that, the modeler
faces a herculean task.
3.1
CATALYSIS
The catalyst plays an important role in just about any aspect of the
chemical reactions 'which ~ccur on its surface. Thus we must first briefly
review the science of catalysis (if such a thing is possible at all) in order
to understand catalytic reaction rates, which we will review in Sec. 3.2.
•
Definition of a Catalyst
•
A catalyst is a material whi<;.h initiates and enhances the rate of a chemical
reaction without being consumed by that reaction. While the catalyst per
se does not appear in the overall reaction statement (for example,
S02 + V202 ) S03), it does not follow that the catalyst is not a partici-
•
..,
-'"
.......'"
-<> ,. - - - -;;--,- - -<>
e
E,
.-
-.... :;::: El
..,
'"
g .:- -r E2
.:<> t.H
-
~
<>
J ___ _
W
>-
.co-.,
<:7'
L -_______________ _ W
-'"
co
·Oistonce" along reactor path "Oistance" along reactor path

(a) (b)
FIG. 3·1 Comparison between (a) a noncatalyzed and (b) a catalyzed reaction.
pant. In fact, it participates in many cases and alters the path of the
:eaction. For e:ll..dmple, S02 oxidation is catalyzed by V20 5 as follows:
V2 0 5 + S02 ) V20 4 -i- S03 (3-1)
V 204 + V202 ) V 205 (3-2)
The catalyst V205 participates but is then regenerated.

A catalyst may a!so be defined as an agent which lowers the free energy
of activation of a thermodynamically permitted reaction. Figure 3-1 pre-
sents two diagrams of the energy of a reaction, one run thermally (at
left) and the other catalytically (at right). An exothermic reaction has
been selected as an example. The reaction must first overcome an energy
ballier by expending the activation energy El' Once the energy level of
the reactants has been increased to the height of the barrier, the reaction .
can proceed and an energy ll.H = E2 - E) is produced. In the case of
the noncatalyzed reaction (left), the amount of energy El to be expended
is quite large, but catalysis reduces E) to a much lower level although
Ilil is unchanged. In nontechnical terms, the catalyst may be considered
to "drill tunnels" through the energy mountain.
Classification of Catalysts
Roughly, catalysts are classified as homogeneous and heterogeneous. Ho-
mogeneous catalysts, which are not discussed in this book, exist in the same
phase as the reactants. Heterogeneous catalysts e;xist in a different phase
than the reactants. Commonly, heterogeneous catalysts are solid sub-
stances catalyzing gas- and/or liquid-phase reactions. This book discusses
exclusively these solid ctltalysts.
Heterogeneous catalysts are classified according to various criteria.
Accordi~g to their electrical conductivity, they are classified as follows:
Commercial catalysts usually do not belong exclusively to any single
•
CATAlYTIC KINETIC MODRS ..9
Conductors g.,nicomiuctors
•
Insulators
Pt, Pd, Fe metals NiO, ZnO MgO, AI,O" Si0 2-

Conductivity in- AI 2 0" solid acids
creases with
temperature
Electron-ex- Electron transfer at
change between high temperatures
metal and
adsorbate
Chemisorb all Chemisorb
gases O 2 , H2 hydrocarbons
Metals generally
found in transi-
•
uon groups
Good oxidation- Good oxidation-re- Good isomerization,
reduction duction catalysts cracking, alkylation,
catalvsts
•
dehydration catalysts
class. For example, the dual function catalysts may have two specific
functions on one particle, each belonging to another group. For example:
PtlSi0 2-AI 20 s
Metallacid
Cond uctor/insulator •
"• •
Hydrogenation site/acidic site

The classification of catalysts has been discussed in great detail by R.
W. Coughlin. I
Properties of Heterogeneous Catalysts

In heterogeneous catalysis at least one reactant must be chemisorbed.
If we call two catalytically active sites on a catalyst surface XI and X 2 ,
the reaction of two chemical species A and B over the catalyst giving a
product ~ can be formulated as follows (Fig. 3-2);
A 8 •
X, x.
~ -
•
FIG. 3-2 Chemisorption of species
A and B on a catalyst surface.
•
-
so CATALYTIC REACTOR DESIGN
x
A+B -~)P (3-3)
•
Catalvst
•
(3-4)
B + x.,- ~) BX.- (3-5)

(3-6)
A +IB~-=;)FP'---- (3-7)
Tht. ovel all resuit of Eqs. (3-4) to (3-6) will be Eq. (3-7), which is
identical to Eq. (3-3). This cycle can be repeated many times but even-
tually the site deteriorates. Thus no fixed relationship exists between
reactant consumption and site X. If only A is chemisorbed, we have:
•
• (3-4)
(3-8)
A + B ) P (3-7)
The reaction velocity or rate deIJends on the amount of acti\-e catalyst

exposed to the reacting fluid. However, in heterogeneous catalysts the
intrinsic relationship between observed reaction rate pardmeters and
catalyst concentration cannot be anticipated a priori. Hence catalytic
reaction rates are expressed per gram of catalyst formulation.
Catalysts C2n only speed up a reaction that is thermodynamically pos-
sible. They cannot change the thermodynamic equilibrium; they can
only alter the path. Consequently, a catalyst that speeds up the forward
reaction also speeds the reverse reaction if placed on the other side of
the equilibrium.
Another important property of the catalysts is their ability to alter
yields and selectivities by speeding up some reactions more than others.
For example, ethyl alc8hol undergoes dehydration or dehydrogenation
as follows:
CH 3 CH 2 OH:"\'c,():I, HoO + CH, CH" (3-9)

- - -
Ethylene
,
Cu
Hq- + CH 3 C (3-10)
•
H
• Acetaldehyde
,
"
Alumina speeds up Reaction (3-9) while copper speeds up Reaction

(3-10) .
•
CATAlYTIC KINETIC MOD8.S 51
The reaction mechanism is not always known definitely. The oxidation

of S02 is catalyzed by V 205 according to:
(3-11)
The mechanism is believed to follow Eqs. (3-1) and (3-2). This is a model,
in other words, a hypothesis. We do not know for certain whether it
represents reality.
If we compare a thermal reaction, which gives a multitude of products,
with the same reaction over a catalyst, we often see that many fewer
products are produced. In other words, the catalyst makes the reaction
more selective. For example, thermal hydrogenation of ethylene gives
a chain reaction and produces not only ethane but also other gases. On
2
the other hand, catalytic hydrogenation of ethylene gives only ethane.
3
Boudart compared the thermal and :he catalytic rates of this reaction:
~-
r(homogeneous) 0-= 10-' exp( - 180,540IRT)Plh (3-12)
~- .
r(catalytic) = 2 x 10-' exp( - 54,390IRT)Pfh (3-13)
At T = 600 K, the rate ratio is:

Catalytic
= 2 exp((l80,540 - 54,390)/600R]
1\ oncatalnic
•
= 1.921 X lOll (3-14 )

We can see that the catalytic reaction is more than 11 orders of magnilude
faster than the thermal, or homogeneous, react,ion.
'. , Some catalysts are dispersed on the surface of catalyst supports, while
others are used alone and undiluted. Some supports are catalytically
inactive or inert and some are not; some supports actually affect the
catalyst. The actual catalytically active material is called the catalytic agent.
Additives which improve the catalytic agent are called promoters. Pro-
moters can work physically or chemically. For example, alumina in iron
catalysts for ammonia synthesis prevents the sinteringof crystallites. This
. is an example of a physical promoter.
It is not always possible to measure the intrinsic rractioll rate directly
on the active sites of the catalyst. For one thing, the sites may be on inner
pores of the catalyst particles. What is normally measured is the global.
reaction rate, which coinprises the following events (Fig. 3-3):
•
. Transport of reactants: Interphase and intraphase (Interphase means "in

the space outside of the catalyst particle'\ intmphasr means "inside the
pores of the catalyst particles.") This is the diffusional step (see Sec.
3.4). .
•
52 . CATAlYTIC REACTOR DESIGN
· Chemisorption: Rate == ka CA(l - 6).

· Surface reaction: Rate = chemical reaction rate = k6 A 9B = kCAC B •
· Desorption: Rate = kd 9prod
where ka = absorption rate constant
kd = desorption rate constant
3
C = molar concentration, Ikmol/m
9 = surface coverage or fraction of catalyst surface covered by
adsorbed species
Subscripts A,B denote species A,B
SuLscript prod denotes product
• Transport of products: interphase and intraphase.
In these steps only the bulk concentrations can be measured. The first •
and third steps are familiar mass-transfer processes. The sec:md step,
which involves adsorption on a solid surface, is discussed below.
Let us now d;gress for a while and take a closer look at the adsorption
phenomenon, which is so crucial to the understanding of catalysis.
There are two types of gas adsorption on catalyst surfaces:
• i>hysical adsorption: At some temperatures and pressures a gas can be
adsorbed on a solid, covering it entirely. The binding forces between
the adsorbing species and the site are of the van der Waals type. This
adsorption resembles liquefaction. If we know that the adsorbed gas
forms a monolayer, this may give us a method for measuring the
adsorbing surface area .
•
• Chemisorption: Some gases are strongly adsorbed on certain sites of a

surface; here the bond is chemical. -
Table 3-1 shows the main characteristics of and differences between
physical adsorption and chemisorption. Physical adsorption isotherms
are used to determine the surface area of catalysts by the BET (Brunauer-
4
Emmett-Teller) method.
1-
,, Interphase .:. lntraphasrl
,
A_·_ ,
I
•
'eact;n; ) ,I
specIes
•
•
Cotolyst
po':icle
FIG. 3-3 Interphase and inbaphase events in the global catalytic reaction.
•
CATALYTIC KINETIC MODELS 53
TABLE 3-1
Comparison of physical with chemisorption
Physical adsorption Chemisorption
Adsorbent All solids Some solids

Adsorbate All gases below critical Some chemically reactive gases
•
polOt
Tern perature Low temperatures Generally high temperatures
range
Heat of adsorption Lo w , ""!!..H·10'1 High, =;; reaction !!..H
Rate and activation Very rapid, low E Nonacti\'ated, low E; activated,
energy high E
Coverage Multilayer Monolayer
- •
Reversibility Hignly reversible Often irreversible

Importance For determining surfaces For determining surface con-
ancl pore sizes centration, rates of adsorption
and desorption; for estimating
active center area; and for elu-
cidation of surface reaction
kinetics_
The nature of the chem!c::orbed complex is still obscure. It cannot yet be

measured.
There are several models (theories) of the relationships among surface
coverage 6, concentration CA, and adsorption rates. For example in the
Langmuir m o d e l : -
Adsorption rate = ka p(l - 6) (3-15)

Desorption rate = kfi (3-16)
where p = partial pressure.

At equilibrium the adsorption and desorption rates are equal
ka PO - 6) = kfi (3-17)
We may set (k)k d ) = K, where K is the adsorption equilibrium constant,

and combine it with Eq. (3-17) to calculate the surface coverage:
.
6 = K'P
---'---- (3-18)
1 + K· P
•
54 CATAlYTIC REACTOR DESIGN •
This is the Langmuir isotherm. Some reactions obey this model, others
obey the Freundlich isotherm: .
n>l (3-19)
Still other reactions obey other isotherms. They will not all be discussed
here. The interested reader is advised to consult standard textbooks on
chemical engineering kinetics5-7; the articles by Brunauer, Love, and
11
Keenan,8 Halsey and Taylor,9 and Beecklfl; and perhaps bOoks by Rideal
l2
and Hayward and Trapnell.
Perhaps the most important property of a heterogeneous catalyst is
its porosity. A good catalyst may have several hundred square meters of
inner pore surface area per gram of catalyst. This inner surface area of
catalysts can be measured by various classical methods (such as the BET
and mercury porosimeter methods), and from the results it is pJssible
to calcUlate the pore distribution, the mean pore radius, and similar
information. As we will discuss later on, the pore structure has a strong
effect on diffusion phenomena and hence on reaction kinetics. The pore
structure also has a strong effect on the poisoning and the selectivity of
catalysts.
When some chemical species are chemisorbed on a catalyst surface
and stay there, we say that the catalyst is poisoned because it loses pa:-t
of its activity. Some poisons such as coke are temporary and can be
removed by heating or by burning. Other poisons are more permanent;
when they are involved, the whole catalY5l must be replaced (e.g., sulfur
on platinum).
If a ...:. ::.-action of pore surface poisoned and
reaction rate poisoned
F=
reaction rate unpoisoned
Curves 1 and 2 in Fig. 3-4 are ordinary cases of selective poisoning. Curve
3 shows non-selective poisoning. Here, the surface is still available and the
relationship is linear:
F=l-a
Curve 4 in Fig. 3-4 represents antiselective poisoning: F =: (l - a) '12. By
fast reaction the poison is distributed homogeneously into the pore struc-
• ture and more of the inner surface of the catalyst can be used by the
13
reaction. Catalyst poisoringconsiderably affects the selectivity of catalvsts.
Catalyst poisoning has been widely studied. Some of the basic work
was done by MaxtedI4'~n England. Current progress has often been
15
reviewed by John Butt in voluminous articles. .16
The poisoning or deactivation behavior of catalysts must be well stud-
•
CATALYTIC KINETIC MOoas 55
1.0
u... 0.8
---'"
>-
~
-- 0.6
-'-'
-~ 0.4
<>
-4
.-
-o
'-'
<>
.:: 0.2
1 2
0.2 0.4 0.6 0.8 1.0

Fraction poisoned a
FIG. 3-4 Selectivity of catalyst pore poisoning. (Reproduced with the pe, lIIission
of the Academic Press and Dr. Ahlbol n Wheeler. IS)
ied and known before any reactor design can begin. There is no amount
of a priori knmdedge that can make up for the lack of such information.
3.2
CATALYTIC REACTION RATE MODELS
There are two well-known models for:! catalytic reaction rate. The first
one is that of Langmuir-HinslzelwoodlHuugen-Watsoll (L-HIH-W).17 The other
is tile power laU'. The L-H/H-W model gives for a reaction of the type
A + B ) D (3-20)
,- -
the reaction rate:
k K 1K 2C ....C S
r = ----------~~~~----~ (3-21)
[1 + K1C ... + K 2C S + K 3CDf
where CA, CB, and Cv are the molar concentrations of species A, B, and
D, respectively. The constants KJ> K 2 , and K3 are adsorption equilibrium
constants and k is the reaction rate constant. In Eq. (3-21) there are too
many coefficients that are difficult to determine. For the same reaction
[Eq. (3-20)] the power law is:
(3-22)
The power law has only one temperature-dependent coefficienrk. One

usually operates at a narrow temperature range of interest. It is at best
\'ery difficult to prove \~hether the one or the other model is closer to
reality. I n general it does not make much sense to retain a complicated
model if the existing data can be made to fit the simpler power law just
as well.
• •
FIG. 3-5 Normal reaction.
The factor kin Eq. (3-22) is called the reaction rate constant and i~ given
by the well-known Arrhenius equation:
k = A exp( - EIRT)
where E = activation energy, kJ/kmol (see Fig. 3-1) .
R = gas constant = 8.314 kJ/(kmol . K)
,. T = absolute temperature, K
A = frequency factor or preexponential factor (the dimension of
this parameter depends on the order of the reaction)
A catalyst affects both the activation energy and the frequency factor of
the reaction rate constant.
:\[ezaki and Kittrell have shown that it is possible to distinguish be-
tween various reaction models by using linear regression techniques.
From the viewpoint of the reactor designer, there can be no justification
in using anything but the power law unless the other model has been
,, significantly differentiated by a better curve fit.
, ,
In Eq. (3-22) r is the reaction rate, which is usually expressed as a
der;'-ative such as r = -dC...ldt, which is the consumption of the species
A during the differential time dt. It also may be expressed as the rate
of formation of a species, such as r = dCr/dt. In this case the sign in
front of the derivative is positive. The reaction rate constant k is related
to temperature by the Arrhenius equation [Eq. (3-22a)].
Reaction Order
The order of reaction is the value of the exponent of the concentration
term of a rate expression., For example, scme reaction rates are inde-
pendent of any concentration. Then Eq. (3-22) can be simplified to
•
r = k (3-23 )
Such reactions are termed zero-order, since Eq. (3-23) can also be written
as
r = kC~C~C~ = k(l)(l)(l)
•
CATALYTIC KINETIC MOORS 57
If a reaction rate is proportional to a single concentration (el III and

is thus described by an equation of the form
r = kC A (3-24)
the reaction is said to be first-order with respect to reactant A. Some

reactions may be second-order:
r = k C~ (3-26)
There are also reactions of fractional order, such as the h~'drodealkylation
of toluene to benzene and methane:
• (3-27)
o.s
r= k Cto" C H2 (3-28)
The reaction order has no relationship to stoichiometry. The only time
the order coincides with stoichiometry is when the reaction occurs "as
.
wntten. "
Not mal and Autocatalytic Reactions

A reaction is called normal if its rate falls off with conversion XA (Fig.
3-5). There are some reactions for which the rate may go up with in-
creasing conversion XA and then fall off after having reached a maximum.
18
This is typical of autocatalytic reactioni (Fig. 3-6). Carbon monoxide
oxidation and many aromatic oxidation reactions are autocatalytic:
co + 'h O
2
Pt, Pd, Rd, Ru. CO
2 (3-29)
In an autocatalytic reaction, the rate at the start is low because little
product is present. It increases to a maximum as more product is formed
MOl
I
,
I
r I
I •
I
I
I
I
,XA
FIG. 3-6 Autocatalytic reaction.
•
•
CATALYTIC RE.A.CTOR DESIGN
•
and then drops again to a low value as reactant is consumed. The rate
expression is usually of the form
- rA = k c;. . C;;rodud (3-30)
Here at the right-hand side of the maximum the order is negative.
3.;i
DETERMINATION OF REACTION RATE
The reactor designer needs an accurate expression for the catalytic re-
action rate which has been determined for the catalyst to be used. Al-
though in most cases someone else will make this determination. it is
important that the reactor designer knows how it was done.
The expression needed is of the general type:
Rate = r = f (CA,CB,Cn , T,A,EL (3-31)
where A,B = reactants
3
C = molar concentration, kmoVm
D = reaction product
T = absolute temperature, K
A = frequency factor
E = activation energy, kJ/kmol
•
This expression represents the intrinsic reaction rate.

There are a number of methods for determining catalytic reaction
rates. Some are batch, some are semibatch, and some are continuous.
The Differentk! Flow Reactor

This method of measuring the reaction rate uses a long, thin tube which
has been packed with a small amount of catalyst. It contains thermo-
couples to measure the temperature before and after the catalyst bed.
The tube must be kept absolutely isothermal by a liquid at constant tem-
perature surrounding the tube. High heat transfer is essential for iso-
thermality (Fig. 3-7).
A series of experiments is carried out in this tube at absolutely iso-
thermal conditions while trying to keep the conversion Iow, so that it
may be considered differential conversion. The concentration CA of a key
reactant is analyzed before and after conversion, and actual moi:'r con-
-+>====~~c=======-
CA.·
__ ~
CA Ca
c~ Calal ysl Co T
T.
FIG. 3·7 Schematic representation of a differential flow reactor.
•
•
Slope is rate rA
I
I
I
I
I
FIG. 3-8 Reaction rate as slope of conversion vs. space time curve.
centrations at reaction conditions are calculated. From the~e concentra-

tions, one calculates conversion XA:
1 - (CA/CAD)
or x ... = (3-32)
I + (eAC ...IC AU )
where C...o is the molar concentration of reactant A at the inlet to the

reactor and eA is the fractional change in volume of the system during
complete conversion of reactant A and is defined by
v,
x .... = 1 -
l"x.\ =0
CA = (3-33)
In Eq. (3-33) v' is the volume of the reactants and V;.,~ I means the value
\. •
of V' when x ... = L Now we can plot x.'\ versus V/F, where F is the
volumetric feed rate in cubic meters per second. The V/F ratio is de filled
by V.
- = T = space time (3-34)
F
We can graphically obtain the derivatives of the curve in Eg. 3-8.
Each derivative, or slope at a tangent, is the reaction rate rA at the
corresponding space time and concentration. We can plot these rate data
versus C .. (Fig. 3-9). If the points fall on a straight line, we can say that
rA is directly proportional to CA, or first-order with respect to CA' If the
points f;ln on a straight line but the straight line is parallel to the abscissa,
we can tell that TA is independent of CA, or zero-order. If the points fall
on a curve, then we may have a case of second-order or fractional-order
reaction. The shortest way of determining the reaction order a in such
a case is to consider, as in Fig. 3-10,
r A = k C~ (3-35)
In r A = In k + a In CA (3-36)
•
Zero order
- - Ifsl order
CA
FIG. 3-9 Detellllination of reaction order•
and to plot In TA versus In GA' The sbpe of the line represents the reaction
order 0:. Of course this method will work for fractional-order reactions
and for second-order reactions of the type TA = kG! but will not work
for second-order reactions of the type
(3-25)
Here we can write:
(3-37)
and plot In TA against In GAGB as shown in Fig. 3-11. If the reaction is

of the type of Eq. (3-25), the plot will be a straight line.
The main drawback of the differential reactor is that it must work
with small conversions, and consequently extremely good analyses of
inlet and outlet streams are required. These are not always available ..
One of the best procedures commonly used in s~arching for a rate
equation is differential analysis, which uses a differential reactor and is
more convenient with complex rate expressions.
The design equation for plug-flow reactors
(3-38)
can be rearranged to
dx A
(3-39)
dV/FAo •
· One makes a series of runs in the packed bed of Fig. 3-7, using fixed
feed concentration GAO byt varying FAO such that a wide range of values
for VIFAO and X A is obtained.
· One plots XA vs. VIF AO for all runs (Fig. 3-8).
· One fits the best curve to the XA vs. VIFAO data, making it pass through
the origin.
•
CATALYTIC KINETIC MODElS 61
· The rate of reaction at any value of XA is the slope of the curve at that
value. For each XA value one can find a rate value and a CA value.
· Now all one has w do is to plot TA vs. CA or In A vs. In CA as in Figs.
3-9 and 3-10, respectively.
Differential reactors are discussed in detail by Levenspiel,18 Smith,7
li
and Hougen and Watson.
The Integral Flow Reactor Integral Analysi~

The same packed laboratory reactor shown in Fig. 3-7 can be used as
an integral flow reactor. However, more catalyst can be packed into it,
so that 20% conversion is obtained. Again, the reactor is operated under
isothermal conditions. Another commonly used procedure in searching
for a rate equation is integral anal)'5is which uses the integral flow reactor.
A specific mechanism with its corresponding rate equation is put to
the test by integrating the rate equatiun for the reactor flow conditions.
For this:
· A series of runs is made in a packed bed, with fixed feed concentration
CA!) but with varying catalyst volume \f and/or feed rate FAo, in such a
manner that a wide range of V/FAil vs. x" data are obtained.
· A rate equation is selected for testing and used in integrating the plug-
flow performance equation to give
V x .• dxA
-- (3-40)
•
\, ,
· For each experimental run, the left and the right sides of Eq. (3-38)
are evaluated numerically.
· The results are plotted one against the other and tested for linearity.
Integral analysis provides a straightforward and fast method for test-
•
a slope
1 •
.l"k
h CA
FIG. 3-10 Detexulination of reaction order and reaction rate constant k for
rates depending on a single cC)Dcentration CA'
•
1- >
.4, CA CB
FIG. 3-11 Dtte.mination of reaction order and reaction rate constant k for
rates depending on two concentrations, CA and CB'
ing simple rat~ expressions. However, with increasing complexity, the

integrated forms of the rate expressions be:ome too messy.
In the tubular packed integral reactor, ideally the gas flow, as rep-
resented by either the feed rate FA or the Reynolds number, should be
constant and the reactor length should be varied. However, this is fre-
quently not done, because it is inconvenient to re pack a laboratory re-
19
actor for every data point. Instead, a fixed length of packed bed is
used while attempting to maintain the pressure, the temperature, and
the reactants ratio constant and varyin~ only the flow rate. After such
a series of experiments is completed, further series are run by varying
7
the flow rate at other levels of constant reactant ratio. This type of
reactor must be kept absolutely isothermal or the data obtained from it
will be worthless.
,
.. According to J. J. Carberry,5.19 a tube diameter equivalent to 5 to 6
particle diameters are the maximum to have in the tube to be certain
that isothermality is maintained. However, this conflict" with the general
packed-bed rule that a minimum of8 to 15 particle diameters is necessary
to minimize wall effects. This means that no matter what is done some
error will be made.
The Continuous Stirred-Tank Reactor (CSTR)

The CSTR can be used in the laboratory as a tool for reaction rate
determination. It is normally used for homogeneous reactions. If it is
perfectly mixed, the reaction rate can be obtained b~- materials balance
(Fig. 3-12): -
• ,
_ rA = (3-41 )
In order to adapt the CSTR to heterogeneous catalysts, Carberry de-

veloped his basket-type experimental CSTR.20 In this reactor, catalyst
•
CATALYTIC KINETIC MODRS 63
pellets are placed in wire baskets, which rotate around a vertical axis in
a cylinder full of the reactant gases, The performance equation becomes:
F x"
-= (3-42)
F "I
••
- rA
from which
(3-43)
Here, each run gives directly a \'alue for the rate at the composition of
the exit fluid.
There is an alternate design for a similar reactor with a fixed catalyst
and recirculated gases. However this alternate design costs considerably
more ~han the Carberry• reactor.
The Recycle Reactor

The recycle reactor can also be used in the laboratory as a tool for
reaction rate determination. It uses a plug-flow reactor and converts it
to a backmixed reactor by adding a recycle (Fig. 3-13). Again a specific
kmetic equation is tested bj' inserting it into the performance equation
for recycle reactors
v
- = (R + 1) (3-44)
FAO Rx:\(R+Il
- rA
•
.
The equation is integrated and a plot of the left-hand and right-hand
:>ides of Eq. (3-44) then tests the linearity.
At high recycle ratio R the reactor approaches a CSTR. The most
critical part of the reactor is the pump. According to J. J. Carberry,2!
the best pump is the all-glass pump developed by M. Boudart.
The CSTR and the recycle reactor do not give the best yields, but at
this stage of learning, no one cares about yields it is the rate constants
that are desired.
Laboratory reactors will be discussed in greater detail in Chap. 10 .
•
- --- -
- - - ..
FIG. 3-12 Schematic representation of a continuous stirred-tank reactor (CSTR).

•
x
•
~25
fiG. 3-13 Schematic of a Iecycle
3.4
EFFECTS OF PORE STRU~TURE AND
TPANSPORT PHENOMENA ON REACTION KINETICS
Most solid catalysts are porous pellets, some having internal surface areas
2
as large as 300 m /g or more. This sort of porous structure strongly
affects the kinetics of chemical reactions, not only with respect to reaction
rate but also by favoring certain products over others. We say that pore
, structure affects the selectivity of the reaction.
A typical heterogeneous catalyst pellet is a small solid (spherical, cy-
lindrical, or irregular in shape) containing a multitude of pores. In Fig.
3-14 such a pellet is shown with exagerated pores. Gases or liquids which
surround the pellet diffuse into the pores, where they react on catalyt-
!cally active sites; the products of the reaction diffuse back to the bulk
phase and are transported by the bulk phase.
Because the actual catalytic reaction takes place 011 the active sites of
the catalyst surface, which are mostly inside the pores, both the tem-
perature and the concentratio~s may vary between the bulk phase and
,
--
the pores.
All properties related to the space inside }he pellets are called intra-
phase properties, while all properties related to the space between pellets
are called interphase properties.
The Global Rate of Reaction

The global rate of reaction is the rate that can be measured. It includes
also the mass transfer. The simple case is a nonporous solid catalyst
plate, as shown in Fig. 3-15. A reactant of initial concentration Co may
approach the solid. The solid is assumed to be covered by a fictitious
film E)f thickness S, which represents a sort of resistance to the reaction
on the surface. The reaqant will penetrate the film and will be adsorbed
on the surface; its surface concentration will then be Cs. The rate of
•
surface reaction will be: _
(3-45)
•
•
CATAlYTIC I(lNETIC MODElS 65
where k = reaction rate constant (units vary according to a)

a = reaction order .
kg = mass-transfer coefficient, m1s
a = the ratio of surface available per unit volume of reactor space,
2 3
m /m
Equation (3-45) simply states that the number of moles of reactant con-
sumed by the surface reaction is equal ~o the number of moles trans-
ferred through the film to the catalyst surface. The coefficient kg is a
phenomenological coefficient, which is also related to the diffusivity D
of the reactant by:
(3-46)
With increasing flow or with increasir,g Reynolds number Re: •
5 )0
Let us solve Eq. (3-45) for Cs. If a = 1, Eq. (3-45) is first-order. Then
C, can be extracted from it:
(3-47)
Substituting C, from Eq. (3-47) into the rate equation ~ = kC, gives:
~ = kCo (3-48)
•
, I + (k/kga)
•
A
B
FIG. 3-14 Schematic representation of a porous catalyst pellet.
-
'---__
• Co
-------------.------
Cs 8 Film Ihi~kness
~
Solid plote
FIG. 3-15 Schematic representation of a nonporous catalyst.
•
•
In Eq. (3-48), the expression kl[ I + (klkga)] is the experimental value of

the rate constant. Thus. this' whole expression, not just k, is the rate
constant.
At low temperatures kga > k; (klkga) ~ 0; ~R = kC o and
kexpcrimcntai == kjflt.rinsk
At higher temperatures kga < k; kI[ 1 + (klk"a)] = (k . kga)/(k[!a + k) )

(k • kga/k) = kga; 5R = kgG Co and
To express the relationship between the experimentally measurable

global reaction and the intrinsic reaction rate we will define an external
5 21
effectiveness factor 1lx • ;
('
.K -- ~\' k CIJ (3-49)
where
I
(3-50)
The dimension of k for first-order reaction is seconds-I. Here the ratio

klkga is dimensionless and is called the Damkohler number (Da). It expresses
the relationship of the chemical reaction to the mass transfer.
The external effectiveness factor 11x should not be confused with the
intraphase effectiveness factor TJ.
" If 11x is plotted against the Damkohler numbel' ;)0 a double logarithmic
chart, the curve on Fig. 3-16 is obtained. The factor 11x can also be
computed in cases of reaction orders different from 1 and plotted on
the same Fig. 3-16. We see that the diffusion intrusion is the more serious,
22
the higher the order of reaction.
If we investigate the Arrhenius relationship of the experimentally
measured reaction rate
(3-51 )
by plotting In kx against IIT in Fig. 3-17, we see that at low temperatures

(high liT), the slope of the curve is - ElRc, where E is the activation
energy of the catalytic intrinsic reaction. At intermediate T we have a
mixed phase with a flatter curve. At very high temperatures (low liT)
most of the reaction will o€cur in the bulk gas phase rather than on the
surface, and we will be measuring the intrinsic reaction rate in bulk gas
phase. Then E will be the activation energy of the thermal reaction and
kexperimental = kintrinsic. thermal' This means that if the measured activation en-
•
CATAlYllC KINETIC MODELS 67
•
10
•
0.Q1 0.1 1.0 10

Do
FIG. 3-16 Plot of the isothellllal extelllal catalytic effectiveness factor for
reaction order a as a function of the Damkohler number Da. (From Cassiere
and Carben'Y,22 by pel mission from the American Society for Engineering E iucation.)
erg)' E is found to be low in studying a reaction, considerable diffusion

is involved.
k
(3-52)
Equation (3-52) works with all reaction orders. In a pure diffusion re-
gion, all reactions appear to be first-order. By obtaining 1), from ob-
servable rate data, it is possible to calculate the real order of the reaction.
Let us consider again a flat catalyst plate (Fig. 3-18). However, let this
be a porous plate instead of the nonporous one of Fig. 3-15. With the
•, •,
porous plate wc' en study the intra phase aspect of the heterogeneous
reaction rate. In order to correlate the observable reaction rate constant
kexperimemal v.;ith kimrinsio we define an effectiveness facto!- 1) .
1) = ---- (3-53)
k.C.
which under isothermal conditions tends to
- lli = ----~ 1.0 (3-54)

C,
Here dl is a differentia!' distance and L is a characteristic dimt:nsion of

the particle.: •
volume of particle - 1
L = - -
external surface area a
•
___ k, =kjnlrinsit
•
I
Thermal I
reaction I
t
I
I I
.l., k ~ I I
Bulk phase I Mixed phose I
I
Intrinsic
I
I I (catalytic!
I I
I I Slope:-t
I I
I t
liT
fiG. 3-17 Arrhenius plot for the experimentally measured reaction rate con-
stant k. in a nonporous catalyst.
Thus
At nonisothermal conditions
1]nonisothennal ~ 1.0
The rate of diffusion of the reactant equals that of its consumption

by the reaction; therefore we can write
2
d L'
D df = kCU (3-55)
For first-order reaction, a = 1 and we have:

,
tf~
-'
D = kC (3-56)
dl ..
We may use the dimensionless forms of some quantities:

1
f = C z =- (3-57)
Cs L
With these quantities, Eq. (3-56) becomes
or (3-58)
-
The value of the quanti,ty in parentheses on the right-hand side of Eq.

(3-58) is equated to qJ2, qJ ~eing the well-known Thiele modulus. Analytical
23
solution of Eq. (3-58) by a complicated and lengthy procedure gives:

tanh qJ
1]; = (3-59)
qJ
•
where tanh 'I' is the hyperbolic tangent of <po A hyperbolic tangent of a

quantity 'I' is given by the relationship:
<P -,.
e - e
tanh 'I' = -q:---_-,. (3-60)
e + e
Let us plot tanh 'I' against 'I' in Fig. 3-19. We see that tanh 'I' increases
almost proportionally to 'I' up to about 'I' = 1, and then fhttens out and
approaches tanh 'I' = 1 asymptotically. Thus
for 'I' < 1 tanh 'I' == 'I'
for 'I' > 3 tanh<p = I
Let us now plot 'T] against 'I' in Fig. 3-20 on double logarithmic paper.
We see that for 'I' < 0.2, 'T] == 1. Then the curve begins declinip.ci; above
about <p = 2 it becomes a straight line and Eq. (3-59) gives 'T]; = 11'1"
When the modulus 'I' is small, the effectiveness is close to unity and
the experimental reaction rate approaches the intrinsic reaction rate:
ill = 'T];kC, ) kC,
where the rate is directly proportional to the intrinsic rate constant k.

When, however, 'I' > 3, the effectiveness facwr is quite small and
equals 1/'1'. The experimental reaction rate is given by:
ill = kC,I<p = kC,IL(klD)o.s = (kD)O.5 C,IL (3-61)
We see that for low effectiveness factors the experimentally measured

reaction rate ~R becomes proportional to the square root of the reaction
rate constant. This means that the reaction slows down.
When the natural logarithm of kx for a reaction over a porous catalyst
is plotted against liT in Fig. 3-21, we observe no effect of particle size
at low temperatures, where diffusion is negligible. The slope of the
Arrhenius line is - EIR and the true activation energy E is obtained.
However, at high temperature (low liT), where diffusion in pores be-
C(Xl
Tlxl
•
Gradienl ole
•
1
FIG. 3-18 Concentration gradients in a porous catalyst plate as a function of
distance I from exterior surface.
•
•
1.0
0.8
...
.c:
0.6
co
E 0.4
0.2
1.0 2.0 3.0 4.0

Thiele modulus,
FIG. 3-19 Plot of tanh 'P vs. 'P.
comes significant, the slope of the Arrhenius line is - El2R, or half the
value at low temperatures. Hence the apparent activation energy meas-.
ured at high temperatures would be half the true acti\'ation energy.
For further information on kinetics and effectiveness of porous ca-
talysts, the reader i~ referred te the excellent treatment of the subject
in Carberry's book."
Yield and Selectivity in Complex Re'ilction Systems

Let us consider two types of reaction systems: consecutiye reactions and
24
simultaneous reactions :
~B
A
•
'. ~C
Consecutive reactions SimMltaneous reactions
In the above schematic equations, subscripts 1 and 2 denote the first

and the second reaction, respectively. In consecutive reactions, the product
B of the first reaction becomes the feed to the second. In simultaneous
reactions, however, fractions of the same species A react simultaneously
according to the two different reaction rates and produce products B
and C.
The yield Y of a reaction is the ratio of the rate of generation rB of a
desired product to the rate of consumption r .... of a key reactant at any
point within the reactor.
The selectivity S at any point of a reactor is the rate of generation rB
of a desired product to the rate of generation re of some undesired
- product.
(3-62)
•
Yield and selectivity are important parameters for the reactor designer.
Under isothermal conditions we can set
(3-C3)
The reaction step 1 is assumed to be a order, while the reaction step 2

is j3 order. The expressions for yield and selectivity can be written as
24
follows :
Y, = - (dCBldC A ) = 1 - (lIK')(C~iG.) (3-64)
Yield
Y, = - (dCsldC,d = 1/0 + c~-aIK') (3-65)
Se = (dCBIdCd = K'(C~/C~) - I (3-66)

Selectivity
S, = (dCsldCd = K' C~-f3 (3-67)
where subscript c and s denote consecutive and simultaneous systelT's,
respectively.
.,.. 1.0
~ 0.7
~
~ 0.5
'">
~ 0.3
:::
L..J
0.2
O. 1 _~----'L-.J_
0.1 0.2 0.4 0.6 1.0 2.0 4.06.0 10.0
Thiele modulus "
FIG. 3-20 Plot of effectiveness factor versus Thiele modulus.
Slope:- E
2R
I
I
I I
I I
I
I I
I I
Effect of L No effecl of L
h kl I
I
I
I
I I
I I Slope = - -
E
I - I R
I I
I I
I I
lIT
High temperature Low temperatures
FIG. 3-21 Arrhenius plot for the experimentally measured [·eaction rate con-
stant k. in a porous catalyst.
•
72 CATAlYTIC REACTOR
Under nonisothermal conditions we can write:

•
Tt)
- - 1 (3-68)
T
where subscript 0 refers to isothermal conditions.

By setting t = (TITo), which is the reduced tempera~ure, and
A _ E2 - El
u€ - RTo
we obtain a simpler expression:
K' = K exp 6.€ !

o t
rL - 1 (3-69)
Here 6.€ refers to apparent rather than intrinsic E difference. Thus yield
and selectivity depend on relative reaction order and actintion energy
, difference 6.€ for a given 6.H change and thermal capacity of the fluid.
For simultaneous reactions, yield is 6.€-dependent and sensitive ro
relative order as long as Cl =1= (3.
NOMENCLATURE
a Ratio of external surface area to particle volume, m-I
A Frequency factor or preexponential factor (dimension de-
pends on reaction order)
3
\.:. , C Molar concentration, kmollm
3
Co Initial or inlet molar concentration, kmollm
3
Cs Molar concentration on the surface of the catalyst, kmollm
Da Damkohler number, dimension less
E Activation energy, kJlkmol
f Dimensionless concentration = CIC,
3
F Volumetric feed rate, m /s or rate ratio of poisoned to non-
poisoned reactions, dimensionless
k Reaction rate constant
Adsorption rate constant
•
Desorption rate constant
-
Mass-transfer coefficient, m/s
Experimentally measured reaction rate
Adsorption equilibrium constant
•
K' Ratio of reaction rates = kl/~
I Distance from porous catalyst surface, m

L Ratio of particle volume to external surface area, m
-
p Partial pressure, Pa or bars (1 bar = 1O~ Pa)
r Reaction rate
R Gas cmlstant = 8.314 kJ/(kmol . K) or recycle ratio in recycle
reactor
Re Reynolds number, dimensionless
3
Rate of global reaction, kmoV(m . s)
s , dimensionless
Selectivitv,
t Tim~, s (unless specifically indicated otherwise)
3
V Catalyst volume, m
3
V' Volume of reactants, m
x Conversion, dimensionless
y Yield, dimensionless •
z Dimensionless distance from catalyst :;urface = IlL

0: Reaction order or fraction of pore surface poisoned
Apparent activation energy difference
Fractional change in volume of the system during complete ,
•
converSIOn
Intraphase effectiveness factor, dimensionless
TJi Intrinsic ellectiveness factor under isothermal conditions,
dimensionless
TJx External effectiveness factor, dimensionless
e Surface coverage of catalysts, i.e., fraction of catalyst surface
covered by an adsorbed chemical species
7 Space time
Thiele modulus
•
•
Subscripts
AB Species A, B
C Consecutive
•
Prod Product
S Simultaneous
REFERENCES
l. Robert W. Coughlin, "Classifyinb Catalysts Some Broad Principles." fnd.
Eng. Chem. 59(9):45-57 (1967'.
2. R. Winkoop and R. H. Wilhelm, "Kinetics of Tubular Flow Reac-
tors Hydrogenation of Ethylene 0'1 OI-MgO Calalyst," Cium. Eng. Progr.
46:300-310 (1950).
3. Michel Boudart, "Kinetics and Mechanism of Catalytic Re:'ctions," ludo chim.
beige, 23:383-396 (1958). (Note: Data were converted to SI units by the author
of this book.)
4. S. Brunauer, P. H. E'llmett, and E. Teller, "Adsorption of Gases in Multi-
molecular Layers," J. Am. Chem. Sac., 60:309-319 (1938).
5. James J. Carberry, Chemical and Catalytic Reaction Engineering. !\tcGraw-Hill,
New York, 1976.
6. A. R. Cooper and G. V. Jeffreys, Chemical Kinetics and Reactor Design, Prentice-
Hall, Englewood Cliffs, N .j., 1971.
7. J.M. Smith, Chemical Engineering Kinetics, 2d ed., McGraw-Hill, New York,
1970.
8. S. Brunauer, K. S. Love, and R. G. Keenan, "Adsorption of Nitrogen and
the Mechanism of Ammonia Decomposition over Iron Catalysts," J. Am.
Chem. Soc., 64:751-758 (!942).
. ,
9. G. Halsey and H. S. Taylor, "The Adsorption of Hydrogen on Tungsten
Powders," J. Chem. Ph)'s., 15:621 630 (1947).
10. Otto Beeck, "Catalysis and the Adsorption of Hydrogen on Metal Catalysts,"
Advan. Catalysis, 2:151-195 (1950).
11. E. Rideal, Surface Chemistry, Cambridge Press, 1930.
12. D. Hayward and B. M. W. Trapnell, Chemisorptioll. Butterworth, London,
1964.
13. Ahlborn Wheeler, "Reaction Rates and Selectivity• in Catalvst
•
Pores," Admn.
Catalysis, 3:250-326 (1951).
14. Edward B. Maxted, "The Poisoning of Metallic Catalysts," Adt'an. Catalysis,
2: 129-178 (1951); "The Nature of Chemisorption Bonds. I. Some Observed
Regularities,"]' Che:;I.'SOC., 1987-1991 (1949); E. B. Maxted and A. Marsden,
"Catalytic Toxicity and Chemical Structure. VI. Poisoning of Pt-Metals by
Metals," Ibid., 469-474 (1940); E. B. Maxted and Robert \\'. D. Morrish,
"Catalytic Toxicity and Chemical Structure. V. Simple Anions Containing
Toxic Elements," Ibid., 252-256 (1940); "Catalytic Toxicity and Chemical
•
CATAlYTIC KINETIC MODELS 75
Structure. VII. Elimination of Catalyst Poisons by Conversion into Deriva-

tives of Shielded Type," Ibid., ·132-136 (1941).
15. John B. Butt, "Catalyst Deactivation," in Chemical Reaction Enginee,ing, Ad-
vances in Chemistry Series, no. 109, 1972, pp. 259 496.
16. John B. Butt and R. M. Billimoria, "Catalyst Deactivation," in Chemical Re-
action Engineering Reviews Houston, American Chemical Society, Symposium
Series no. 72, 1978, pp. 288-322.
17. Olaf A. Hougen and Kenneth M. Watson, Chemical Process Principles, part
3: Kinetics and Catalysis, John \viley, New York, 19-i7.
18. Octave Levenspiel, Chemical Reaction Enginuring, 2d ed., John \Viler, New
York, 1972.
19. J ames J. Carberry, Unpublished notes from the First Catalytic Reactor De-
sign Course at Lehigh University, Bethlehem, Pa.,June 21,1971.
20. James J. Carberry, "Designing Laboratory Catalytic Reactors," fnd. Eng.
Chem., 56(11):39 46 (1964).
.
21. James J. Carberry: Unpublished notes from the "Catalytic Reactor Design
Course" at Pocono Manor, Pa., June 19, 1972.
22. G. Cassiere and James J. Carberry, 'The Interphase Catalytic Effectiveness
Factor: Activity, Yield and Non-isothermalitv," Chem. ":ng. Educ., Wimer pp.
22-26, 1973.
23. E. W. ThieIe, "Relation between Catalytic Activity and Size of Particles," fnd.
Eng. Chem., 31(7):916-920 (1939).
24. James J. Carberry, "Yield in Chemical Reaction Engineering," fnd. Eng.
Chem., 58(10):40-58 (1966).
•
•
•
TRANSPORT PHENOMENA
Chapter
FIXED-BED GAS REACTORS
Fixed-bed gas reactors will be the subject of this and next chapter. First,
the concept of fixed bed must be defined.
4.1
DEFINITION
A fixed-bed reactor is a chemical reactor containing a bed of solid catalyst
particles that is filled into a usually cylindrical vessel and stays there until
it is dumped. However, the stay of the solid catalyst in the reactor vessel
is by no means eventless. The catalyst activity changes with time. Nor-
. . mally activity declines from some kind of surface "fG"uling, coking, or
poisoning. It is also possible for activity to increase at the beginning
before it starts to decline. The designer must make a judgment as to
how much the activity should be allowed to decrease before something
has to be done with the catalyst. Either the catalyst charge is dumped
and a fresh catalyst charge is filled into the reactor, or the spent catalyst
is regenerated in situ. The choice is of course dictated by economics
(price of catalyst, loss of on-stream time by regeneration in situ, cost of
regeneration equipment, etc.) It is also possible to dump the catalyst,
regenerate it somewhere else, and recharge it later.
Most catalysts lose some of their activity on regeneration. Figure 4-1
shows the change in cata:lyst activity with time in a typical fixed-bed
reactor. In the first hOl..\.rs and days of the operation activity declines
fairly rapidly, but thereaf!er the rate of decline is slower. When activity
reaches a point at which it is uneconomical tG use the lOuled catalyst,
the bed is regenerated, either in situ or outside the reactor. \Vhen the
regenerated catalyst is put back on stream, its initial activity is somewhat
below the initial activity of the first period ef use. Consequently, after
•
17
•
ACliyily decline per compaign
---,---------------
-.-
.>-
-
u
co
Fir:! campaign
Second
•
campOlgn
-o
-o
<..> Shldown and
regeneration - _
Time. days on stream

FIG. 4-1 Change in catalytic activity in a fixed bed.
a number of regeneratiom the catalyst beu must be dumped and fresh

catalyst must be charged. That is the extent to which a so-called fixed
bed is reallv, fixed.
,
4.2
CLASSIFICATION OF FIXED-BED GAS REACTORS
Fixed-bed gas reactors can be classified into three categories:
1. Isothennal reactors, which remain at the same constant temperature
•
at every pomt.
2. Adiabatic reactors, which exchange no heat with the surroundings. If
an exotheI mic reaction is run in an adiabatic reactor, the temperature
• of the gas stream will increase from the inlet toward the outlet. If,
on the other hand, an endothermic reaction is run in the same reactor,
the fluid temperature will drop along the reactor length.
3. Nonisothermal, nonadiabatic fIXed-bed gas reactors, which are sidewall-
cooled or sidewall-heated and usually are bundled up like heat ex-
changer tubes. This type of reactor has an extremely long, awkward
name, which can be shortened to the more convenient acronym
NINAF reactor. The acronym is made up of the first letters of the full
l
name. The temperature in KIKAF reactors varies from one point
to another and heat is exchanged with the surroundings through the
side walL •
In order to begin with the process design of any type of reactor, the
designer must have complete information on transport phenomena in
the reactor. Therefore, this chapter will discuss this kind of information
for fixed-bed gas reactors.
Transport phenomena in a fixed bed of catalyst can be classified in
two categories: those which occur in the void space in the catalyst bed
•
TRANSPORT PHENOMENA IN FIXED-BED GAS REACTORS 79
are called interphase phenomena, while those which occur inside the catalyst
pores and on the surface of the catalyst are called intraphase phenomena.
4.3
INTERPHASE TRANSPORT IN FIXED-BED GAS REACTORS
Interphase transport phenomena in fixed-bed gas reactors include mo-
.mentum transport phenomena, mass-related transport phenomena, and
heat-related transport phenomena. The expression mass-n:{atl'd strictly
means "concentration-related."
Interphase Flow of Gas

• •
We are interested in the resistance to gas flow when Cl (Tas ~
IS passmg
through a fixed bed and in the uniformity of this flow.
Pressure Drop across Fixed-Bed Gas Reactors

The resistance to the gas flow is measured by the pressure drop across
2
the bed. The pressure drop is given by the well-known Ergun law
(~P/Zg() = 150 X 10-"0 - £fI-LUm/(E:\d~)
+ 1.7S X
5
10- 0 - 3
£)Gu m /(E d p) bars/m (4-1)
where tlP = pressure drop, force units, bars

Z = height of bed, m
\. g, = force-to-mass conversion factor = 1.0 kg' m,i:-': . S2)
'" i
G = mass flow rate of fluid = up, kg/(s . m!!)

E = fractional void volume in bed, dimensionless
I-L = absolute viscosity of fluid, Pa . s = kg/(m . s)
Urn = superficial fluid velocity based on empty reactor cross
section, measured at aye rage pressure bet\\'een inlet and
outlet, m1s .
dp = effective diameter of particles, rn, as defined bY
(4-2)
•
2
Ac = cross-sectional area of the empty reactor. m
• 2
S, = total geometric surface area of the solids (catalysts), m
.
u = superficial fluid velocity based on empl~' reactor cross
section, m1s
p = density of fluid (gas), kg/m3
,
•
The bar. which is very close to 1 atm, was selected as the SI unit for
5
pressure. This is what required the factor of 10- in the right-hand side
of Eq. (4-1).
'.
o
o
00
00 " Radial Distribution of Axial Flow Rate

" -<
•
!,~-,
It was first learned in the early 1950s that the distribution of gas flow
•
3
"""-
,
"-,
through packed beds of catalyst is not uniform. Schwartz and Smith
",
r ,-
o
found that gas flow at the reactor wall and at the reactor center is the
lowest and that it ;ncreases considerably along a ring located approxi-
,
,,. mately one catalyst particle diameter from the reactor wall. Figure 4-2
,, , ,
"
, shows four velocity profiles in pipes packed with IIB-in (3.1i-mm) and
,
{ 'v'
i/4-in (6.35-mm) "square cylinders" (a square cylinder is a cylinder with
r·",
'~'f -,
,
,
~--"
'.-
equal height and diameter). The abscissa represents the radial pos:tion
or the ratio 2rlD r and the ordinate represents vlu where: •
r = distance from reactor axis or radial position, m

Dr = reactor inside diameter, m
v - point velocity at a distance r from {he axis, m/s
u = average or superficial velocity through the reactor, m/s
This profile becomes flatter with increasing Dr and decreasing particle
diameter dp- For small aspect ratio Dr/dp the rilaximum flow was found
to be as high as double the flow at the reactor axis. On the other hand,
for aspect ratios greater than 30 and a uniform velocity through the
reactor, the profile diverged no more than 20% from the true flow
profile. .
This study suggested that the void fraction £ (the ratio of ,'oids to the
total bed volume) in a packed bed is constant at its minimum value up
to a distance of two particle diameters from the wall. Then £ increases
4
up to 1.0 at the wall. This conclusion has been yerified by M. R. Shaffer.
5
Benenati and Brosilow showed that the void fraction in a bed of spheres
decreased from 1.0 at the wall to a minimum of 0.23 according to a
damped oscillation function toward the center of the reactor.
Schliindero calculated the gas flow in the high and low void areas of
the reactor cross section and estimated the fraction f of the cross-sec-
tional area with the larger voids near the wall:
(4-3)
•
In most industrial-size gas reactors f should be ::;0.01. Consequently,
the reactor designer caii for all piactical purposes assume the gas flow
in commercial catalyst beds to be uniform. The error by doing so would
probably be much less than the error caused b, inadvertently stepping
•
TRANSPORT PHENOMENA IN FIXED-BED GAS REACTORS .,
1.4
1.3 •
Velocity profiles for 2-in pipe Velocity profiles for <Hn pipe
1.2
. . . .
::>
......
,.
"1.0 1/8-in cylinder
.
1I8-in cylinder
0.9
O.B
0.7 . '.
1.2 2-in pipe

4-in pipe
1.1
10
1I4-in cylinder.
09 ,- -'
::>
...... 1/4-in cylinder •
,. 0.8
•
0.7 j
•
,,
06 ,
,,
0.5 I I I I I I I
0 0.2 0.4 0.6 O.B 1.0 0 0.2 0.4 0.6 0.8 1.0
Radial position 21/0T Radial position 2r/OT
FIG. 4-2 Velocity profiles in fixed beds. (Adapted from C. E. Schwartz and J.
M. Smith, "Flow Distribution in Packed Beds," Ind. Eng. Chem., 45:1214-1215
(1953), by pellnission.)
•
on the catalyst bed during catalyst charging and thus compressing some
, . parts of the bed.
For most labontory and pilot-plant reactors f will be greater than
0.3. The nonuniformity of gas flow through such reactors does not
present any serious design problems, since such reactors are almost al-
ways overdesigned to allow experimentation over a broad range of pa-
rameters_ However, it is of serious concern to those who must interpret
the data collected in these small reactors_ This is one area where the
reactor designer should very carefully scrutinize the pilot data obtained
to make certain that proper allowance has been made for the correct
flow conditions in the pilot-plant reactor results.
Interphase Mass Transport Phenomena

•
Phenomena related to tj1e transport of mass, i.e., variation in concen-
tration of chemical species, in the '-oid space of fixed-bed gas reactors
include the radial dispersion of mass, the axial disper:,ion of mass, and
interphase mass transfer.
•
r,,'.
0)
-.-
",> ••
Radial Dispersion of Mass
\\/ Besides the radial variation 'of the bulk flow of gas in the catalyst bed~
, --'
,'..
"
•.•. '.' there is a different type of radial variation of mass flow, namely radial
." :<. dispersion. Radial dispersion is just a particular aspect of a general mass
.
," ~-c.' - ,_ ..
", ••
,
,- " backmixing phenomenon that occurs in fixed-bed reactors as a result of
--'--
•
a combination of molecular diffusion and bulk flow turbulence in the
" •
•
tortuous path of the fluid through the catalyst bed. The backmixing in
• , -- <
the axial direction is called axial dispersion and that in the radial direction
'---:
--- ---
-../-
"
is called radial dispersion. The tatter will be discussed first.
In industrial-size reactors in which no heat is exchanged with the
outside, radial dispersion of mass does not create any significant con-
centration gradients and hence is neglected in design. HO\\'ever, radial
dispersion must be taken in consideration in NINAF reactors. in which
both concentration gradients and temperature gradients exist in the
radial direction.
Radial dispersion of mass in fixed-bed gas reactors is usualh exrressed
by a dimensionless group, the radial Pee/et numler for mass flow .8:
(4-4)
with dh = Dr/(l.S (Drldp)(1 - E) -+ I] (4-5)
where dh =-= hydraulic diameter. m
u = superficial velocity of gas, m/s
dp = catalyst particle diameter, m
, Dr = reactor inside diameter. m .
~\ = radial dispersion coefficient, m /s 2
Pe", is the product of the Reynolds and Schmidt numbers:

Re'Sc = Pe m (4-6)
At low Reynolds numbers Pe", is proportional to Re. HOKever, at tur-
bulent flow (Re> 40) Pe", becomes independent of Re and acquires a
constant value of about 10. Although different theories and experimen-
tal results suggest a constant between 8 and 12, the reactor designer can
confidently use the value Pe m = 10. This subject is thoroughh' discussed
in Chaps. 4 and 10 of Carberry's book.s
•
•
Axial Dispersion of Mass
~
The mass dispersion in the axial dii'ee-!ion can be expressed in two ways:
1. A backmixed fixed-bed can be compared with a system of perfectly
mixed reactors in series, such as a series of CSTRs. If it is completely
backmixed, we can say that it is equivalent to one CSTR. As we
• •
•
increase the number n of CSTRs in series, the corresponding fixed-

bed system becomes less and less backmixed, and finally an infinity
ofCSTRs in series (n = 00) corresponds to a perfeclt plug-flow reactor,
in which there is no backmixing at all.
2. The backmixing in a fixed-bed reactor can also be expressed by an
axial Fidel number for mass Pea which is a dimensionless group
Pea = dpul'l\ (4-7)
where ':1\ = axial dispersion coefficient for mass in square meters per
second.
Carberry and Wender' studied and discussed the significance of Pe"
in adiabatic as \\"ell as in nonadiabatic fixed-bed reactors. They found
that the effects of axial dispersion of mass and heat upon conversion
appear to be negligible for practical industrial red lengths. For any bed
length ZT greater than about 50 particle diameters,
Pea = 2.0 (4-8)
Only very shallow industrial reactors or small la!.>orat:JrY reactors deviate
from this fixed ,"alue. Thus, axial dispersion in fixed beds can be com-
pletely neglected in reactor design. It will be seen in Chaps. 5 and 7 that
axial dispersion is completely omitted from design calculations.
The two types of expressions of axial dispersion of ma~s are related
lo ll
as follows . :
(4-9)
where n is the number of equivalent CSTRs and ZT is the reactor bed
• lerigth in meters .
"
Interphase Mass Transfer

The concentration of the key reactant on the external catalyst surface
in a fixed-bed gas reactor is related to the concentration of the same
reactant in the bulk gas phase by the equation:
kga (C - C.) = 1l1k1C; = ~Ii. (3-45)
where kf{ = interphase mass-transfer coefficient. m/s

a = ratio of external particle-surface-area/particle-volume, m-I
C, = concentrativn of key reactant on exterior particle surface,
kmol!m~
••
111 = effectiveness factor of reaction I

kl = reaction rate constant of reaction I
J
- reaction order
•
84 CATAlYTIC· REACTOR
The left-hand side ofEq. (3-45) expresses the interphase mass transfer
and the right-hand side expresses the depletion of the key reactant by
the global reaction gt as observed from the catalyst surface. The left- .
hand side of Eq. (3-45) is the product of a driving force, C - Cs> by a
constant value kga.Since the constant a can be easily measured for any
catalyst, we will be mainly interested in kg. Some aspects of the relation-
ship represented by Eq. (3-45) have already been discussed in Sec. 3.4,
including the derivation of the Damkohler number from it. In Sec. 5.3
we will use this relationship in the design of the NINAF reactor in the
form
C = C, [(1}1 k/kga) + 1] = C, [Dam + I] (4-10)
This is the desired relationship between the bulk gas concentration C

and the c::mcentration C, of the key reactant on the catalyst surface. This •
relationship is further improved by making it dimensionless. Let us di-
vide both sides of Eq. (4-10) by the inlet concentration Co and let us set:
C,Ir:o = Cn = reduced concenn-ation on catalyst surface
CICo = C r = reduced concentration in the bulk gas phase
Thus, we can write:
(4-11 )
where Da., = Damkohler number for mass. Dam relates the effective
reaction rate to the interphase mass transfer. In the following we will
be mainly interested in the interphase mass transfer coefficient kl{ and
\ in its calculation.
Ergun 12 and CarberryI3.14 reviewed past studies on kg and Carberry
arrived at the following correlation, based on a "developing boundary
layer concept":
JD = (kglu)e Sc~' = 1.15 Re-I,.. = JH = (hlpcpu) Pr'" (4-12)
where JD = J factor for mass

JH = J factor for heat
u = superficial velocity, m1s
e = void fraction, dimensionless •
Sc = Schmidt number = ~pDI"" dimensionless

•
= viscosity, Pa . s
-
Dim = molecular diffusion coefficient for diffusing species in
multiple component mixtures, m 2/s
3
p = gas density, kg/m
•
TRANSPORT PHENOMENA IN FIXED-BED GAS RE,J\CTORS 85
Re = Reynolds number = dpG/~, dimensionless

G = mass velocity of gas, kg/(m2 . s)
2
h = interphase heat transfer coefficient, kj/(m • s . K)
cp = heat capacity, kJ/(kg . K)
Pr = Prandtl number = Cp~Ag, dimensionless
Ag = thermal conductivity of gas, kj/(s' m . K)
Equation (4-12) shows that the mass-transfer coefficient R.I( correlates
not only with the flow characteristics of the gas, as expressed by the
Reynolds number, but also with the heat-transfer coefficient h. The
applicability of this correlation has some limits, however:
1. It is applicable below the Reynolds number, corresponding to tur-
bulent boundary-layer development, which probably has a value of ,
se\'eral hundred 13 •
"C>, ""
~.,
I
'I w"?','e / ' --'; ',':;::;1 / ' " ,,' li' ",
n-"
""'ul~-:""'~'
\\'~""_'-,j",,,\
',_
\"";:) ''''", ,-
'~
'.
2. It is applicable in the region where radiant heat transfer is negligible. v

Radiant heat transfer would at least do away with the correlation
between mass and heat transfer. The effect of radiant heat will be
discussed further below.
Interphase Heat Tt ansport

Heat transport phenomena in the void spaces of the catalyst bed include
the radial dispersion of heat, the transfer of heat between the catalyst
surface and the bulk gas, and radiant heat transfer in the bed.
Radial Dispersion of Heat

The general backmixing phenomenon in fixed-bed reactors, which we
already discussed in relation to mass dispersion, also causes some radial
dispersion of heat. This heat dispersion is of no practical consequence
in isothermal and adiabatic gas reactors. However, it must be definitely
taken into account in sidewall-cooled NINAF reactors.
The radial dispe~~~()n of heat is eA-pressed by a radial Peelet number
for heat flow:
•
(4-13)
where Kr is the radial dispersion coefficient for heat in square meters
per second. The value of Peh lies between 5 and 10. In Chap. 5 we used
a value of Peh = 7.
•
Interphase Heat Transfer

The temperature of a key reactant on the external catalyst surface in a
fixed-bed gas reactor is related to the temperature in the bulk gas phase
by the equation:
ha (Ts - T) = (- tlH) 9{ (4-14)
where h = interphase heat tr~nsfer coefficient, kJ/(m 2
• s . K)
( - JlH) - reaction heat, kJ Ikmol
T = temperature of the gas in the bulk phase, K
T, = temperature on catalyst surface, K
a = surface area-to-volume ratio for the catalyst, m-I
Equation (4-14) can be rearranged into
T, = T + [(-tlH)~Klha] (4-15)
which can be made dimensionles" by dividing both sides by .. he inlet

temperature Tn:
(TjTfI ) = (TlTn) + [(-tlHYRIT"ha] (4-16)
If we set (TJTfI) equal to T", the reduced surfare temperature of catalyst,

and (T1To) equal to TT' the reduced temperuture in the bulk gas phase,
•
we can wr~te
.
(- tlH)~R
T" Tr + ahTo ( 4-17)
• ,
• =
The term (- tlH)Yl..lahTo is another dimensionless ~roup relating the heat

produced by reaction (numerator) to the interphase heat transfer (de-
nominator) and is called the Damkiihla 1wmberfor heat:
( 4-18)
Equation (4-17) will be used in the NINAF reactor design problem in

Chap.5.
The interphase heat transfer coefficient can be calculated from the
correlation of theJD andJH factors in Eq. (4-12). As mentioned abm'e,
Eq. (4-12) is not applicable to turbulent flow conditions or to high tem- .
l5
peratures at which radiant heat transfer becomes significant. Martin
•
used a different approach to obtain h. He had observed that for low
-
Peclet numbers most or the experimentally obtained particle-to-fluid
heat transfer coefficients in packed beds were several orders of mag-
nitude below the values predicted for a single spherical panicle in cross
flO\,'. Martin attempted to establish a relationship between the heat trans-
•
TRANSPORT PHENOMENA IN FIXED-BED GAS REACTORS 87 ,
fer coefficient of the single particle and that of the packed bed and to
calculate the latter from the fprmer. In the range Pe > 100 the N usselt
number of a packed bed can be calculated from the following equations:
Nu = [1 + 1.5(1- E)] . r\u" (4-19)
NUl' = 2 + F· (Pe/E)'" IY',· (4-20)
where Nl1 is the !\usselt number for the packed bed = lld/A and Nul' is
the Nusselt number for a single sphere and equals ht/VA, A being thermal
conductivity. In the laminar region the factor F has values between 0.6
and 0.664 as found by different workers. For intermediate turbulence
l6
le\'els. F can be calculated from Gnielinski's correlation :
0.0557 (Re/E )11:1 Pr"1
F = 0.664 I +
I + 2.44(Pr"I - 1)(Re/Er"I
(PI' > 0.6) (4-21 )
Here hp is the interphase heat transfer coefficient for a single sphere
and h :s thp interphase heat transfer coefficient for a fixed bed in ki-
lojoules per square meter per second per keh'in.
Calculations with the above equations show that for the same super-
ficial velocity and for intermediate Reynolds numbers. the heat transfer
•
coefficient of a p?cked bed of spheres is about 3 times that of a single

sphere. Equatic<1s (4-19) to (4-21) assume uniformity of flow rate
throughout the packed bed. The question of now uniformity through
packed-bed ga~ reactors was discussed under radial distribution of axial
flow rate. If this assumption is not true, local heat and mass transfer
coefficients must be used in radial increments when making design
calculations.
Radiant Heat Transfer

Radiant heat transfer was studied by" Vortl1le\'erl7,l~ in \\'est German\,.
.
among others. He showed that, at temperatures where radiant heat
becomes significant. heat transfer in fixed-bed gas reactors can be cal-
culated by using the following differential equation:
upcl'(dTldz) - [(d(Af/ + A.)/dz] (dTldz) = ( - M/) (4-22)
"'here u = superficial gas velocity, m/s
p = density, .kg/m3
cl' = specific heat of the gas, kJ/(kg . K)
Aa = axial !leat conductivity, kJ/(m . s . K)
Ar = radiation conductivity, kJ/(m . s . K)
•
When boun<.iary conditions are defined and Eq. (4-22) is integrated

simultaneously with a mass differential equation of the type:
dCldz = - j(C, T) (4-23)
we obtain the temperature profile and the concentr~tion profile in an
adiabatic reactor. Equation (4-22) is valid only for moderately exothermic
reactions; it cannot be used for reactors with steep temperature rises.
The value of AT can be estimated from:
A =
T
2B + E(l - B) . 4 kB Td (4-24)
2(1 - B) - E(l - E) P
where B = radiation passage number, defining the fraction of the

incident radiation that is allowed t:) pass through the pack-
ing, dimensionless
E = emission coefficient of the particle surface, dimensionless
• kB = Boltzmann's constant
l7
Vortmeyer calculated B = 0.1 and confirmed it by comparison with
other studies. A reasonable value for E is given by the same author as
E = 1/3 • The value of Aa' which measures heat transport by ordinary
conduction and convection, must be obtained by some other means.
In NINAF reactors that are cooled from the sidewalls, similarly to
heat exchanger tubes, significant temperature profiles occur in the packed
bed. Such temperature profiles are shown in Fig. 4-3, where the radial
--+----\ T.
I
FIG. 4-3 Typical tempefature profile of a NINAF reactor. (From E. U. SchlUn-

der, "Transport Phenomena in Packed Bed Reactors," in D. Luss and V. W. Week-
man, Jr. (eds.), Chemical Reaction Engineering Reviews Houston, American
Chemical Society Symposium Series 72, 128 (1978) by pel'mission.)
•
. TRANSPORT PHENOMENA IN FIXED-BED GAS REACTORS 89
profile of catalyst surface temperatures is shown by the curve marked

T,(r) and the radial profile of bulk gas temperatUlres is shown by the
curve marked Tc(r). Catalyst particles are shown as spheres. However,.
other particle shapes would not change the temperature profiles
considerably.
Heat Transfer between Reactor Walls a"d Packed Beds

6
Schliinrler derived the following formula to calculate the heat transfer
coefficient hu. between catalyst packing and tube walls in NINAF reactors:
(J' d"
hu. = (4A.1dp) d + 1 In 1 + - 1 + E.C,(T",/IOO)3 (4-25)
p <r
where (J' = 4 (J'o(2 - "1)/"1

E = radiation emissivity
C, = radiation of the blackbudy
= heat conductivity of the gas
(J'o = mean free path of gas molecules
= accommodation coefficient
T .. = average temperature between the wall and the fir:;t layer
of the packed bed
An extensive study of some 5000 data from various authors revealed
unsuspected complexities in the relationships of hw to other reactor pa-
\ ., rameters such as Peh and Dr/ZT' Schliinder concedes
--
that much
~~-.---
about hw
is not yet fully understood. ""c';," •.
4.4
INTRAPHASE TRANSPORT IN FIXED-BED GAS REACTORS
Gaseous chemical species move In catalyst pores by diffusion. The in-
terested reader is referred to various thorough treatments of pore dif-
fusion by Thiele,19 Weisz and Prater,20 Wheeler,21 Satterfield,22 Chap. 9
23
in Carberry,8 and Smith.
•
Intt aphase Mass Transfer
When a chemical reaction occurs on the internal pore surface of a catalyst'
pellet, a concentration, gradient is created between the outside bulk gas
phase and the inside of the porous catalyst. Since the reactants are con-
sumed in the pore reaction, the concentration of key reactant decreases
from the outside toward the inside of the pores. The movement of the
• -
chemical species by diffusion through the pores and the return of the
reaction products by the same path but in the reverse direction constitute
a mass transfer resistance to the reaction. A reaction which occurs rmly
on the outside surface of a catalyst is always much faster than the same
reaction would be if it occurred inside deep pores. The ratio of the
reaction rate in a porous catalyst to the rate on a nonporous catalyst is
called the effectiveness factor 1]. Of course we have to assume UHt both
the porous and the nonporous catalyst are made of the sa1l1~ material
and have the same surface area. Furthermore we must assume that the
concentrations and temperatures over both catalysts are the salT'~. The
rate of a reaction that has no mass transfer resistance to overcome is
called the intrinsic reaction rate. That would be the rate of the reaction
catalyzed on the outside particle surface.
In a porous catalyst one always measures the global reaction rate,
which is much slower than the intrinsic rate. One rough, but practical,
way of measuring the intrinsic rate is to crush the catalyst to a very fine
powder so that all the internal surface area is exposed to the full bulk-
phase concentration and temperature.
Effectiveness factors were briefly discussed in Sec. 3.4. \Ve will add
only, a short discussion of the Biot number for mass.
The BiD! number for mass (Bi m ) is a dimensionless group that relates
interphase mass transfer to intraphase mass transfer.
(4-26)
where ~; is the intraphase diffusivity in square meters per second. Biot

numbers are obtained by equating bulk mass transfer to mass diffusive
flow:
dC
kiCo - Cs) = -'J" d .< (4-27)
z ----a
This expression can be converted to a dimensionless one by setting Cn =

(C/Go ) and Z = z/a, replacing Gs and z by the dimensionless parameters,
and rearranging:
I - C rs I I
- - -- (4-28)
(dCrJdZ) Z=1 kg a/<j", Bim
-
Thus Biot numbers are obtained
•
. Bim = kg a/'J"', (4-26)
Values for Bi m can be calculated from three sources:

1. The value of kg is calculated from Carberry's correlation [Eq. (4-12)].
•
IDANSPORT PHENOMENA IN FIXED-BED GAS REACTORS 91
2. The value of a can be measured for each catalyst.

3. can be estimated from the practical methods for estimating dif-
g'li
22
fusivities given by Satterfield.
The Bi m values rangeS from 10 2
to
-
10".
Intraphase Heat Trar•.;fe:-

Heat phenomena in fi~ed-bed gas r.,actors include temperature gra-
dients through the catalyst particles and the bulk gas phase and heat
transport through the packed bed and the wall.
Since the chemical reaction occurs on the internal
. and external sur-
,
faces of the catalyst particle, the heat generaled by an exothermic re-

, to n'~lintain the desired
action must be removed from. inside the catalyst
reaction temperature. In the case of endmhermic reaclions, the heat
consumed inside the particle must be replaced, or else the catalyst would
cool and the reaction would slow down or even stop entirely. Thus
temperature gradients are created between the inside and the outside
surfaces of the particle and between the catalys~ panicle and the bulk
gas phase.
Intraphase Temperature Gradients

The temperature gradient IlTi between the centerline of the catalyst
pellet and the catalyst outside surface is called the intraphase temperature
24
gradient. This gradient is expressed according to Prater by
.. •.
IlT; = T - T, = -IlH D,(C, - C)!>.. ( 4-27)
•
where T = temperature at all points of the particle having a reactant

concentration C, K
Ts = temperature at the surface of the ca[<lIyst, K
-1lH = heat of reaction, kJ/kmol (negative values mean exo-
thermic reaction)
2
D, = effective diffusivity of the particle, m !s
iI. = thermal conductivity of the catalyst, kJ/(s . m . K)
3
C = molar concentration of key reactant, kmollm
C, = molar. concentration of key reactant on the catalyst sur~
3
face, k\l101Im
It is advantageous to discuss both intraphase and interphase temperature
gradients together in this section.
•
Interphase Temperature Gradients

The external temperature gradient !J.T. between the catalyst surface and
the bulk gas phase is called the interphase temperature gradient. This gra-
dient is obtained by a heat balance across the fluid film 25
heT, - T) = ~R( - !J.JJ) (4-28)
where h = interphase heat transfer coefficient

T = bulk gas temperature
9{ = observable global reaction rate
From Eq. (4-28) we can obtain:
aT. = T, - T = Hi (- t:Jf)/h (4-29)
All three quantities in the right-hand side of this equation can be evaluated.
. , It is also of interest to know the ratio of the external gradient !1T. to
the total temperature gradient aT•. Carberry25 calculated this ratio as
follows:
(4-30)
where 1)0 -
- overall effectiveness factor
Bim - Biot number for mass
Bin - Biot number for heat •
" , ,
Da - Damkohler number
In Eq. (4-30), !1T)!J.T. is expressed in terms of an observed rate

TJo Da and the ratio of Biot numbers. We will discuss thermal Biot num-
bers further below. The significance of this ratio derives from the fact
that !1T. makes up a far larger fraction of !1Tn than does aT,. Thus, in
fixed-bed gas reactors the major seat of thermal resistance is likeiy to be
external.
The,.mal Biot Numbers.

In analogy to Biot nUIllbers for mass, there is a Biot number for heat
(Bi h ), defined by
Bin = hat" (4-31)

•
PHENOMENA IN FIXED-BED GAS REACTORS 93
•
where A = thermal conductivity of the catalyst particle, kJ/(m . s . K)

2
h = interphase heat transfer coefficient, kJ/(m • s . K)
a = outside surface area-to-volurne ratio of the catalyst, m-I
This thermal Biot number relates interphase heat transfer (numerator) to

intraphase heat transfer (denominator). Its values range~ between 10
3
and 10 • Thermal Biot numbers are derived as described below.
For the outside surface of the catalyst particle, where the interphase
borders on the intraphase, we can write:
hdT
h(T - T) = - - (4-32)
S d7
A" :=(1
where T, = catalyst surface temperature, K

T = bulk gas temperature, K
2
h = interphase heat transfer coefficient, kJ/(m • S • K)
in dimensionless form with Trs = T)T we have:

I
(4-33)
There is also i:i wall Biot number (Bi u.) defined by:
Biu. = h. Dr/(2K,pcp ) (4-34)
which relates the heat transfer through the main body of the catalyst
bed (numerator) to the heat transfer through ·the wall (denominator).
Here KT is the radial dispersion coefficient for heat and can be calculated
from the Peh number.
Obviously the concept of BiU' is only applicable to I\"IKAF reactors,
since there is no heat transfer through the walls of adiabatic reactors.
1 2
Values of Biu. rangeS between 10- and 10 •
Intraphase and Interphase Heat Transfer

Interphase heat transfer has already been discussed above. Because of
the necessity of reviewing the joint treatments of interphase and intra-
phase heat transfer, it must be discussed again here.
Heat transport through the bulk gas phase in fixed-bed gas reactors
can be characterized by a heat transport coefficient h, which we can
define as a flux divided by a driving force:
..
diffusive flux of heat
h = ---------------- (4-35)
T, - T
•
The diffusive heat flux can then be expressed for both the bulk gas
phase (interphase) and the solid catalyst phase (intraphase), according
to Fourier's law:
qG = - AGO aTlaz (4-36)
q, = - A,ij aT/az (4-37)
\V hel e AGO ~ apparent heat conductivity in gas phase

Arl) = apl-'arent heat conductivity in catalyst (solid) phase
T = bulk gas temperature, K
T, - temperature of catalyst surface, K
;: = space variable
qc = intcrpha~~ heat flux
q, = intra phase heat flux
The evaluation of these thermal fluxes require that a transport model

be developed and that the boundary conditions be well defined (see pp.
6
200-201 of Ref. 8). Schlunder has rliscussed a "most widely used model"
for heat transport through catalyst beds. This model assumes that: (1)
both the gas and solid phases follow Fourier's law, and (2) both heat
fluxes qG and qs penetrate through the fixed bed along the radial space
variable r simultaneously and independently. The total heat flux q is
then:
(4-38)
In the absence of any chemical reaction T, = T and

q = - (A.,o + AGo)(aTlar) (4-39)
Assumption (1) is arbitrary and has yet to be experimentally verified.

Assumption (2) has been v~rified by Schliinder,6 who reviewed this ap-
parently quite complex model.
NOMENCLATURE
a External particle surface-area/particle-volume ratio, m-I
2
Cross-sectional area of the empty reactor, m •
B Radiation passage number, or fraction of the incident ra-

diation that is allowed to pass through the packing,
dimensionless
Bi< Biot number for heat, dimensionless
Bi~ Biot number for mass, dimensionless
•

•
Heat capacity or specific heat of gas, kJ/(kg . K)

. 3
Inlet concentration, kmol/m
r
Co' ,- Reduced concentration, dimension less
e" Reduced surface concentration, dimensionless
c, ivIolar concentration of key reactant on exterior particle sur-
face, kmol/m~. or radiation of the blackbodv •
Hydraulic diameter, m
Catalyst particle diameter, m
Effective diffusivity of the particle, m~/s
Molecular diffusion coefficient for diffusing species in mul- •
2
tiple component mixtures, m 1s
Reactor inside diameter, m
':1\ Axial dispersion coei'ficient for mass, m~/s
2
'J.... i Intraphase diffusivity, m /s
'.!\ Radial dispersion coefficient for mass
Dah Damkohler number for heat, di"lensionless
Dam Damkohler number for mass, dimensionless
f Fraction of the reactor cross-sectional area with larger voids,
dimensionless
Force-to-mass conversion factor = 1.0 kg . m/(r\ . S2)
,
q
\,
-- -,
G Mass flow rate of gas, kg/(s . m-)
2
h Interphase heat transfer coefficient, kJ/(m • s . K)
Interphase heat transfer coefficient for single sphere,
2
kJ/(m • s . K)
h. Heat transfer coefficient between catalyst packing and tube
2
walls, kJ/(m • s . K)
hJ Rate constant of reaction I
ha Boltzmann's constant
kg Interphase mass-transfer coefficient, m/s
-
2
KT Radial dispersion coefficient for heat, m /s
•
n Number of CSTR equivalents
I\u Nusselt number for packed bed, dimensionless
l\:up Nusselt number for single sphere, dimensionless
Pea Mass Peelet number for axial dispersion, dimensionless
•
96 CATAlYTIC REACTOR DESIGN •

•
Peh Radial Peclet number for heat, dimensionless

•
Pe m Radial Peciet number for mass, dimensionless

Pr Prandtl number, dimensionless
"
qc Interphase heat flux. kJ/(m- . s)
2
q, Intraphase heat flux. kJl(m • s)
r Radial position or distance from reactor axis, m
~R
3
Global rate of reaction, kmol/(s . m )
Sc Schmidt number, dimensionless

2
St Total geometric surface area of catalyst, m
T Absolute temperature of the bulk gas phase, K
To Inlet temperature of the bulk gas phase, K
Tm Average temperature between the wall and the first layer of
the packed bed, K
TT Reduced bulk gas temperature = TITo, dimensionless
T,., Reduced surface temperature = T)To, dimensionless
T, Absolute temperature at the catalyst surface, K
u Superficial fluid velocity hased on empty reactor cross sec-
tion, mls
Su!)erficial gas velocitv based on empty reactor cross section
between inlet and outlet, mls
v Point velocity at a distance r from the axis, mls ..
z Longitudinal reactor coordinate

ZT Total reactor length. m
(-IlH) Reaction heat, kJ/kmol
Pressure drop, force units, bar
llTi Intraphase temperature gradient, K
llTo Overall thermal gradient, K
•
Interphase temperature gradient, K
111 Effectiveness factor of reaction 1
a •
Reaction oreter
E Void fraction or fractional void volume in bed, dimensionless
E Emission coefficient of the particle surface, dimensionless
•
TRANSPORT PHENOMENA IN RXED-BED GAS REACTORS 97
•
•
Thermal conductivity of the catalyst particle, kJ/(s . m . K)
Aa Axial thellual conductivity, kj/(s . m . K)
>"1: Thel1nal conductivity of gas, kj/(s . m . K)
>"r Radiation conductivity, kj/(m . s . K)
Absolute viscosity of gas, Pa . s
p Density of gas, kg/m~
0'0 Mean free path of gas molecules, m
REFERENCES
1. M. Orhan Tarhan and William E. Schiesser, "Computer-Aided Design of
Nonisothermal Nonadiabatic Fixed-Bed (NINAF) Gas Reactors," paper pre-
sented at the 74th AIChE National Meeting in New Orleans, March 11-15,
1973.
2. Sabri Ergun, "Fluid Flow Through Packed Columns," Chem. Eng. Progr.
48:89-94 (1952).
3. C. E. Schwartz and J. M. Smith, "Flow Distribution in Packed Beds," Ind.
Eng. Chem. 45:1209-1218 (1953).
4. M. R. Shaffer, M.S. thesis, Purdue LJniversity, Lafayette, Ind. (1952).
5. R. F. Benenati and C. B. Brosilow, "Voicl Fraction Distribution in a Bed of
Spheres," AlChE]. 3:359-361 (1962).
6. E. U. Schliinder, "Transport Phenomelia in Packed-Bed Reactors," in Chem-
ical ReactWn Engineeling Reviews Houston, American Chemical Society, Sym-
..
•
\.
' posium Series 72, 1978, pp. 110-161.
7. Richard H. Wilhelm, "Rate Processes in Chemical Reactors," Chem. Eng.
Progr. 49:150-154 (1953).
8. James J. Carberry, Chemical and Calnlytic ReactUm Engineering, McGraw-Hill,
New York, 1976.
9. lames]. Carberryand Martin M. Wendel, "A Computer Model of the Fixed-
Bed Catalytic Reactor The Adiabatic and Quasi-Adiabatic Cases," AlChE
]. 9:129-133 (1963).
10. James J. Carberry, "First Order Rate Processes and Axial Dispersion in
Packed Bed Reactors," Can.]. Chem. Eng. 36: 207-209 (1958).
11. James J. Carberry and R. H. Bretton, "Axial Dispersion of Mass in Flow
Throllgh Fixed Beds," AlChE]. 4:367-375 (1958) .
•
12. Sabri Ergun, "Mass-Tri!nsfer Rate in Packed Columns Its Analogy to Pres-
sure Loss," Chem. Eng. Progr. 48:227-236 (1952).
13. James J. Carberry, "A Boundary-Layer Model of Fluid-Particle Mass Trans-
fer in Fixed Beds," AIChE]. 6:460 463 (1960).
•
,
•
14. James J. Carberry and Donald White, "The Role of Transpon Phenomena
in Catalytic Reactor Behavior," [nd. Eng. Goon. 61(7):27-35 (1969).
15. Holger Martin, "Low Peelet Number Panicle-To-Fluid Heat and Mass Transfer
in Packed Beds," Glum. Eng. Sci. 33:913-919 (1978).
16. VolkerGnielinski, "Berechnung mittlerer War me- und Stoffiibergangskoef-
fizienten an laminar und turbulent iiberstromten Einzelkorpern rnit Hilfe
einer einheitlichen Gleichung," Forsch. lngr.-H"esen. 41: 145-153 (1975).
17. D. Vortmeyer and C. J. Barner, "Die Str.thlungsdurchlasszahl in Schiittun-
gen," Ghem.-lngr.-Tech. 38:1077-1079 (1966).
18. D. Vortmeyer, "Del' Energietranspon durch \\"armestrahlung in Festbetten
mit exothermpr Reaktion," Ber. BU)IS{,llgl'S, ph)'sik. C/iNn. 74: 127-130 (1970).
19. E. W. Thiele, "Relation between Catalvtic
•
Acti\·it\· and Size of Panicles," lnd.
•
Eng. Ghem. 31(7):916-920 (1939).

20. Paul Burg Weisz and C. D. PrateI'. "Interpretation of Measurements in
Experimental Catalysis," in Ad"Gllces ill Catalyi". \'01. G. Academic Press,
New York, 1954 pp. 143-146.
21. Ahlborn Wheeler, "Reaction Rates and Selecti\'il\'. in Calalvs[
, Pores," in P.
H. Emmett (ed.), Cata(\'Sis, VoL 2, Reinhold, i\e\\' York. 1955, Chap. 2, pp.
105-\65.
22. Charles N. Satterfield, Mass Tramfer in He/lTogl'w'oIlS Cata(rsi" ;''[IT Press,
CamLridge, 1970, Chap. 1.
23. J. M. Smith, Chemical Engineering Kinetics, 2d ed. ;"fcGraw-Hill. :\ew York,
1970, Chap. 11.
24. Charles D. PrateI', "The Temperature Produced by Heat of Reaction in the
Interior of Porous Particles," Chem. Eng. Sci. '8:C)S-!-~8G (1958).
25. James J. Carberry, "On the Relative Importance of External-Internal Tem-
perature Gradients in Heterogeneous Catalysis:' JI/d. Eng. Ghem. Fundamen-
tals 14:129-131 (1975).
•
•
PROCESS DESIGN OF
Chapter
FIXED-BED GAS REACTORS
This chapter deals with the process design of various t\'pes of fixed-bed
reactors. Isothermal reactors are treated first, mainlv ;n order to intro-
•
duce a simple procedure. As we progress through the treatment of

adiabatic and later KINAF reactors, things will become increasingly
•
complex.
5.1
ISOTHERMAL REACTORS
There are various ways of making a fixed-bed gas reactor behave iso-
thtrr:aIly. It is hard to imagine a chemical reaction that has a reaction
heat of zero. B"• definition such a reaction would not occur at all. Con-
sequently, one way to obtain an isothermal reactor is to achievej)erfect
heat transfer with the surroundings so that all points of the fixed bed
may be maintained at the same temperature. This may be nearly achieved
only in very small laboratory reactors.
Sometimes the reactant is diluted in the feed and the heat of reaction
is hardly noticeable. In such cases a fixed bed may be operated practically
as an isothermal reactor. Also. a very weakly exothermic or endothermic
reaction behaves practically like an isothermal reaction. Thus isothermal
reactors are not designed very often for full-scale plants. In spite of this,
we will discuss the design of an isothermal reactor as an introductory
and relatively simple examfJle .
•
..
-
General Design Procedure
The general procedure for designing isothermal gas reactors consists of
setting up rate equations and a design equation. Rate equations may be
•
•
•
expressed in the practical power law form:

•
ffi = TlTv = TI A exp( - EIRT) e: ef (5-1) .

3
where = apparent reaction rate, kmoll(s . m )
3
Tv = intrinsic reaction rate, kmol/(s . m )
'Tj = intraphase effectiveness factor, dimensionless

3
C = molar concentration of reactant or product. kmol/m
E = activation energy, kJ/kmol
R = gas constant = 8.314 kJ/(kmol . K)
Subscripts a ancl. b relate to the concentrations of particular reactants
or products in a reaction of the type
A+B+ ... )P+Q+ ...
Superscripts a and ~ are exponents indicating reaction order.
Sometimes the rate equations are expressed in terms of partial pres-
sures instead of cr-ncentrations:
..,1' = A exp( - EIRT) p~ P: (5-2)
where p is the partial pressure of a reactant or product in bars.

The relationship between Tv and Tvp is given by:
. . (5-3)
where it is the gas constant (c" . pressed in different units from R) = 0.08314
3
m • bar/(kmol . K).
In most "real-life cases" the reacting system is not a simple one. There
is more than one reaction going on and these reactions are consecutive,
simultaneous, parallel, or combinations of these types. However we will
simplify our first problem by assuming a single reaction.
The so-called design equation is the same for all types of fixed~bed
reactors. It is developed as follows: Let us consider a fixed-bed reactor
of cross-sectional area Ac and bed height z (Fig. 5-1). Let us considf'T a
differential volume dV of this fixed bed limited by two paldlel surfaces,
each perpendicular tq the axis oz of the cylindrical bed. If the distance
between these cross-sectional surfaces is a differential dz, the differential
.
volume dV wIll be:
-
(5-4)
•
PROCESS DESIGN OF FIXED-BED GAS REACTORS 101
•
•
F, kmol/s
o -
I
I
",-
-- - --- - .....
FIG. 5-1 Development of the design eqnation fer isothermal or adiabatic fixed· •
bed reactors.
Let us assume that F km oils of a feedstock containing Yu mole fraction

of the key reactant enters the reactor and that the fractional conversion
of that reactant is x. Let us also designate the rate of Lhemical reaction
occurring in the reactor as 1~. The dimensions of this rate are kilomoles
per second per cubic meter. The volume includes bot!' the catalysts and
the voids. The balance between the incoming and the outgoing materials
can be written:
Incoming moles = outgoing moles + accumulating moles
+ moles disappearing by reaction (5-5)
.. .
In steady-state operation no material accumulates in or is depleted from
the reactor. Equation (5-5) can then be expressed as
fyo = FJu(l - dx) + r,. dY (5-6)
Here F)'I) is the number of moles of the key n:actant and I - x is the
un reacted fraction of F)·o when lea\-ing the differential yolume dV, thus
Fyo( I - dx) is the unreacted feed leaving dV and rrdV is the extent of
•
reaction occurring in differential volume dV. Equation (5-6) can be rear-

ranged to give
Fyo - F)'I) + Fy" dx - dl'
1"..•
(5-7)
Fy"
- dx = r,. d\'
•
or on replacing d\' by its ~alue in Eg. (5-4)
Fyo dx = r, it( dz (5-8)
•
102 CATAlYTIC REACTOR DESIGN ,
In addition to the rate and design equations, it is 'l.ecessary to develop

a pressure drop equation to c.ompute the pressure at even' point of the
reactor. The pressure drop is given b\' the Ergun law, discussed in Sec.
4.3:
+ 1.75 (4-1 )
The value of ~P/Z can be calculated at the start, and at e\'ery step proper
pressure corrections can be made.
Once the design equation, rate equation, and pressure drop equation
have been set up, the designer must express the concentration or partial
pt cssure terms in the rate equation in terms of the fractional conversion
x and simultaneously solve the three equations for the reactor height Z,
If there is more than one rate equation, that system of rate equations
must be prepared for use in the simultaneous solution. This preparation
will be discussed further below in the treatment of l\1l\AF reactors.
Example: Design of an Isothel"mal Reactor

Let us considpr a simple hydrogenation reaction
(5-9)
Ethylene Ethane
This is an exothermic reaction, but it can be run in a \'erY• small isothermal

1
reactor, which was done by Wynkoop and Wilhelm. These investigators
used a copper-magnesia catalyst, which they prepared and packed in a
9.35-mm ID, 280-mm-Iong yellow brass reactor tube provided with a
water jacket. By recirculating 37.85 Umin of water through this jacket,
2
a water film coefficient of more than 5.67 kJ/(m • S • K) and a practically
constant tube-wall temperature were obtained. Experiments made at
various constant temperatures in the 9 to igoe range in this reactor
showed that the reaction of Eq. (5-9) is first-order \\'ith respect to hy-
drogen. The rate equation can then be written by setting
Cl = 1 f3 = 0 a = H2 A exp( - ElRT) = k
•
C~ = CH
k being the reaction rate constant, Thus Eq, (5-1) becomes
•
(5-10)
in which lj is implicitly set equal to I, The reactor \olume can be cal-

culated by simultaneously solving the design and rate equations [Eqs,
•
•
PROCESS DESIGN OF FIXED-BED GAS REACTORS '103
•
(5-7) and (5-10), respectively]. (In this small reactor!::.P can be neglected.)
This can be done, if CH is expressed in terms of x.
Let us combine Eq. (5-7) and Eq. (5-10) and rearrange:
F •Vu dx -- k CH dV
dV - dx
(5-11 )
Fy(, '< . C Il
Since the reaction involves a change in volume. ;ve must take account
of it in order to integrate Eq. (5-11). [Pt us c:msid~'r the reaction
aA + bB ) pp + qQ (5-12)
where a, b, p, and q are stoichiometric coeaicients. A and B are reacting

species, and P and Q are reaction products. Suppose thf' feedstock con
sists only of A and B, not necessarily in the stoichiometric proportion.
Let A be the limiting reactant, i.e., :Y~/lv~ < alb, where N is the m:mber
of moles passing through the reactor per unit time and let the su perscri pt
o denote ill/et and let the subscripts T and A denote lotal and ethylene.
Initiallv• we have:
(5-13 )
1 - Ju
where N.(~ = )'0 N;. ,,0
IVA (5-14)
•
VU
After a fractional conversion XA:
• •
+lJ.~x
A A
a (5-15 )
- · \,{l _ HA'A
,,1') X
b P q
I + - - - - -
- T
a a a
a+b-p-q a + b
- :Vi - N(. )'0 x.-\
a + b a
. If we set d' = (P + q)
- (a + b)
(5-16)
a + b
• a + b d'xA
NT = Ni- + N'j..--"0 a
(5-17)
a + b d'
NT = Ni- l + )'0
a
X.\
•
'104 CATALYTIC REACTOR DESIGN
•
In the case of ethylene hydrogenation:

•
I rnol ethylene + I rnol Hz ) I rnol ethane (5-18)

a=l b=1 p= I q= 0
d' (1) - (I + I) = - -I a +b
=2
1 + I 2 a (5-19)
, • rtl
N r = (1 - ,Vu X .,.)iYi
where at start x.-\ = 0 NT = Ni and

at end x" I N T = (I - \'o)l\/;,
=
-
If we write a rnate} ials balance equation for reactant B across the reactor,
the nurnber of rnoles of 13, NB, may be expressed as a function of x\
•
b 0
- -xAN A (5-20)
a
=(1
b
=(1 - ,Vu - -a Yn x\' ) NTO
T (5-21)
In the case of ethylene hydrogenation:

NB = (1 - Yo - Yo XA) N~ (5-22)
= N~ - YoN~.(1 + x.\)
\
= N~ - N~(l + XA) (5-23)
Cornbining Eq. (5-19) with Eq. (5-23) gives:
NB _ N~ - N1(l + XA) _ I N1(l + XA)
- -- (5-24)
NT N~ (1 - ]0 x A ) 1 - Yo X A N~(l - Yo x.-\)
In Eq. (5-10) CH rnay be expressed as:
P I
- . - . (5-25)
RT 1 - Yo XA 1 - Yo XA
•
where P is the total p~essure.
Now CH in Eq. (5-10) may be replaced by
its value frorn Eq. (5-25), taking in consideration that (N1IN~) = Yo -
P I I + x.-\
T" = k CH = k:-,-.-
1 - Yo
- ,Vo 1 (5-26)
RT XA - Yo x.\
•
•
Substituting Eq. (5-26) into the design equation, Eq. (5-11)

•
dV RT
-=- (5-27)
Fyo kP
kP v XA - I + )0 XA dx
• dV = (5-28)
RTFvo <
0 o Yo - 1 + Yo X A
Equation (5-28) can be integrated by using the following integration

formula
, a + bx dx __ bx + (a~ - ab)
":-="---:')~"':" In (a + I3x) (5-29)
() a + I3x ~ W
where a = -1 b = Vu
- a = Yn - I 13 = Y"
x., 1 + Yo XA
- L
In Y° - 1 .1. Y x
. 0 A
u.( = x'" +
o )'0 - I + Yo XA . Yo - 1
Substituting th:s value into Eg. (5-28) alid integrating dV gives
.
kPV = XA
I Yo - 1 + Yo XA
+ n "-'-----".::........:.;
RTFyo Yo - 1
•
RTFyo + In )'-I+YoxA
_,:..:o'--_ _....<.:::.__=.:
V = kP x..~ .:... 1
(5-30)
. . Yo '-
If an equal number of moles of ethylene and hydrogen is fed to the

reactor, or if )'0 = 0.5, Eq. (5-30) reduces to
•
RTF
V = 2kP x .... - In(1 - XA) (5-31)
Let us assume some values for X.A and calculate the value of the bracket
in Eq. (5-31)
x = 0 . 0.5 0.9 0.99 0.999 1.0

x - In( 1 - x) = 0 1.193 3.2025 5.595 7.9068
•
" These numbers show that with an equimola_r mixture of reactants, com-
plete conversion of ethylene cannot be attained in a finite-sized reactor.
But with a slight excess of hydrogen, e.g., with yo = 0.49 instead of
yo = 0.5, the value of the bracket in Eq. (5-30) drops to 4.1 065 for x ... = I.
•
i06 CATALYTIC REACTOR DESIGN
Let us now calculate the design of an actual laboratory reactor. We

can use Eq. (5-30) with]o = 0.49. Other quantities in Eq. (5-30) are:
• F = 2.0 X 10-8 kmolls of total feed
· k = 0.08314 m 3
• bar/(kmol . K) gas constant
· R = 8.314 kJ/(kmol . K) gas constant
· T = f)7°C + 273.2 = 340.2 K
6 S
· k = 5.96 X 10 exp(-55,7311RT) kmoll(s' m ) determined by
Winkoop and Wilhelm,1 at T = 340.2 K, k = 0.0165
• XA = 1.0 desired
· p = 1.0 bar assumed.
V =~0.08314)(2 x I0-8)(34~.2) f4.106] = 0.00007038 m S

(2)(1.0) (0.0165) l
3
= 70.38 cm
If a I-cm-inside diameter reactor tube is used, the reactor length Z will

3 2
be (70 cm hr 0.5 ) = 89.1 cm.
This whole calculation is only of academic value, since experimental
reactors are not designed by this tYl~e of calculation and commercial-
size reactors cannot be operated completely isothermally.
It is of interest to note that this isothermal reactor design example
was computed analytically. In case a complex reacting system is involved
or even in case the single reaction is reversible and the rate equation
: "
becomes messy, it may become necessary to resort to numerical integra-
tion using a digital computer.
5.2
ADIABATIC GAS REACTORS
Let us review the conditions of Zidiabaticity.
Definition
An adiabatic reactor is one which exchanges no heat \,·ith the surround-
ings. Consequently, if an exothermic reaction is run in an adiabatic fixed-
bed reactor, the temperature of the gas stream will increase from the .
inlet toward the outlet . .If, on the other hand, an endothermic reaction
is run in the same reactqr, the temperature of the gas stream will drop
along the reactor length.
Most industrial fixed-bed gas reactors are designed as adiabatic re-
actors. A good insulation around the reactor vessel usually provides
complete isolation and adiabaticity.
,
•
One-Dimensional Plug-Flow Model

The simplest model of an adiabatic gas rea,ctor is the one-dimensional plug-
flow model. A reactor must meet the following conditions in order to
conform to this model:
· There should be no heat exchange between reactor and surroundings
(cvndition of adiabaticity) .
•
•
· The flow pattern through the fixed catalyst bed should be such that
linear velocities of the reacting stream are the same at at:y point of
the bed.
· There should be no axial dispersion.
· There should be no radial dispersion.
The first Lvndition can be met by an efficient insulation around the
reactor. The second condition can be met by using appropriate flow
distribu~ors at the inlet of the catalyst bed. Without ~Jch flow distributors
the flow pattern would be somewhat parabolic, with lower velocities near
the wall and higher velocities a few particle diameters from the wall (Fig.
4-2). The third condition (no axial dispersion) is easy to meet for fixed-
bed gas reactors. Axial dispersion is fundamentalh local backn~ixing of
reactantl' and products in the axial, or longitudinal. direction in the small
interstices of the packed bed, which is due to molecular diffusion, con-
vection, and turbulence. Axial dispersion has been shown to be negligible
in fixed-bed gas reactors (see Sec. 4.3). The fourth condition (no radial
dispersion) can be met if the flow pattern through the bed already meets
the second condition. If the velocitY, of flow in the axial direction ~·s
.' .
constant through the entire cross section and if the reactor vessel is well
insulated (first conditio~:). there can be no radial dispersion to speak of
in gas reactors. Thus the one-dimensional adiabatic reactor model may
be actualized without great difficulties.
Development of Design Equations for Adiabatic Gas Reactors

Basically, the design of adiabatic fixed-bed gas reactors according to the
one-dimensional model consists in the simultaneous solution of three
types of equations. The first type is the rate equation or a system of rate
equations, similar to Eq. (5-1) or Eq. (5-2). The second type is the design
equation proper, typifi~d by Eq. (5-7)
fo •v() dx = r"dV = r t • Ac dz (5-7)
..
just as in the case of isothermal reactors. The third type of equation is

developed from an energy balance. In case of an exothermic process, this
balance equates the amount of heat generated by the reaction with the
•
108 CATAlYTIC REACTOR DESIGN' •
•
•
heat absorbed by all reaction gases in order to increase their temperature.

In the case of an endothermic process, the amount of heat absorbed by
the reaction is equated to the heat supplied by all reaction gases from
their decrease in temperature. This balance can be written as:
F )0 dx( - M-/) = km; Gp; dT (5-32)
where (- All) = the heat of reaction of the entire reacting system

mi = the molar flow of each reacting species (this includes
both reactants and products), kmolls
C,,, = the molar heat :apacity of each reacting species. kJI
(kmol· K)
The design eguation Eg. (5-7) is sometimes written in a variety of
forms. The difference stems from the basis of the rate equation. In Eqs.
(5-1), (5-2), and (5-7) we used a rate expression that is based on moles
reacted per second and per volume of fixed bed. This volume includes
both the catalyst volume and the void space. This preference is based
on the fact that in the United States catalysts are sold by volume. In the
literature one often comes across various bases for expressing rate
•
equations:
· U nit weight of catalyst bed
· Unit void volume of catalyst bed
· Unit surface area of the catalyst
When catalyst weight is used as .'1 hsis. then Eq. (5-7) can be modified
to
(5-33)
where ru. is the reaction rate in moles converted per unit time per unit
weight of catalyst and PB is the bulk density of the catalyst in kilograms
per cubic meter.
When void volume of the catalyst is used as a basis, Eq. (5-7) can be
modified to
F ]0 dx = r,,. E Ac dz (5-34)
where r,i is the reaction rate in moles converted per unit time per unit
void space of catalyst ~md E is the fractional void space ir. the catalyst
bed.
* .
When the surface area er the catalysl bed is used as a basis, Eq. (5-7)
. can be modified to:
(5-35)
.. .
•
•
•
where T, is the reaction rate in moles converted per unit time per unit
surface area of catalyst and Sg.is the catalyst surface area in unit surface
area per unit weight. Catalyst surface area is almost always given in
square meters per gram. Consequently, in order to make the system of
units in Eq. (5-35) a consistent one, we must convert SI: into units con-
sistent with the system employed, as follows:
.) q
F (kmol/s) r, [kmol/(s . m-)] Sf( (m-/kg)
Ps (kg/ms) z(m)
Thus, it makes no difference on what basis the reaction rate is expressed
as long as this basis is known and the proper units are used. In practice,
the actual process design work for the reactor consists in finding the
various kinetic and thermal data needed for Eqs. (5-1), (5-32), and any
one of Eqs. (5-7), (5-33), (5-34), and (5-35), as the case may be, and in
solving the three simultaneous equations. Details and complications will
be seen in the treatment of examples that follows.
The Problem of Designing Fixed-Bed Gas

2
Reactors for ExothellUic Reactions
Moderately exothermic gas reactions are usually run in ordinary fixed-
bed reactors. The limitation {O an adiabatic reactor is set by the limiting
outlet temperature tmaX' attainment of which may mark the beginning of
some undesirable event such as a side reaction, poor selectivity, or ex-
cessivecatalyst fouling (Fig. 5-2). If the limiting te'J1perature is reached
•
t
tmol - - - - - - - - - - - - - - -..,...--
•
to
;0 ,-
x
•I ....;:-.==-.--'
1.0 -----==::.~
•
.,..,."- '"
•
I
• /'
-'
.-'
-'
I o /'
t
1mox------------ ..------
x
10
;0 ,
.I
•
1.0
..... ---- X" .S
-
,•
I
• ...... -.'
.. -.
-
I 0/
FIG. 5-2 Running exothennic reactions in adiabatic reactors.
. .
•
ttO CATALYTIC REACTOR DESIGN
,
•
I' I'
"
;
I'
- ,~ r
/
J
"- Y
fIG. 5-3 Inditect cooling bet"een two caLlyst beds.
before the desirable fractional conversion x, then one of several methods

may be applied to extend x to the desired value Kithout exceeding I rna,.
Onc such method, illustrated in Fig. 5-3, consists of (I) subdividing
the catalyst volume into two or more beds so as to allow each bed to
reach only t max and (2) cooling the reactant 3'ases between consecutive
beds back to the inlet temperature to of the first bed by using indirect
heat exchangers. The temperature vs. conversion diagram \\'ould then look
like Fig. 5-4, or after optimizati()n like Fig. 5-5.
If the reaction temperature is too high for the use of indirect heat
exchangers, a second method can be employed in which one of the
reactants is injected cold into the reaction stream between consecutive
beds, thus cooling them to 11) (Fig. 5-6). This direct cooling, or quenching,
method has the added advantage of pushing the reaction in the desired
direction by replenishing one of the deplFted reactants.
A third method is the old German technique of step'(eise quenching (Fig.
5-7). Although this method does work, it has the disadvantage that it is
somewhat sloppy and is difficult to design for.
A fourth method consists of adding an inert gas or an excess of one of
the reactants to the reactor feed, The inert gas or the excess reactant acts
as a heat sink by absorbing a large part of the exothermic heat and thus
reduces the temperature increase for a given cOI1\'ersion. This method
has a serious disadvantage mer the other methods in that it requires an
increase in the size of the reactor in order to accommodate the inert
gases or the excess reactant.
In a variant,of Method 4, one adds an inert liquid with a boiling point
at the prevailing pressure that is close to the reaction temperature. The
exothermic heat causes the inert liquid to vaporize, thus absorbing con-
siderable heat to meet tatent heat requiremen~s. As Satterfield and "'ay
have pointed out, in some cases with this method the reaction rate would
u
be slower than it is in purel~ gas-phase rnethods.: The disad\'antage,
therefore, would be the requirement of large, costly reactors.
•
PROCESS DESIGN OF FIXED-BED GAS REACTORS Ut
If no one of the methods offers a satisfactory solution to the problem

of handling exothermic heat, consideration must be given to running
the gas reaction in one of the following:
· A fluidized-bed reactor
· A gas-liquid-phase reactor "'ith an inert liquid
· A NINAF gas reactor
The gas-liquid-phase reactors "'ill be discussed in later chapters. The
NINAF reactor will be discussed later in this chapter.
Example of Adiabatic Fixed-Bed Gas Reactor Design:

Design of a Toluene Hydrodealkylation Reactor
Toluene can be hvdrodealkrlated
. to benzene and n1Lthane in the ores-
,/ .
ence of certain calalyslsj-7 according to the equation:
(5-36)
We will try to design a plant that willlndrodealkylate 66,000 metric tons

of toluene per ~'ear to pure benzene using a fictitious cat::lytic process.
It is necessary to resort to this assumption because there are no puulished
or publishable data that can be used for any of the existing commercial
hydrodealkylation processes, The author believes that it is perfectly all
right to carry out a design procedure by using assumed data as long as
\
these -:lata are in the appropriate range of \'alues, The purpose of this
. •.
.
book is to teach design methods and this purpose will be met even if the
calculations result in a reactor that should not be built. Anvone • ~"ho
•
actually wants to design a toluene hydrodealkylation reactor should either

obtain a license from one of the commercial processes or deyelop a new
process. In both cases reliable yalues will be obtained for all the param-
eters, which usually are not published. By using the general method of
I
'mOl---- --- -- -- -.... - - - - - - -
to L'---_ _ _ _ _ ~:::::::::::::.
1 ' ~)~
... .. :::-..=-.-
1.0 -----.--~
I " .. -
i --....-
i - 0 ,...'/'
FIG. 5-4 Partition of an adiabatic reactor into two beds by cutting the first
bed at t ......
•
,
•
this book and the acquired data, it should be possible to make a reliable
design that can be incorporated into an actual reactor.
Side reactions to the process of Eq. (5-36), such as the formation of
biphenyl, are too slow to have any influence on reactor design. and
therefore they will be ignored. The rate equation is:
ri.' = (5-37)
. !
where C\ = concentration of toluene, kmol/m'
3
CB = concentration of hydrogen, kmol/m
k = reaction rate constant for tolulene hydrodealkylation
E = activation enagy = 148,114 kJ/kmol
= -49,974 kJ/kmol toluene converted
e- residence time, s
The published value for the activation energy E is 35.4 kcal/(g . mol)
but no published value for the frequency factor A is available. This value
depends on the particuLr catalyst and will be assumed to be
6
A = 5.73 X 10 • The reaction temperature at reactor inlet is assumed
to be To = 600°C + 273.2 -= 873.2 K. The reactor pressure can be 35
to 70 atm abs. It will be assumed to be about 50 atm abs, or 50 bars.
,. ,
- The hydrogen/aromatics ratio can be assumed to be 5.0 from general
experience in 'hydrogenating aromatics.
For the energy balance equation, Eq. (5-32), the molar heat capacities
of toluene. hydrogen, benzene, and methane between 600°C and 635°C
are needed. Published cl' data~ have been assumed to be linear between
800 and 1000 K and linear equations developed expressing cl' as a func-
R
tion of temperature. The cl' of hydrogen is constant over this temper-
I
1",0' - - - - - - - - - - - - - - - - - - - - -
Optimized
10 ' - - - - -
•
x
"-• 1.0 - - - - - - - : ; : :::._~,;:-'="-
...
:
...
I, --.---_. ",..
I• 0/'/"'--"
I
FIG. 5-5 Partition of an adiabatic reactor into two beds by optimizing the
cutting point of i.he first bed.
•
PROCESS DESIGN 01= FIXED-BED GAS REACTORS 113
•
• •
Quench
FIG. 5-6 Direct cooling, or quenching, between two catalyst beds.
Quench - •IT"" - Quench
"\., .
FIG. 5-7 Stepwise direct cooling in a catalyst bed.
ature interval. The following cp data have the dimensions of kilojoules

per kilomoles per kelvin.
Hydrogen: Gp = 20.786
Methane: Gp = 0.04414T + 27.87
Benzene: Gp = 0.1067T + 103.18
Toluene: Gp = 0.03535T + 124.85
The economics of any hydrogen-consuming hydrocarbon process de-
pends upon the way the spCnl hyd!"oger. is purified and reused. In this
problem, it will be assumed that the spent hydrogen is purified according
59
to Fig. 5_8 • and that the purity of the combined hydrogen stream at
the inlet to the hydrodealKylation unit is 90%, the balance being methane.
The toluene hydrodealkylation process provides a good example for
exothermic heat removal by quenching the reaction gases with a "hy-
drogen gas," which in this case contains 90% hydrogen and 10% meth-
ane. Of course the first bed operates with only the inlet feedstock and
•
•
tt4 CATALYTIC REACTOR DESIGN

•
the inlet hydrogen gas. However, the second and subsequent beds op-
erate with a mixture of the effluent from the previous bed plus the
quench. The design equations that will be de\'eloped in the following
are applicable to any bed.
The system of equations, Eqs. (5-7), (5-32), and (5-37), can be solved
simultaneously if the concentrations in Eq. (5-37) are expressed in terms
of fractional conversion x. Let us do this. At any conversion x. the moles
of each reactant or product are:
Toluene Fyo (l - x)
Benzene Fyo x
Hydrogen Fyo (5 - x) + 0.9 quench
Methane Fyo (5/9 + x) + 0.1 quench
, .
Total moles Fyo (l + 5 + 5/9) + quench, or
6.5555 Fyo + quench .
The mol fractions of each component are:

Toluene: Yl = F)'o (l - x)/(6.5555 F)'o + quench) ..\ )
( =)'
Benzene: )'2 = F)'o x/(6.5555 Fyo + quench)

Hydrogen: )'3 = (Fyo (5 - x) + 0.9 quench)/(6.5555 F,'" +
quench) (= YB)
Methane: Y4 = (Fyo (5/9 + x) + 0.1 quench)/(6.55SI) Fyo + quench)
•
Concentration terms can be written as:
N Np P
c = V = NR~T = R~T
since p = yP
•
C = '¥PlRcT
•
where p -- partial pressure, bars

- 3
C - molar concentration, kmol/m
R~ -
3
gas constant = 0.0831417 bar' m /(kmol . K)
T - absolute temperature, K •
- mole frd~tion of individual reactants and products

-
Y
P -- total presSllre, bars
CA =. P Fyo( 1 - x)
. Rc T(6.5555 Fyo + quench)
C _ P (F)'o (5 - x) + 0.9 quench)
B - R~ T(6.5555 Fyo + quench)
•
Let us substitute these CA and CB terms into Eg. (5-37):

•
dC
rl' = de" =A exp( - EIR GT)[PIR;;T(6.5555 F)'o + quench)]1.5
5
• Fyo (1 - x) . [F)'o (5 - x) + 0.9 quencht·
which can be combined with Eq. (5-7) and rearranged:
o·
• [F)'o (5 - x) + 0.9 quench] -" (5-38)
Let us now calculate the quench at the end of each bed (except the
last bed, of course):
2,1lI1Cpl (T - To)
Quench = -'-'--- (5-39)
(Cp;)quench (T - 298.2)
(Cp;)quench = (0.9)(20.786) + (0.1)(6o.4I~) = 25.349 kJ/(kmol . K)
The pressure term P in Eq. (5-38) must be corrected at each step of

the numerical computation according to the pressure drop per unit
reactor length, which is calculated by means of th!' Ergun equation [Eq.
(4-1)]. This calculation is quite involved.
In the Erguil equation, G is the mass flow rate in kilograms per second
per square meter.
G = (92.141 FYoIA() + (2.016)(5)F)'oIA( + (l6.043)(5/9)FYoIA(

+ [(0.9)(2.016) + (0.l)fl6.043)]quenchIA c
G = (111.1338 Fyo + 3.4187 quench)/A(
CH~
Hz plonl CH~ rejection
unit
Fresh Hydrogen
Hz compressor Recovered Back -pressure
~ ..... H2 corn pressor cont roller ..
Recycle .:.:OS~_...,
•
Recycle compressor Effluent hydrogen gas
y
Hydrode alk yl alion Product

Feed process
FIG. 5-8 Block diagram showing the recycle, purification, and make up of
effluent hydrogen gas from the hydrodealkylation plant.
•
. .
•
•
The equati~n for U m, the superficial fluid velocity based on the empty
•
reactor, IS: •
U
(6.5555 Fyo + quench) (22.414 To 1.01325)
= -'--------"-"---'----.:.. .
m A( 273.2 P
Um = 0.0831295 (6.5555 Fyo + quench) To/A, P
The effective diameter of catalyst particles, dp, is defined by dp = 6

A,Z(l - E)/SI' where SI is the total surface area of the catalyst load. On
dividing both the numerator and the denominator of this expression by
the number of catalyst particles in the entire catalyst load we obtain:
d = 6(particle volume)
(5-40)
P particle surface area
If we use a catalyst shape such as a "square" cylinder, i.e., a cylinder

having its diameter equal to its height, then with 1p = particle radius,
6(r~11'){2rp) = 2 r
(211'rp)(2rp) + 21;11' P
Thus, if .ve set 2 rp = 3 mm, then dp = 0.003 m.

The viscosity IL of the reaction mixture can ,be computed from the
individual viscosities ILh 1L2, 1L3, and JJ.-I by using the elaborate relationship
1o
developed by C. R. Wilke. This is necessary because hydrogen does
not conform to simpler relationships. The equation is:
(5-41 )
-
with
•
[ ..+ (JJ./lLjt (MjlM;)' O]2
1 2 /t
i ::F J'
<Pij = (4/V2)[1 + (M/M)],!.
The term ij can be 12, 13, 14,21,23,24,31,32,34,41,42,43, and M;

and M j are molecular weights of components. In the computer program,
molecular weights will be designated MW!, MW2, MW3, and MW4, in
•
•
PROCESS DESIGN OF FIXED-SED GAS REACTORS 117
•
•
order to diaerentiate them from ml, 7n2, m:l, and Jn4, which are designated
MI, M2, M3, and M4, respectively, and denote mass quantities.
Now Ergun's equation can be evaluated. The expression (d/dz)g, in .
it is designated DELPZ in the computer program.
Now, we can substitute the proper numerical "alues into Eqs. (5-32)
and (5-38), and these equations will be ready f()r computer solutions.
Let us calculate these numerical valups:
(66,000 tlyr}(1000 :,g/t) 0.025122 kmol/s

Flu = ---~-':---.!......,;~-:---~~--:-/:------:- =
- (330 SD/yr)(24)(3600)(92.141 k~~ knw ) 1 t()iuene feed
For a plant of this kind 330 on-stream days, where SD stands for stream
days/year, are assumed.
Hydrogen feed = 5F)'1I = 0.12561 kmol/s

Methane feed = 0.5555 ho•
= 0.013955 kmol/s
Total feed = 0.164687 kmol/s
Initial mole fraction of toluene )'" •
= 0.15254
The reactor cross-sectional area A, is generall y limited at its maxinlUm

by mechanical design considerations. The maximum for this process is
not known, The internal diameter of 2 m assumed for this application
seems to be a perfectly practical size.
In integrating Eq. (5-32), neither x nor T can be used as an inde-
, pendent variable. Both are dependent variables. This difficulty can be
•
circumvented by dividing both sides of Eq. (5-32) by dz and rearranging
to:
dT dx F)',,( - M/)
-= .- (5-42)
dz
Equation (5-42) can be integrated with respect to dz, like Eq. (5-38).
This integration is implemented by means of a computer program,
named RDMOTI, written in the Fortran IV language and run on an
. IBM 3032 !'l1achine. The entire source program and computer output
are given in the following pages. Figure 5-9 is a block diagram of the
•
computer program RDMOTl: it displays the general organization of
the program. Figure 5-rO is a listing of definitions of computer symbols
and terms used in the RDMOTI program. Figure 5-11 is a listing of the
RDMOT 1 source program. At the end of the listing, the input data used
in RDMOT1 are given. Figure 5-12 is a printout of two RDMOTl run
outputs, with Fyo = 0.02512 and Fyo = 0.0345, respectively.
•
DIMENSION YI2l, F(21
P<O
DATA
INITIALIZE
•
WRITE TITLE
EOUIVALENCE
Y(11 X Y121.T YES F(O"O
WRITE INP'JT
DO 6 1=1. IeED
WRITE TITLE OF OUTPUT
INITIALIZE
Z, Ylll, YI2l,
P, ICOUNT
NO
3
YES
K=RUNGE 2
4
- YES lCOU~!T=ICOUNT +1
YES
NO ~100 1
YES
X<O
NO
YES
7
WRITE Z, P,
E Y (ll, Y I 2::.:-)
ERGUN
EQUATION
'------ ICOUNT=O
. ,
LWRITE Z.Y(ll. 7 WRITE Z,Y(ll.

Y121. P Y(2I,P_.J
COMPUTE WRITE
QUENCH TITL==.E../
/ WRITE 7
QUENCH END
L WRITE I •
6 SAVE DELPZ.Z.Y( 1)
FIG. 5-9 Block diagram of the RDMOTI progl'am.
118
•
DE~IHITIOH OF SYMBOLS IN R080T1

A FREQUEIICY nCTOR .
AC
DELPZ
CROSS-SECTIONAL AREA OF REACTOR,
PRESSURE DROP PER UNIT LENGTH, BAR/"
"··2
OH HEAT OF REACTION. ~J/K"OL
DP CATALYST PARTICLE DI1KETER. 8
E ACTIYATION ENERGY. ~J/KKCL
El'S VOIO FRACTION IN BED, DIKENSIONLESS
F DERIVATIVE IN FUNCTICN !HlNGE
FIO TOL'lENE FE::D. K"OL/S
G S[JP~RFICIAt !lASS FLOW RATE. KG/S.h U 2
H STEP SIZE. ~
I SE~aENTIAL NU~BER OF BEDS, DI~,N~IONLESS
IBED NUMBER Of ~AXIKUK BEDS, DIKENSIC~LSSS
ICOUNT COONTER Of STEPS fOR PRINTING fRE~UENCY, DI~fNSIONLESS
lfHEQ ?RINTING Y2EQUENCT. DI~ENSIONLESS
I( COUNTER OF PAsses IN FUNCTION tmN~E, DI'ENSIONLESS
!I COUNTER IN FIINC1'ION SlING!!
110 VISCOSITY Of IiEACTING CAS KIITUBE, PAS
1101 VISCOSITY OF TOLUEN! AT RlACTION CCNDITIONS, PAS
"U2 VISCOSITY OF BENZENE AT REACTION CONDITI~NS. PAS
KU3 VISCOSITY OF HYDROGEN AT REAC1ICN CCNDITIONS. PAS
1104 VISCOSITY Of !!ETHANE AT BEACTIGN CCN;JlTfONS, PAS
11111 ~OLECULAa WEICHT OF TOLUENE
.'! Ii 2 1I0L~CULAR ,EIGHT OF BE~ZENE
11113 1I0LEcnLAR .EIGHT OF HYDROCEN
/11/4 'IOLF-CULAR .EIGHT OF PI ET RA ME
111 PlOLAR FLO. OF TOLUENE, KIIOL/S
112 '10LAR FIO. OF BENZE~E, K~CL/S
(13 1101 AR FLOW OF HYDROGEN,KIIOL/S
"4 ~OLAR fLOii OF PlETHANE, KIIOL/S
P PRESSURE, ilAR
PAR DU~PlY VARIAilLE IN CClIpUTING f(1)
PHI •• DUIIIIY VARIABLES FOR VISCOSITY CO~PU1!TIOM
PHI (J) VARIABLE IN fUNCTION aUKr,!
QU P.NCll HYDROGEN CAS INJECTED AT THE END OP 7HE BED, KPlCL/S
RG CAS CONSTA~T = 8.316 KJ/KKCL.K
BSTAR CAS CONS:A.T = U.0831Q BAR*II •• 3/KIIOl.K
SAYEP DU~I\Y VARI~BLE fOR RECYCLING P
SAVEX DU~P\Y VARIABLE FOB BECTCLING X
S1VEZ DU~IIY VARIABLE FOB FECYCLING Z
SUII DOIIIIY VARIABLE IN COlIpOTING F(2)
S1 S2 S3 SQ DOII~Y YARIABLES FOR VISCOSITY COKPUTATION
• T TElIPEBATIlBE OF R!1CTION • "
I"AX IIAXIIIUII TE~PERATURE ALLOWABLE EEPOBE COOLING BED, K
TO TEIIPERAIUBE AT INLET, K
Of'( SU?EBFICIA: VELOCITY IN SABRI ERGUH EQUATION
I CONVEBSION OF TOLUENE, DIftENSIOMLESS
XO CONVERSICfi OF TOLUE~E AT INLet, DI~EHSIOHLESS
Y (1) ; x
Y 12) = T
Y1 ~OL FRACTION OF TOLUENE, DIKENSIONLESS
I2 ~OL fRACIleN OF BENZENE. CI~ENSICNL!SS
Y3 nCL FRAClICN Of HYDROGEN, DI!lENSICNL~~S
Iq !lOL FRAC!ION OF !lETHANE. DIKENSIONLESS
Z AXIAL COOR~INATE. 8
FIG. 5-10 Definition of symbols in the RDMOTl computer program .
119
•
DJ~ENSroN
Y(Zl.F(Z)
OATA IFREQ/I01
OATA OutNCH.SAVE7,SAVEX,SAVEP/O.O.O.O.O.O.O •• ,
I1'1TFGER PUN cr •
REAL Hl."Z."3.H4,HU,HU1."U2,~U3,HU4,H~1.HW2."W3.~W4
WRITE (6.150) .
150 FOR"AT elHl.20X.38HAOIAPATIC FIXED-SED GAS REACTOR nfSIGN/IHO.20X.
1 36MTOLUENE HVDROOEAlKYlATION TO eEN7ENE'
C •••• ReAO ANO PRINT nATA ••••
EQUIVALENCE (Y(ll.XI.(Y(Zl,TJ
REAO(5,100. ~O.TO,T"AX,RG,P,r.H,AC.H.E.fYO.RSTAR,A,JqED,HU1,HU?
1 "U3."U4.EPS,DP,"Wl,HW2,HW3,HW4
108 FORHAT(7fl0.3'Zfl0.3.2fI0.5.E1Z.4.4X,I2/6fl0.7/4FI0.61
WRITE (6.Z001 XO,TO.THAX,cYO,RG,RSTAR,P.H.OH,AC,~,A.HU1.HU2,HU3,
1 ~4,~PS,~,HW1,HW2,HW3,HW4,I~fO
ZOO fORHATIIHO.5X.3HXO=.f6.4,5X,~hTO= ,f6.1,ZH K.eX,6HTHAX= ,f6.1,
1ZK KitH .5X,5HfY~= .f7.5.7H KHOL/S,15X.5~PG =,f9.3,10H KJ/KHOl.KI
Zlft .5X.6HRS~~R=.Fe. 5. HI' eAl>. H'''3/KHOL. K ,4X.ZHi?=, f5 .1, 8H BAR A~S,
35X.2HM=.F5.3/1H .5X,3HOH=.f~.1.8H kJ/KHOL.15X.3HAC=.F5.3,5H H•• ZI
4 ~H .5X,lHE=,f3.1.8H KJ/KHOL,15X,ZH4=,E15.1'lH .5X,4H"Ul=.F~.7,
j 5H HUZ=.FQ.7. lX.4HHU3=, f9.7,ZX.'"HU4=. f9.7.4H PAS/1H ,5X.
6 SH£PS= ,F5.3,4X.SHCP = .f7.5.ZH HilI' .Sy.5HHWi= ,F7.3.2X.SHMWZ= •
7 F7.3.6X.5HHM~= .F7.3,4X.5HHW~= .f7.3/1H .5X,5HI8FO=,I?)
00 6 1=1. HIED
w!tI1' (6,1511 I
151 fORH.T (IH1.35X,10HFIXEO eEe .121
WMITEe6.201l
ZOl FORMAT C5X, 17HREACTOk LENGTH. M. 4X.I0HCONVERSION,4X.
113HTfMPER.TUP~.K.4X.12HPRESSURE.8AR'
C
C •••• INITIALIZE Z, Yll1. VIZl. P AND ICDUNT ••••
Z = 0.0 + SAYfZ
YC11 = XO + SaVEX
YC21 = TO
P = P - ISAVEP.Hl
ICOUNT = 0
C •••• CAlL ON THE FOURTH-ORDER RUNGE-KUTTA fUNCTION ••••
2 K=RUftGEeZ.Y,F.Z,HI
C IF ~=1. COMPUTE DERIVATIVE .aLUES
If(K.NE.IJ GO TO 3
C •••• MATERIAL BALANCE EOUATION ••••
I"C~.LT.O.1 1:=0.
If eX.GE •• 9991 GO TO 7
COHPUTE GASH1X VISCOSITY HU ••••

V1= FYO·ll.-XI/C6.55554fYO + QUENCHI
"2= FY04XI C6. 5555"fYO + OUENC .. '
Y3= IfY04C5.-X) • O.q·QUENCH"C~.55554Fya • QUENCHl
Y~ CFYO·(0.5555 • XI • O.1 4 0UENCHJ/C6.5555"FYO + QUENCH)
PHI12= Cl.+(SQRT(MUl/MUZJ'.((HW2/MW11 •• S.25)!'.ZI
1 ez.aZ~44e1.+{MWI/H~2J'·"O.5)
PIII13= Cl.+(SORTIMU1'HU3,,4(CHW3'"Wl,··O.Z5',·"Z'
1 e2.eZe4·el.+(H~1,"W3)1··O.51
PHrt4= (!.+(SOPTeHUI/HC41,·e(HW4/HWIJ··O.2511··ZI
1 e2.8Z84·el.+(HW1/HW~}I··O.51
P>iIZ1= C1. + (SORT UWZ/I'!(!1 " . ICHW1,,",w7l •• 0. 251 J ."21
1 (2.8Z~4·ll.+CHWZ/HW11'''''O.5J
Pl'I23= Cl.+(SORTCHU2/~U31)·(IHW3/HW2)"·O.25114·ZI
1 eZ.8284 4 (1.+(HW2/MW31)··O.51
PIlIl"= 11.+(SORT(MU2/MU41'·«MW4 / MW21··0.2SI'··ZI
1 (2.8284·(1.+(HW2/~W4J)··O.~1
PilI H= (1.+csaRT(MUl/~CIIJ·«MWI/HW3)·"0.Z51'·"ZI
1 e2.8264·C1.+(M~3/~Wl11··O.SJ
PIIIl?= (1.+lsaPT(HU3'~U2)I·C(HW2'H~3)"·8.2511·"2'
1 CZ.~2e~·ll •• (HW3/~H~II··O.~1
P"I34= (1.+($CRT(HU1/HL41'·C{HH4/HW~I··O.25"··2/
1 (Z.~264~(1.+(HH3/MH411··O.51
PI1T41= 11.+csaRTCMU4'~Ull'·(HW1'H"41"·O.Z~II··2'
1 C2. '17114' (.t •• I'''H4/11 Ht 11·· O. S 1
FIG. 5-11 The RDMOTl computer progtam for the design of an adiabatic
fixed·bed reactor for the hydrodealkylation of toluene to benzene.
120
•
P"I~Z; (1.+(~OPT(HU4'HCZl)-(MWZ'MW4l--0.2SI'--2'
1 (Z.8Z84.(1.+("W4'~W2')-.O.SI
•
PMI43~ (1 • • (SORT(HU~'HU3l'·(I"W3'HW4'--O.2S"--Z'
•
1 (2.82e~·(1 •• (HW4/"W31)··O.~1
S1;\I.0
S2=0.1I •
S3=0.0
SIo=O.O
IF(Yl.GT.O.l~1=HU1'(1.+(Y2/Yll·PHI12 • (YJ/Yll'PHII3 •
1 (Y4'Yll-PHI141
IF(YZ.GT.O.IS2=HU?'(l.+(Yl'Y7l·PHI21 + IY3/YZI·PHIZ3 +
1 IY4'YZ).p~IZ41
IF(Y3.r.T.O.IS3=HU3'(1 •• (YI/Y~I"PHJ31 • (YZ/v3,·PHI3Z •
1 CY4'Y31'PHn<t1
IFIY4.GT.O')S4=HtJ4'11"(Yl'Y~I"PHI~1 • (Y2'Y41"PHr4Z • ,
1 (Y3'Y~l.P~I431
HU= SI • S2 • 53 • S4
c COMPUTE THo ~~8RI ERGUN EQU~TION FCP PRESSURE OPOP ••••
UH: 0.O~313·116.SSS5.FYCI + OUENCHI+TO/IAC·PI
G = (111.13+FYOI + (!.4157"QUENCHII/AC
OElPl; 11.5f-03 ·1(1.-fPSI"·ZI·HU+~~/(fPS"·31·ICP."211'.
1 11.75E-05 "' 1.-fPS'·G-UM/«([PS··31-(OP111
P = P - (OELPZ"HI
IFIP.lT.n.1 GO TO 7
PA~= (P/(~STAR.T·(6.S5SS·FYO • O~EN~H)" •• 1.5
FIll; ~C·A·EXP(-E/(Pt,.TII·PAP.(l.-X)·
1 (IFYO·(S.-XI • O.q·QUENCH1··0.SI
IF IFllI.lT.C.1 FUI=O.O
C
C •••• ENERGY ~ALANCF EQU~T!ON •••.
"1=FYO"(1.0-),)
HZ=Fyn+X
M~=FYO·(S.O-~) + IO.~·OL£NCPI
H4=FYO·IO.5SSS+Xl IO.l·CUENCHI +
SUH=Hl·1124.~S.(O.03S~5·TI) •
1 "Z"(i03.1~+(O.1067.TII +
2 H3·I~O.786) +
3 H4·(27.87+(O.04~1~-TII
F(Z)=Frl'-FYO-OHISUH
IF (F(ZI.LT.O.1 F(ZI:O.Q
GO TO Z
c
c •••• IF T fXCEFOS T"AX. TfR~INATf INTfGRATION ••••
3 IF(YI21.L[.THAXI GO TO 4
GO TO 5
~ ICOUMT = ICOUNT + 1
•
IF IZ.GE.ln~.O) GO TO 7
•
IF (ICOUNT.NE.IFREQI GC TO 2
MR!TE (6.2021 Z.Yll'.YI2',P
zaz FURHAT 11~ • 7X.F8.3.13X.F5.3.10X.F6.1.11X.F6.?1
ICOUM" = 0
GO TO 2
5" WRITf" (6 .. ~OZ' Z.Y(1.' .. Y(l'.,P
saVEO = QlIENCH
QUENCH=SUH-(T-TOI/12S.34q·(TO-2QS.ZJI
WRITE (6.2~3) QUENCH
Z03 FOqHAT(lHn.5x.l1HfNn OF efo •• ~x.qPCL~NCH = • F 10.5. 7H l(HOL IS I
Q~ENCH = QUENCH + SAVEQ
saVEP = OELPZ
SAYEZ = Z
WRITE(6.qqQI I
~9 FOR"AT(tH .5l. 7H8EO NO=.131
6 SAVEl = TUI
7 WRITE(6.Z021 Z.Y(I'.Y(ZI~?
IIRITEI6.20 .. ,
Z84 fOR".TI~H .5X.1SH~NO OF REACTOR.I
S",O"
[HO
FIG. 5-11 The RDMOTl computer program for the design of an adiabatic
fixed·bed Ieactor for the hydrodealkylation of toluene to benzene (continued).
121
•
c
FUNCTION RUNG£ IN.T.F,1,H'
I1HE6ER RUNGE •
DIMENSIUN PHIt"SOhSAYfYlSO) .YINI ,FIN)

DIITA 'VV
c •
" = " + 1
GO TU 11.2.3.4,51, "
c PIl:'S 1
1 RUN(;£ = 1
R!:TtmN
C PIlSS 2
Z DO ZZ J=l.N
SAYETIJ)=yeJI
PKI(J'~ <.!.
Z2 yeJI=SAVEY 1.1' +C.5 • H • Fe.!)
Z = 2 0.5 • H
y
RONe£ = 1
RI!TURN
C nj.S~ 3
3 00 JJ J=1.11
PIU t.n = PHIf.!) + 2.0 • FIJI
33 VlJ) = SAVEYIJI + 0.5 • H • FIJI
RllHGE = 1
RfTURN
C
.. 00 .... J=1.N
PASS. 4
PIU 1.1' = PHIfJ' + 2.0 • F(Jl

It .. TIJ. = SAYfYfJl + H • FIJI
Z = Z + 0.5 . • H
RUNIiE = 1
RfTU!?N
C PASS <;
5 DO 5'5 J - 1.N
55 yt.!, = SAYfVIJ. + ePHHJI + FtJ"· "'6.0
"=0
R!lNG£ = 0
RHORN
ENO
!l'\PUT DATA; CASE I: fYO = 0.02512

, . , 0.0 873.2 908.2 11.3110 50. 109974.0
0.05 148114.0 0.02512 0.98314 5.73 £+86 6
O.OOOOZ 0.0000224 0.0000182 0.eOl1026 O.3S 0.003
92.141 78.114 2.016 11; .043
•
[l'\PUT DATA; CASE 2: FYO = ll.03390
0.0 H3.2 '>08.2 11.314 50. 4'3'31".0 3.142

0.115 14811".0 0.033'>0 a.0831" 5.73 E+06 6
0.00002 0.0000224 O.1I0001~2 n.000026 D.le 0.003
92.141 18.1H 2.016 16.043
FIG. 5-11 The RDMOTI computer program for the design of an adiabatic
fixed-bed reactor for the hydrodealkylation of toluene to benzene (continued) .
122
TOlUE~E HYOPOO£AlKYLATION TO SEN1EN~
XO=O.OOOO TO= 873.2 K THAX= '306.2 I(

FYO= .02512 KHOt,S . RC = 6.314 KJ'KMOl.1(
RSTAR= .0831' BAQ.H··~IKHOl.K P= 50.0 BAR A~S H= .050
OH= ~9974.0 KJ'KMOL . AC=3.142 ... ··2
E= 1~~11~.0 KJ'KHOl A= .5730000E+01
HUI= .0000200 HU2= .~O~0?24 MU3= .0000182 MU4= .0000260 PAS
EPS= .3~O OP = .00300 M
MW1= ~?141 HW2= 78.114 2.016
lBEll= 6
"PFO B£O 1
REACTOP LENGTH. M CONVERSION TEMPfRAT~:.K P"fSSU~E. BAR
.500 .040 e7~.6 "9.'3'3
1.000
1.500
.063
.131
6~7.0
&'34.'1
"9. '37
4'3.'3f>
2.000 .16S 49.95
2.31!0 .220 "'l.g4
END OF BED. QUfNCH = .01'3<;1' KHOl'S

BEU "0= 1
FIXE!: QrV ?
IlfACTOR LfNGTH. H CONVERSION TEt\PEPATUP~.K PPfSSURf.BAP
2.1100 .247 '177.1 4'>.'3?
~. 3~O
3.1100
.274
.304
8P~.2
~I'-S.5
"".'11
4'l •• 9
1t.300 .~~4 APt;.q "'3,88
'.800 .366 6'34.4 1t'3.86
'5.300 • .39':: 8~~.2 "'3. Re;
'.600 .433 <;0".0 "9. 6:!
6.250 .4&5 "QQP.4 "9.~2
£NO OF IlHl. OU£NCI< =

BED NO= "
FIXED ftEn .
•
, REACTO!> LENG TH.

{,. 7'50
H CONVEI1SION
.4e1
Tf""'(PATtJRf. K
~75.3
p,~:SSUQ'~ ~ 8~ ,~.
c.q. "C
7.250 .'~7 877." 4'l.7Q
7.750 .513 879.5 4 0 .17
11.2'50 .530 ~A1.6 Itn.7e;
!I.750 .~46 ~·:r.7 4 0 • 7 ;>1
Q.2'j0 .5E~ 88S.'! 4 0 .72
~.75U .57'3 8~~.n 4G.70
10.2'50 .596 ~90 .1 "-9. ~ A
10.750 .EL! P'32.3 4C?.66
11.250 .62'3 89".'t 4 0 .6<;
It.7'50 . f 46 11'36.5 4'l.63
1Z.250 .66< e'la.5 "Cl.61
12.750 .E-7Q '?00.6 "~.5,?
13.250 .6~5 00<'.& 4Q.511
13.750 .711 904.'" 100.5'"
14.;>50
1".700
.727
.741
90t.«7
'308.2
"".54
"q.5~
ENt' OF 81"0. QUENCH =

IlEO ,.0= 3
FIG. 5-12 Printouts of two RDMOTI computer runs.

..
123
.. .
•
FIXEO SEO 4
REACTOR LEN1>TH, M CON¥ERSIOtf TEMPERATURE ,I( PRESSURF, eAR •
l~.ZDO .747 1174.8 49.t;1 •
15.780 .7'S1t 1171t.7 'It'). It')
16.Z00 .760 1175.t; It') .lt7
.16.700 •.767 876.2 1t'l.lt5
17.Z80 .773 1177.0 1t'l.43
17.70e .77<J 877.7 1t'l.lt1
111.200 .7M 878.4 "9.3'l
1.11.7041 .792 879.1 ""'.37
19.200 .798 879.11 49.35
1".700 .en3 1180.5 "'l.33
•
•
•
•
•
4"i.700 .972 8'l9.0; 1t8.27
"6.200 .~7.3 899.7 .. e.25
"6.700 .97" 8':19.8 "S.23
1t7.200 .'375 899.') .. e.21
"7.700 .glE gOO.O 411.1q
"11.200 .q77 900.1 .. ~.17
"8.7110 .978 900.2 .. ~.15
1t9.200 .'37'3 900.3 .. ~.13
"9.700 .4!'lO 900." .. ~.11
511.200 .9~1 900.5 108.09
50.700 .'382 'lOO.£. •
"'1.07
51.200 .9~3 900.7 Io~.05
51.700 .«383 900.11 Io~. 03
52.200 .~84 900.8 "~.01
•
•
•
•
•
78.700 .'l'38 902.1t 46.90

7'3.200 .'l'38 ':102 .... 106.88
79.700 .'l'3'l ':102." .. 6.86
lID. 200 .'399 902.5 "6.810
80.700 .'l99 902.5 "6.81
81.200 .99'3 'l02.5 "'£..7'l
IIl.70D ... 99 902.5 "6.17
IIZ.ZOO .,)99 902.5 "'6.75
112.700 .'39'3 9l1Z.S 46.73
1I~.20a .9'1') ')02.5 "6.71
• 113.700 • .9'3'3 902.5 "6.6')
•. .
" ... 200 .'3'3'3 ')112.5 "6.67
8"."25 .'399 902.5 "6.66
ENO OF REACTOR.
FIG. 5·12 Printouts of two RDMOTl computer ruIllS (continued) •
..
124
•
ADIABATIC FIXED-SED GAS REACTOR DESIGN
,
TOLUENE ~DROOEALKYLATION TO BENZENE
•
xo=o.oooo TO= ~73.Z K Tl1AX= 908.2 K
FYO= .03390 KHOL/S RG = 8.314 KJ/KHOL.K
RSTAR= .oe314 BAR.H •• 3'~OL.K p= 50.0 BAR ABS H= .050
OH= 49974.0 KJ/KHOl AC=3.142 H.... 2
E= 148114.0 KJ/KHOl A= .5730000E+07
HU1= .0000200 HU2= .0808224 "U3= .0000182 ~U4= .0000260 PAS
EPS= .380 OP = .00300 H
MW1= 92.141 HW2= 78.114 "W3= 2.016 MW4= 16.0"3
I8EO= 6
FIxED BED 1
REACTOR LENGTH. H CONV£RSION TEHPERATURE. K PRESSURE. BAR
.500 .02'3 878.0 "9.98
1.000 .060 883.2 49.96
1.500 .11'33 e8e.7 "9.93
2.000 .130 89/0.6 1,9. 'a
2.500 .169 "901f .8 ..9.89
3.000 .211 CJ 07.5 49.117
3.050 .215 90e.2 49.e7
ENt) OF BE{). a~NCH =
('EO NO= 1
FIXED BED 2
REACTOR LENGTH. H CONVERSION TEHPERATURE.K PRESSURE.BAP
3.550 .235 876.1 49.S4
4.050 .255 e79.1 49.82
... 550 .276 882.3 49.79
5.050 .298 885.4 "9.76
'5.550 .321 8811.7 "9.7"
6.050 .3.... 892.1 "9.71
6.550 .3611 895.5 "'3.69
7.1l51l .393 899.1 49.66
7.550 ... le '302.7 49.6 ..
8.050 ..... 5 91l6.3 49.61
8.350 ... 61 908.6 "9.60
ENO OF BED. QUENCH =
,
EEO NO= 2
FIXE{) BED <I

"
REACTOR LENGTH, CONVERSION

8.850
9.350
" ...72
.4-e4
TEHPERATURE.K
874.7
876.3
PRESSURE,BAR
"9.57
9.850 "9.5"
... 96 877.9 49.51
10.350 .501l 879.4 ..9 ... 8
10.851l .520 881.0 49.45
11.351l .532 882.6 .. 9 ... 2
11.850 .545 8e4.2 "9.39
12.350 .557 885.8 "9.31
12.850 • 569 887 ... "9.3"
13.350 .582 889.0 49.31
13.1150 .59" 1190.6 49.28
1'+.350 .6117 892.1 "9.25
14.850 .619 893.7 "9.22
15.350 .631 895.3 ..9.19
15.85() .6 .... 896.8 "9.16
16.350 • • 656 898 ... "9.13
16.850 .668 8'39.9 "9.10
•
FIG. 5-12 Printouts of two RDMOTI computer runs (continued).
125
•
17.350 • 680 901 ... 49.07
17.850 .692 902.9 "9.04
18.350 .701t 904." "'3.02 ,
18.050 .716 905.11 ,,6.9'3
19.350 .727 907.3 ..0.96
19.700 .n.5 908.2 "8 •."'1t
EN!! OF 8EO. QUENCH =
BEO"O= 3
FIXED BED ..
REACTOR LENGTH, H CONVERSION TEHPERATURE,K P~ESSUIlE, BAR
211.2110 .7"0 813.8 "8.90
20.700 .7.. 5 87"." "8.87
21.20'0 .750 871t.'" "S.83
21.700 .755 875.5 "8. eo
22.200
22.700
.760 876.0 "e.77
.76" 876.6 "8.13
23.200 .169 817.1 "8.10
23.700 .17" lI71.7 "8.67
2".200 .778 1178.2 "8.63
2 ... 700 .783 lI78.7 1t8.60
•
•
•
•
•
53.200 .949 897.6 46.1;2
53.700 ."'51 897.8 "6.59
54.200 .952 897.9 "6.55
5 ... 711 0 ."'54 898.1 106.52
55.200 .955 898.2 "6 ... e
55.100 .• 956 896.1t "6.45
56.200 .951 8911.5 .. 6 ... 1
56.100 .'359 896.7 46. '3 6
51.200 .960 898.8 "6.3"
51.700 ."'61 898.9 .. 6.30
58.200 .962 899.0 "6.27
58.100 .963 899.2 "6.23
•
•
•
• ,
•
• •
93.200 .995 '302.7 43.70
93.71!0 .995 902.7 43.66
S4.200 .995 902.7 "3.62
94.700 .996 902.7 .. 3.59
95.200 .CJ96 CJ02.8 "3.55
95.700 .996 902.8 "3.51
96.200
"'6.700
.996
.'996
902.8
",oz.e "3." 7
"3."~
91.200 .996 902.8 103.40
97.700 .996 902.8 "3.36
98.200 .996 902.8 "3.32
98.700 .996 902.8 "3.28
99.200 .997 902.9 43.24
99.700 .997 902.9 103.21
100.050 .997 902.9 43.18
:Nll OF REACTOR.
FIG.. 5-12 Printouts of two RDMOTI computer runs (continued) •
126
•
,
Most aspects of RDMOT 1 are self-explanatory. However, the follow-
ing comments and the diagram of Fig. 5-9 should be helpfuL
· RDMOTI is an application of the fourth-order Runge-Kutta program
explained in Sec. 2.5 for solving initial-value ODEs. It uses the FUNC-
TION RUl'\GE.
· The step size H is not varied inside the program. It is read in along
with other input data. The program can be tested with various H
values until one is found below which the results stay constant. For
this purpose it suffices to test only a single bed.
· iZDMOTl is designed for a multibed reactor with intermediate gas
quench. The program stops the integration of the ODEs when the
reaction temperature T exceeds the Olcximum temperature Tlllax> com-
putes the amount of H2 gas required to quellch the reaction gases
from T max to the iplet temperature To, adds this H2 gas to the reaction
stream, and proceeds with the calculation of the next bed. The pro-
gram can be run with any number of beds; however, by setting IBED = 6
we make it stop after the sixth bed, if it has not stopped for some
other reason before. The computation also stops when the conversion
approaches completion. At the end, the reaction slows down consid-
erably and x approaches unity asymptotically. For tt-is reason the pro-
gram is stopped when x = 0.999. The program can also be stopped
when the pressure P falls to zero or to any desired level.
. If RDMOTl is used for a different reaction, it can b<:easily adapted
to use a liquid quench, a gas-liquid quench, or indirect intermediate
woling.
. The program prints the results after every IFREQ calculation. Tt counts
the steps by adding 1 to ICOUNT. When ICOUNT = IFREQ, it prints
and starts all over again.
The results of the RDMOTl program are given in Table 5-1. They
show that most of the conversion occurs in the front part of the reactor
and that it approaches unity asymptotically. Only four beds were cal-
culated and the calculations were stopped at x = 0.999.
These results show that the conversion reaches 0.741 at the end of
the third bed and that the fourth bed becomes unreasonably tall and •
slow. In such a case, it is more economical to build only three reactors

and to distil! and fractionate the product of the third reactor to obtain
pure benzene overhead. and toluene at the bottom. This toluene must
.. be recycled to the inlet of the first,reactor. The first three reactors may
127
•
128 CATALYTlC REACTOR DESIGN
•
TABLE 5-1
Results of the RDMOTl Proglam
•
Bed length, m Conversion

AT/AZ, QUENCH,
NBED Z x Km l:AP kmolls
1 2.3 2.3 0.22 0.22 15.56 0.06 0.06 0.01966

2 3.95 6.25 0.245 0.465 8.91 0.12 0.18 0.0219
3 8.45 14.70 0.276 0.741 4.098 0.29 0.47 0.0246
4 43.00 57.70 0.258 0.999 0.658 l.7S 2.22
be grouped as shown in Fig. 5-13 and the fractionation setup may be

designed as shown in Fig . .')-14. The selection of the total reactor length
versus the extent of the fractionation must be based on sound eco-
nomics a subjectthatwill not be discussed here.
Our problem was to convert 66,000 tlyr or 0.02512 kmol/s of toluene
to benzene. However, the just designed reactor system will only convert
74.1 % of this quantity. In order to increase the production of the plant
to the full amount, we can eitl'er increase the reactor cross-sectional area
Ar by l/x, which correspon<!s to a reactor diameter DT = 2.323 m, run
the 2.0-m-diameter reactor with a feed of 0.0339 kmolls of toluene, or
select a combination of lalger diameter and faster flow. First it must be
\.
'. ,
T
2.3 m I
8.45 m
:m
]I
3.95 m
DT = 2.323 m
Hz quench •
FIG. 5-13 Configuration o(1'uee consecutive adiabatic fixed beds for toluene
hydrodealkylation with inteullediate hydrogen quench.
•
PROCESS DESIGN OF FIXED-BED GAS REACTORS 129·
•
Benzene
F*' Corrected toluene copacity •
...
F10' Fyolx
------
Fyo Hydro-
dealkytation
kmol/s process
Toluene recycle
.FYo(l-x}
FIG. 5-14 Block diagram showing product distillation and toluene recycle in
toluene hydrodealkylation.
ascertained that the choice of larger reactor diameter is really available.

At high temperatures and pressures certain reactor designs set a practical
limit to the reactor diameter.
A computer rUll with a diameter of DT = 2 m and a high feed flow
of 0.0339 kmoVs of toluene is shown in the third and fourth sheets of
Fig. 5- I 2. \Ve can see that the catalyst required in both design cases is
about the same as summarized by the following results:
2
DT = 2.323 m Ac = 4.240 m Z = 14.70 m
3
l' = 62.228 m x = 0.741
2
DT = 2.000 m Ac = 3.142 m Z = 19.70 m
3
V = 61.89 m x = 0.735
The choice will be decided by reactor metallurgy and of course by
•
economICs.
5.3
NONISOTHERMAL, NONADIABATIC
FIXED-BED (NINAF) GAS REACTORS
K!:-\AF gas reactors have been defined in Sec. 4.2 as packed tubular
reactors which are side wall-cooled or sidewall-heated and usually are
bundled up like heat-exchanger ~ubes. The ratio of sidewall surface area
to the catalyst volume becomes an important design parameter with
KIKAF reactors. Anoth~r important design consideration is that sidewall
cooling creates a radial v.ariation of temperature and concentrations in
the reactor that considerably complicates calculations.
•
•
Existing Models of the NINAF Gas

Over the years, several NINAF gas reactor models have been developed:
a simplifted model, a semirigorous model, and a rigorous modeL Discussions
af simplified and semirigorous models, which were developed by a num-
ber of workers, were included in J. M. Smith's 1956 textbook 11 but were
12
not substantially updated in his 1970 second edition. The simplified
model is too inaccurate to be of any practical use, especially because
NE\, AF reactors are extremely temperature-sensitive.
The semirigorous model assumes that: (1) the thermal conductivity
is constant in the whole catalyst bed, and (2) there is no difference in
temperature between the solid catalyst and the bulk gas flow. These
assumptions have resulted in the concept of a two-dimensional reactor model
in which the catalyst particles and the bulk gas flow are replaced by a
hypothetical solid in which cont:uction is the only mechanism of heat
transfer. The thermal conductivity of the solid is called the effective ther-
mal conductivity. The main objection to this model is simply that it is too
far from reality. The fact of the matter is that the overall thermal con-
ductivity of the catalyst bed plus the gas does change in the radial di-
rection and that the temperature difference between catalyst and bulk
gas does increase with increasing exothermicity of the chemical reaction.
Precisely because a NINAF reactor "'ould be selected only because of
the high exothermicity of the reactions, tile assumption_ that catalyst
temperatures and bulk gas temperatures are equal just does not make
sense.
Another objection to the semirigorous model is that, philosophically,
• the term semi-rigorous is self-contradictory. Something can be either rig-
orous or not but it cannot be semirigorous.
13
Carberry has described a steady-state NINA F gas reactor model .14
which appears to be the closest yet to reality. On the basis of experimental
l5
evidence that axial dispersion is not significant in gas reactors, this
model rightly neglects this factor. However, the model takes full account
of the radial dispersion of mass and heat. The bulk gas flow and the
catalyst pellets are not assumed to be at the same temperature. Because
the thermal conductivity of the solid catalyst is usually very high, no
temperature gradient is assumed in any catalyst particle, although var-
ious particles are expected to be at different temperatures. Heat transfer
between the catalyst and the bulk gas is assumed to occur across the
exterior surface of the catalyst particle. The isothermal catalyst particle
temperature is assumea to represent the reaction temperature at any
point of the bed. We witl henceforth refer to this model as the rigorous
•
NIXAF model.
•
Because NINAF gas reactors for exothermic reaLtions are extremely

temperature-sensitive, it would be both unsafe and uneconomical to use
anything but the most rigorous model to design them. In past decades
various difficulties discouraged the use of such rigorous models, but
today the proper computer software is widely available and there can
be no more excuse for not using a really rigorous model.
Development of Design Equations for a NINAF

Gas Reactor for a First-Order Reaction
Let us now consider an elongated tubular packed reactor of bed height
or axial coordinate z and internal diameter D r , fully packed with a het-
erogeneous catalyst of particle diameter dp and jacketed on the sidewall
in vrder to maintain a desired temperature along the wall of the long
reactor c;hell, as shown on Fig. 5-15. Let us subdivide this reactor into
five radial increments M and into a number of axial increments Llz. In
this way, we will have five annular shells, each one subdivided into a
numbCl' of annular sections, commonly called "onion rings." One such
onion ring is shown in detail in Fig. 5-15. The values of both the radial
increment aR and the axial increment az are constant. It is possible to
vary th~ step size during the course of integration as needed, but this
refinement aud complication was not deemed necessary in this book.
F (R,Z)
Tw T (R,ll
F(R,O) ,--
.... . .. • J
"', .. •
Dr - I • \ , •
- I
--
•
T(R,O)
\<1'
- ~
,
\
,
z
R
Differential
annular section
-tJz-
•
FIG. 5-15 Schematic representation of the NINAF gas reactor with details of
a differential annular section.
•
,
The concentration of the key reactant at the inlet of the reactor is Co-
The absolute temperature of the reaction mixture is To. The inlet tem-
perature is assumed to be somewhat above that maintained in the jacket.
A mass balance around any particular annular section leads to the
development of the design equation. At steady state we ca;l write:
Molar molar molar molar

inflow - outflow + inflow - outtlow
axially axially radially radiully
,
molar
- disappearance - 0 (543)
by reaction
The cross-sectional area of the onion ring in the Z direction is 2'lTrAr.

With it, the above balance equation can be expressed mathemetically as
follows, using Fick's law, i.e., molar flow = D r(27rrAr)dCldr .
•
ac
(27rrAr)u(Cl z - clz.uJ + -D r 27rrAz-
ar r
- - (27rrArAz) 91.= 0 (5-44)

,- +.6r
where u = fluid velocity in bed, m1s

3
C = molar concentration, kmoVm
2
Dr = radial mass diffusivity, m /s
Clz = molar concentration at axial distance z from the inlet
!R = reaction rate function based on unit catalvst
, bed volume,
3
kmol of reactant converted l(m • s)
Equation (5-44), divided by 27rrArAzu and rearranged, gives:
- - (5-45)
Az u rAr u
At limitinl') conditions.: ) 0, r ) 0, and Eq. (5-45) can be written:

•
•
(aClaz) = (D/ur)a(riJc/ar)ar - Wu (5-46)
-
A heat balance around any particular annular section leads to the
development of the heat balance equation:
•
•
PROCESS DESIGN OF RXED-BED GAS REACTORS 133
•
(Heat inflow axially) - (heat outflow axially)

+ (heat inflow radially) - (heat outflow radially)
+ (heat generated by reaction) = 0 (5-47)
, aT
(27TrAr)upcp(TL - 7l+AJ + - Kr27rrAz p cl'
ar r
.
aT
- - K27r(r+ -1 '·) ..h-- pc" + f27rrb. ~Az)( - AJ/)~R = 0 (5-48)
ar r+Ar
where cl> = specifir he::t of gas, KJlkg (includes all gases)

p = specific gravity of gas, kg/m:l (includes all reacting gases)
KT = radial thermal diffusivity if' packed bed, m:!ls
When divided by 27rr~TAz cpup and rearrangeJ, Eq. 15-48) gives:
n - 7tH:
~----~~ + -Kr(aTlar)
.
z uAr r
- Kr(r + Ar)(aTfar)
- (5-49)
u r~r r+ar
[TI,+.1: - TI,]/Az = (K'/u) .. [(r + Ar)(aTfiJr)L+~r - "(aTlo7')lr]lrAr

+ (-AHhRlcpup (5-50)
When Az ) 0 and flr = 0, •
[TI,+, - TU/Ilz ) aTliJz
[(r + Ilr)(aTfar)lr.ur - r(iJTfi1r)irJlrllr ) (1/r) .. i1(raTfiJr)/iJr

The derivative of a product can be expressed as follows:
d(roTlor)lar = ro2Tfal + (aTfiJr)(orlar)
Thus Eq. (5-50) becomes:

(dTliJz) = (K/u)[(rPTlar ) + (aT/ror)] 2
+ (- AH)~R./cpup (5-51)
Equations (5 .. 46) and (5-51) are the two PDEs that describe the NINAF
reactor. Together with the proper rate equations and auxiliary condition
expressions, they can be conveniently solved by the computer technique
developed in Chap. 2 for PDEs. However, it is more desirable to trans- •
form Eqs. (5-46) and (5-51) into forms that contain dimensionless var-
iable~, not because the mathematical solution will be any easier it will •
not but because the res,!iting equations contain a number of dimen-

sionless groups which are more generally applicable and thereby make
designing considerably easier.
•
Let us use the following dimensionless va.·iables:

•
C, = CICo reduced concentration of key reactant

3
Co = molar concentration of key reactant at inlet, kmol/m
T, = TITo reduced gas temperature
To = absolute temperature of reactant at inlet, K
Z = zldp reduced axial coordinate
dp = catalyst particle diameter (for catalyst particles of cylin-
drical shapes, dp represents the diameter of the sphere
having the same surface as the cylinder)
reduced radial coordinate
With these dimensionless variables Eq. (5-46) becomes:
Again, the derivative of a product can be written as
[a{R(Jc/aR)JIaR = R . a«(JC/aR)I(JR + (aC/aR)

= (Ra~C/aR2) + (aC/aR)
Thus, considering that dpulD, is called the radial Ph/et number Jor mass
(Pem ), we obtain (see Chap. 4)
2
aCT 1 a c, 1 aCT dp,j(
(5-52)
az = Pe m aR 2 +R. iJR - Coli
Similarly, Eq. (5-51) becomes, upon substitution \rith dimensionless

variables,
aT, =
I
_. (5-53)
az
where K/wlp has been replaced by the di,nensionless group called radial
Ptclet number Jor heat, wqich is designated by the symbol Pe".
In Eqs. (5-52) and (5-~3) the left-hand terms represent the axial gra-
dients, the middle terms the radial gradients, and the right-hand terms
the specie~ generation terms, which include the apparent reaction rate ~R..
•

•
Finally, we need the auxiliary values of the PDEs (5-52) and (5-53),
in order to integrate them. The auxiliary values are:
Bed inlet Z = 1 C,(R, C) = I T,(R, 0) = I (5-54)
aC,(O,Z) = 0 T,(O,Z)
Centerline --.:...;.......:.-.:. = 0 (5-55)
aR aR
aC,(R T , Z)
Reactor wall . = U (5-56)
aR
iJT,(R T , Z)
(5-57)
aR
The boundary conditions, Eq. (5-54), mean that at :he reactor inlet both
reduced concentration and reduced temperature are unit\·. The bound-
ary condition, Eq. (5-55), states that at centerLle or reactor axis, the
reduced concentrations and reduced temperatares do not change with
radial coordinates. The boundary condition, Eg. (5-56). !>tates that no
mass transfer can take place through the reactor wall. The boundary
condition, Eq. (5-57), states that the heat flux at the wall. as expressed
by the modified version of the Fourier law, is equal to the product of
the wall heat transfer coefficient It", by the temperature driving force
between reduced bulk gas temperature T, and the reduce(! inside wall
temperature Tu" The reactor wall expression can be rearranged as:
-aT,
= Bi". (5-58)
iJR(T, - T.J
The Biu. numbers were discussed in Chap. 4.
The calculation of flu presents some difficulties. Reliable data are not
l6
available. Froment gives a plot of hu. d/Ag vs. Re with a number of
scattered lines obtained by various workers. Obviously the heat transfer
coefficient at the wall is one of the most important data and one should
be determined carefully if it turns out that a new pf()('ess might be run
in ;\I;\AF reactors. Howner, if such information cannot be obtained.
a conservative way to design a l'\Il'\AF reactor would be to use a rather
lower h". value corresponding to a given Reynolds number. If it turns
out that more heat transfer is obtained at the wall during the startup
tests of che reactors than the selected h". value would provide, there is
nothing to fear since the reactors would then be more stable than intended.
The system (If Egs. (5-.52), (5-53), and (4-1), the kinetic equation of
the type (5-1), (3-45), (4-11), (4-12), (4-11), (4-17), and (3-59), and aux-
iliary conditions given by Eqs. (5-54), (5-55), (5-56), and (5-57) adequately
describe a single first-order reaction occurring in a I'\I:,\AF reactor.
•
136 CATALYTIC REACTOR DESIGN •
However, it must be modified to handle a system of several first-order

reactions by replacing the ( -I1H R I) expression in Eq. (5-53) by I( - aH ;Ri)
in order to take account of all heat developed by all reactions taking
place in the reactor. In the case of two consecutive reactions
Ri = TJ1k l Cs R2 = TJ2k2Cn (5-59)
where CB is the concentration of the product of reaction I on the catalyst

surface. The v,lue of CB can be calculated for a "macromicropore model,"
accurding to Carberry.17
In .;olving this system of equations, we must use the computer pro-
gram developed in Chap. 2 to solve PDEs. However, we cannot start at
the inlet of the reactor and apply the PDE technique to compute TT and
C step by step for each Z, because at the inlet of the reactor we start
T
with bulk g-as conditions er and Tr and have to calculate catalyst surface
conditiom C" and T" using Eqs. (4-26) and (4-28), which relate bulk
conditions to cataly~t surface conditions. Such calculations car only be
done by iteration, as will be seen in great detail in the example of the
oxidation of naphthalene to phthalic anhydride, which will be discussed
next.
Example of NINAF Reactor Design: Air Oxidation

of Naphthalene to Phthalic Anhydride
This example was chosen because it has been widely discussed by
l8 19
Carberry l3.14 and others • and sufficient published data are available
to design a reactor. \Vhen this oxidation reaction is conducted in an •
excess of oxygen, the reaction system may be summarized by the fol-

lowing simplified equations:
*,
CIOHS + 4.502 -~) C 6 HiCOhO + 2C0 2 + 2H 20 (5-60)
Naphthalene Phthalic
anhydride
k.
C 6 HiCOhO + 7.502 .) 8C0 2 + 2H 20 (5-60a)
Here, kl and k2 are the rate constants of the two consecutive reactions.
Input data for designing a NINAF reactor for this reaction system are
given in Table 5-2. Kinetic studies reported by DeMaria '8 for a catalyst
with small fluidizable particles suggest that all reactions at:e pseudo-first-
order in naphthalene and phthalic anhydride and zero-order in oxygen.
Oxygen is always present in vast stoichiometric excess. The oxygen/
naphthalene ratio was sdected slightly outside the explosive region. The
excess of air constitutes both an excess of reactant and an inert diluent
-
and hence forms a beneficial heat sink. On the other hand, it also (on-
•
PROCESS DESIGN OF FIXED-BED Gf\S REACTORS 137
•
•
stitutes a factor for increasing the number of reactor tubes, since the
reactor diameter cannot be enlarged without badly affecting heat transfer.
The sources of the data used in this example are indicated in Table
5-2. Some data were recalculated. For most of the data the correctness
of information given in the literature was relied on.
The computer program RDMOT2 developed to solve this type of
problem is explained in detail in the following, with the assistance of
Figs. 5-16 to 5-20.
Fir~t, all the input data are read in and also printed in order to define
the problem. In the unlikely event that the temperature would run away,
TR~IAX = 2.0T" is also read in as a limit. A fixed step size is read in.
Next, dependent variable Y and its derivatives F are dimensioned in the
form of two-dimensional arrays. There are two types of PDEs and each
has six I values. An equivalence statement establishes corresFondence
between e" T" and their Y equivalents. Some information such as the
highest I value, NR, and the frequency of printing, IFREQ, is supplied
in form of data statements. Next Z, Y(I,I), Y(I,2), and ICOUNT are
initialized. A DO loop assigns I values from 1 to 6 to all the \,'s. Then
nine quantities, p, cp' Re, Pr, Sc, kl(, It, BiOI, and ~T are calculated.
0:ow, dummy variables CSI and TSI are initialized in order to com-
plHe the catalyst-surface concentration CS(I) and catalyst-surface r~m
perature TS(I). As a starting point, CSI is assumed to be the same as
the concentration on the axis and inlet of the reactor, namely CSI = CS( 1).
This statement calls on the function CS(I) which is set up as one of the
several separate functions. On Fig. 5-17, the sequence of computatiori
which gives CSt.!) is shown by an arrow diagram. We will come back to
this sequence of computation.
The FUNCTION RUNGE is called. This function is set up to process
a one-dimensional array of differential equations. Since there-is one
material balance ODE and one heat balance ODE, each with six I values,
N = 12. The FUNCTION RUNGE works exactly as discussed in the
adiabatic reactor examples. A DO loop assigns values between 1 and 6
to I. For I = I or on the reactor axis, special ODEs apply. For I = 2,
3,4,5, the regular ODEs apply and for I = 6 or at the reactor wall, the
ODEs include the boundary conditions.
The calculation of I-dependent quantities, such as the temperature-
•
corrected RHOC, Sc, Kg, HTC, and Bi"" also have to be located inside
the DO loop in which the value of I is defined.
Following the FUNCl'ION RUNGE a temperature limit is set: if the
bulk temperature exceeds-2.0 times the inlet temperature, the integra-
tion is terminated and the program writes its final statements and stops.
Otherwise, it continues. Here, the axis points are taken as the temper-
•
TABLE 5-2
Input Data for the Computer Program RDMOT2 to Design a NINAF Reactor
for the Oxidation of Naphthalene to Phthalic Anhydride
Data
Text Computer source
symbol sym601 Value Dimensions (ref. no.)
-I
a A 1200. m
13 -I
Al Al 5.809 x 10 s C.lculated from 14
•
-I
A2 A2 2.222 x 10' s 14
Bi" BIW Note 1 T)imensionless
cp CP 30.334 kJl(mol'K) 14
• .,
('
- D 10-' m'/s 14
•
Dim DIM 2.05 10-' m2Js 14
DglD ... DBDA 0.93 Dimensionless 14
dp DP 0.001 m 14
DT DT 0.05 m 20
El El 158990. kJlkmol 14
Eo- E2 83680. kJ/kmol 14
H H 0.1 Dimensionless
kl Kl 7.0 S
-I 14
k2 K2 0.035 s-I 14
•
•, MI M''\' I 128.174
M.. MW2 28.860
Pe rn PEM 10.0 Dimensionless 14
Peh PEH 7.0 Dimensionless 14
D
He RC 8.316 kJ/(kmol·K)
To TO 643.2 K 14
T rm:u TRMAX 2.0 Dimensionless
ature sensing points, since the peak is expected to show up there.

Each time that a certain number of integration steps are compiled,
the results are printed. -The number of integration steps between each
printing is designated as-IFREQ.
Various quantities needed for the calculation of the ODEs are com-
puted as separate functions. The relationships between these functions
is shown in Fig. 5-17. There are some problems in these relationships
which require a detailed explanation. Thus, starting with the bulk gas
•
PROCESS DESIGN OF AXED-BED GAS REA<:TORS 139

•
•
TABLE 5-2
Input Data for the Computer Program RDMOn to Design a NINAF Reactor
for the Oxidation of Naphthalene to Phthalic Anhydride (Colztinued)
Data
Text Computer source
symbol syml>ol Value Dimensions (ref. no.)
Tu. TW 0.983 Dimensionltss

u U 8.0 m/s
yo YO Note 2 Dimensionless
VIS 0.0000305 kg/m's 14
At; LG 3.853 x 10-5
kJ!(s·m· K) 14
f1H, DHl -1.8 x 106 kJ/kmol Note 3
f1H,- DH2 - 1.82 x 1O~ kJlkmol Note 3
KOTEl: Heat transfer across the reactor walls of Kli'\AF reactors is reponed'o to be in the order of
200 tu 400 Btu/(h·ft 2 .oF). which corresponds to 1.1356 - 2.2712 kjl(s·m 2 'K). The author selected the
upper range and calculated
but
•
Bi. = h" Pe,/pcpu = (2.27)(7 .)/{0.56094)( 1.0246)(8.) = 3.456
Too Iowa Bi", would make the NINAF reactor approach an adiabatic react" ... This is exactly what
would happen if the above calculated Biw figure were used. We have used Bi,.. = 92.0 to demonstrate
a strong wall effect. Heat transfer in the process side is reponed to bew 32 Btul(h·ft'·oF) or 0.1817
kJ/s·m 2 ·K), which is 6.46 times lower than the value calculated by fOllllula. We prefer to use the
. experimental data.
'. NOTE 2: One must be very careful in selecting the naphthalene mole fraction in air because of the
explosi\ity of air-naphthalene mixtures:
•
Lower explosive limit: 0.9 mol ~ naphthalene in air

Upper explosive limit: 5.9 mol \k' naphthalene in air
Thus )'0 = 0.0075 (¥.\k' naphthalene) is probably the highest safe concentration. However, it is also
kno,,"n that some industrial reactors are being operated e,'en in the explosive range.'"
NOTE 3: Literature data on I1HI and I1H2 are spread oyer an order of magnitude. Data of Coleman
and Pilcher}1 G. C. Parks et al.." L. M. Elkin.'" and a pri"ate source were compared and the following
data were adopted: -~, = 0.18 X 10' kJfkmol and -;;;H. = 0.182 x 10' kJfkmol.
concentration CR(I) and bulk gas temperature TR(I), it is not possible

to calculate the catalyst surface concentration CS(I) and temperature
TS(I) explicitly from the differential equations. The reason is that the
terms 1'/1> kl> RI> and I/lJi'R, all of which depend on temperature and
.
concentration, must be evaluated as functions of CS(I) and TS(I). This
means that CS(I) and TS(I) appear implicitly in the system of equations
and must therefore be computed by iteration. Thus, CS(I) and TS(I)
are assumed; 1'/1, k l, RI, and I/lH·R are computed based on these as-
•
•
NO
YES
YES
YES
YES
'- YES
NO
FIG. 5-'16 Block diagram of the RDMOT2 computer proglam.
sumed values; new values of CS(I) and TS(I) are computed from the set
of equations; and the entire calculation is then repeated until conver-
gence on CS(I) and TS(I) is obtained. Specifically, th.e call to RI (I) in
calculating F(I, 1) initiates the iterative calculation of the catalyst surface
concentration and temperature:
I I
RI +-.- EFFI . . . - PHI! <-.- Kt ......- TSI <- DHR
CS~.==========~------------
The initial values of Cs and T, are set equal to the bulk fluid concentra-
tions and temperature; respectively, and are designated as the dummy
variables CSI and TSI. Now CSI and TSI are computed by the equations:
CSI = CO CJ(l + (111 kl/kg a»
•
PROCESS DESIGN OF FIXED-BED GAS REACTORS i4i
•
•
TSI = To T, + (L(-6.Hj Ryha)
,
The number of iterations is set at NITER=3.

The function DHR sta:1ds for 'i,( -lllIj Ri)' where j is the number of
reactions. In the calculation of the function DHR. RI in the expression
(- 6.H I )R I + (- 6.H 2 )R 2 is computed locally to a\'oid a recursive call to
the function CS [CSI is used instead uf CS(I)} .-\ recursive call is for-
bidden and by the USE' of intermediate dummy \"ari1.bles the computer
is, so to speak, "chea,ed" and induced to ,-10 wildt it \\'ould not do othenvise.
TSI CSl ~
FUNCTION CS FUNCTION RI ,
EFFI Kl cs
,
EFFl DHR
~
I
1" T
FUNCTION EFF 1
I
PHI I
-- FUNCTION PHll
KI
,
-
T
FUNCTION Kl
r
TSl
FUNCTION DHR
EFFl Kl CSI R2
:J
.l:,
FUNCTION CB FUNCTION R2
Kl KZ MM~CSI EFFZ K2 CB
't
r FUNCTION SMMPM
EFF1 Ml M2 PHI1 PH12 EFF2
1=
FUNCTiON 1041
1 FUNCTION 1.12
H.PHI~ PHI2
I
FUNCTION EFF2
I FUNCTION PHl2
PHI2~ K2
•
FUNCTION K2 ,
TSI
-
FIG. 5-17 Arrow diagram of calculation sequence of various functions in the
RDMOT2 program.
•
1 CAT1LYST ftASS-TBAISFER SURFACE llEl /OIlT VOLUSE. l/S
11 FaEQUEHCY F1CTOR FOR REICTIO. 1
12 FREQUENCY FACTOR FOB IE1CTION 2 "
BIB BlOT RUBBER FOR B1SS. DIRERSIORLESS •

BIV BlOT MURBER FOR RE1CTOR V1L~. DIRENSICRLESS
CB REDUCED COHCENTR1TlOH OF PHTa&LIC lNHYDRIDE. DIRENSIONLESS
CP HEAT CAPACITY OF GAS .IJ/KG
CR REDUCED CONCENTR1TION OF HAPHTHALEIE,DISERSICILESS
CRS REDUCED CONCENTRATION OF NAPHTB1LENE OB CATALYST SURF1CE
CSI DUSIIY ""RIABLE = CS(I)
CO B'PHTHALEHE CONCEHTRATIOB IT REACTOR I~LET.K!OL/K •• 3
D IHTRAPBASE DIFFUSIVITY. K•• 2/S
DBDA DB/DA ;DB=DIFFUSIVITY OF THE PRODUCT, 5**2/S ;
DA=DIFfUSIVITY Of THE REACTANT, ~ •• 2/S
DEL TAB RADI1L IHCBEItEHT
DHl BEAT OP REACTION 1, KJjK!!OL
DB2 HEAT OP REACTION 2. KJ/K~OL
DP C1TALYST PARTICLE DIA!lETER, !I
OR RADIAL !lASS DIPPUSIVITY. 1I**2/S
Dl!! !!OLECULlR DIFfUSIVITY III /lDLTICCl'lPOIIEH~ III nURE. /I •• 2/S
EFFl EFFECTIVENESS FACTOR OF REACTICN 1 , DIIIENSIONLESS
EPF2 EFFECTIVENESS FACTOR OF REACTIC8 2 , ~I~ENSIOHLESS
El ACTIVATION ENERGY POR REAC~ION 1 , gJ/g~OL
E2 ACTIVATICN F.NEBGY FOB REACTION 2 , ~J/~~OL
F DERIVATIVE Df/DZ
H STEPSIZE IN INTEGBATIOIi
HTC INTERPHASE HEAT TRAHSFER COEFfICIENT, 7.J/S.K.II •• 2
ICOIJM! COUIiTER FOR PRINTING FREQIJENCY
IFBEQ PRINTING fREQUENCY, DIftENSIONLESS
KG IHT3RPHASE ~lSS-TBANSFER COEFfICIENT, ~/S
KR RADIAL HEAT DIfFUSIVITY. !I*.2/S
Kl RAT~ CONSTANT OF REACTION 1
K2 RATE C~NSTANT Of REACTION 2
LG TREa~AL CON~UCTIVITY OF GAS, KJ/S.~.K
~Wl ~OLECDLAR WZIGHT OF NAPHTHALENE
/l1l2 ~OLECULAR IIEIGHT OF AIR
N NUIIBER OF ORDINARY DIFFERENTIAL EQUl'IIOS
NITER ITERATION COUNTER IN FUNCTICN CS (I)
NR THE LAST (iALL) TER~ Of 1=2,3, •• , NR IN RACI AI. IlICREIIENT AT lOll
PEH PECLET NU!lDeR FOR HEAT TRANSFER, DIIIENSICNLESS=(DP*U/KR)
PE!! PECLET :;UMBER POR /lASS TRANSFER, DI/lENS~CNLESS= (OP.U/DR)
PHI DJ~I\ Y VARIABLE OF FUNCTION RUNGE, EH1 (I), EFI'2 (I)
FR PllAN OIL NUIISE., DI!!ENSIONLESS = (CP.VIS/LG)
R REaaCED RADIAL COORDINATE, DI~ENSICHLESS
RE REYlIOLDS ~U~DER, DI~EIiSIOIILESS=12. 189·D?·~O.U/{VIS.TO.TR(I) I
RG GAS CONSTAN! = 8.]16 KJ/KIICL.r.
RHO FLUID DENSITY AT IHLgT, KG/II**3
RHOC FLUID DENSITY A: ANY POINT, KG/II*.3
Ri DI~~MSIOMLESS RADIUS OF REACTOR
Rl EFFECl'IVl: BATE OF REACTION 1
R2 EFFECTIVE RATE OF REACTIOH 2
SAVEY DUII~Y VARIABLE 01' FUNCTION R!lNGE TO SA E Y
TR RE:JUCED GAS TE~PERATURE. DI!IEMSIGNLESS = T/TO
TRIIAX IIAXIMUI\ ALLOWABLE REDUCED TElIPERATURE, JIeEfiSICNLESS
lSI DUt:~Y VARIADLE = TS (I)
:11 WALL T E:1P eRnfJe E, DIIIENSICNLESS
TO A3S0LUTE TE~PERATURE OP REACTANTS AT ISL~, K
IT FLUID VELOCITY IN BED, e/s
VIS YISCOSITY Of FLUID. KG/II.5 (=PAS)
Y DEnNDENT VARIABLE IN IN!EGRA~ION
YO IICL fRAC'rION 01' NAPH"rHllLENE AT INLET, DI)!fNSIOIlL ESS
Z RE!l:JCED UIAL COORDlNA7E, DIlIENSICNLESS
ZZ AXIAL COORDINATE, ~.
FIG. 5-18 Definition of symbols in the POMOT2 computer program .
142
•
C PROCESS DESIGI' OF lUll' GAS RBlC'l'OR
C POll
C lIR-OIIDArIOII OF 11PHTHlLEIE 'l'O PHTHlLIC ANHYDRIDE
C
COKftO' A,Al,12,BI",CO,D.DBDl,DH1,D82.DP.£l,E2,HTC.~G,R~.TO,
1 CSI,TS1,CR.TR
REAL ftO,LG,KG,8Vl.ftW2 .
1IITEGER RU"GE
DIIIEII510II CR(61. TR(61
DIKENSIOII T(6,21.F(6.2)
EOOIV ALEIIC! IT,CR), (Y (1, 2).TR)
WRITE (6, 1501
150 FOI"AT(181,21X,27HDESIGN OF IIIIIAF GAS REACTOR/1HO,11X,
1S0HAII OXIDATION OF NAPHTHALENE TO PHTHALIC ANHYDRIDE)
C •••• READ AND PRINT DATA ••••
IEAD(5,100)PE",PEH,DP,CP,U.TO,~"A~.El,E2.Al,A2,DH1.0H2,VIS.BIW.
1 LG,01K.0,A.YO.RG,DBOA.DT.H,TW,nWl,"W2
lOO FOl8AT (7110. 4/3E20. 6/3£20. 6/3E20.6/2E20.6,21'10.4/71'10. 41
DATA 11/6/
DATA II'REQ/2S0/
iRlrE(6,200ITO,U,TR~AX,A,YO,CP,"W1_~k2.PEn,e1,A1.VT.H,PER.E2.A2,
1 DBDA,TW,DP,Bli.VrS.DH1,Lj,RG,DH2.o,01"
2~0 FOR"Af(1HO,21,48TO= ,PS.1.78 ~ U=,F6.3.128 "/5 TR"AX=,F6.3,8X,
, 2H&=,F7.1,4H 1/n/1H ,2X,~HYO= ,E9.3.QH CP=,F6.J,BH KJ/KftOL,2X,
2 488W1=,1'7.3,4X,48"92=,1'6.3,58 PE"=,~6.3/1R ,2I,48El= ,P.9.3,
] 48 &1=,£10.4,4B OT=,F6.3,2H ft,~X,2HH=,Y5.3,7R PEH=,F6.3/1H ,2X,
q 48E2= ,E9.3,4H A2=,E10.4, .
5 68 GBO&=,1'S.3,10X,3HTW=,FS.3,5R DP=,PS.3,2H ~/1H ,2L.4H5IW=,
6 E9.3,15X,4RVIS=,E9.3,4H PAS,3X,4HDH1=,F.9.3,BH KJ/K"OL/1H ,2X,
7 4HLG= ,E9.3,9H 1(.J/S.!l.K,6X,38RG=,FS.3,12R KJ/KIIOL.K ,480H2=,
8 E9.3,8H KJ/KIIOL/1H ,2X,4HD= ,E9.3,1H II •• 2/5,8X,4801"=,£9.3,
9 78 ,,0*2/5)
C •••• CALCULATE CO, 110, ~Ii •..•
CO=12.189*YO/TO
/lO=(YO*ftIl11 + «(1.-YO) */11/2)
RW=DT/ (2. * OP)
C •••• INITIALIZE Z,Y(I,1I,Y(!,2), AND ICCUMT ••••
Z = 0.0
DO lI=1,IIR
T(I,11 = 1.0
1 T(I,21 = 1.0
ICOO NT=O
C •••• CALCULATE RHO, CP, RE, PR, SC, KG, HTC, BI~, OELTAR ••••
RHO=273.16·~0/(22.414*TO)
CP=CP/1I0
R£=12.1888*OP*1I0*O/(VIS*TO)
PR=Cp*VrS/L::
1'A:TOR=1.15*U/5QR7(R£)
SC=VI5/ (RHO*01K) .
KG=FA:TOB*(5C)**C-2./3.)
C flTC=I'ACTOR*RHO*CP* (PR) .* (- 2. /3.)
RTC = 0.182
B II'I=I(G/ (D*AI
DELTAR = R9/5.0
C •••• INITIALIZE CSI, TSI VIA FUNCTION CS(I) ••••
CSI = CS (1)
C •••• :ILL ON T!!E 1'OURTH-OROER HUIIGE-KOTTA FO~CTIOIl ••••
2 K=RONGE (12,r,I',Z,8)
C IF K=1 COI'IPUTE DERIVATIVE VALUE5
II' (K. liE. 11 GO TO 3
DO 10 I = 1,IIB
C •••• CALCULATE RROC, RE, SC, KG, HTC, AND BIll ••••
RB:>: = RBO/TR(II
RE=12.1888*DP*"O*U/(VIS.TO*T~(III
SC=VIS/ CRBor*Dl!)
Kr.=1'AC"OR* (SC)*. 1-2. /3. 1
HTC=FAcroa*RHOC*CP*(PRj*.(-2./3.1
BI!!=K:;/(D*AI
•
FIG. 5-19 The RDMOT2 computer program for the design of a NINAF reactor
for the oxidation of naphtlialene to phthalic anhydride.
143
•
•
Il'(CB(II.LT.O.ICB(II~O.
=, .
I P (CR (II • GT. 1. ) CII ( II
I'(I.IE.1)40 TO "
P (1,1) ,,(11. IFEI! 1* (CR (I+l) -CR (I) I / (DELTllI**2) - (DP*R 1 (Ill (CO*lll ) •
1 (1.2) " (11. /PElf) * (TB (1 + 1) -TB (1) 1 I (DEL TAR **2)
1 +OHR(I)*DP/(CP*ll*RBOC*rO)
GO TO 10 .
11 11(1.£Q.IB) ~O TO 12
WALL" (rR(H1) -TB (1-1)) 1(2.*OELTU!)
F (1,1) "p./pE!!). ({CR (Ul) -2. "CB (1) +CR (1-1»)1 (OELTAR •• 2, +
1 (1./«1-1) "DELTAS)) *(CB (I+l)-CI> (I-1,)/(2.*DELTAR))
2 - :DP.Rl{l)/(CO.ll))
1 (1,21 = (1./PEBl * «TB (1+ 11 -2 •• TR (11 +rB (1-1) )1 (OELT1R**2) +
1 (1./( (I-11*OELTAR)) .WUL)
2 + (DHR (1) *DPI (CP*u *RH:JC*TO)I
GO TO 10
12 l!ALL~BliI" (TlI-TB (IIR))
F (I, 1) = (2. /PE!!) • (Cl! (1 -1) -CR (I) ) I (DELTAR**Z)
1 -(D~*Rl(I)/(CO*U))
l" (1,2) = (Z./pEH) *«TR (1-11 -TB (I) ) I (DELTA n**z) +
1 (1./( (I- l l*OELTAII»*1I1LLI
2 +(DHR(I) *OP/(CP*0*1I110C*'1'0)
10 CONTIIIUE
GO TO 2
3ZZ=Z"DP
c
C ••.•• IF
TB EXCEEDS TP.IIAX, T..lR'IIIIAT.1'! INrEGRATION ••••
Il"(TB(l).LE.TRlIll.l, GO T~ 4
GO TO 5
4 ICOUNT " lCOUNT + 1
IF(CS(H.U.O.Ml) GO TO 5
IF (ZZ. GE. 1.5) GO TO 5
Il"IICO{JIIT.IIE.IFREQ) GO TO 2
C
C •••• PRINT SOLGTIOM ••••
C
WRITE (6,Z02) Z, ZZ
WRITE (6,203) (CR(I) ,I=l,NR)
WRIrE {6,2041 (T!!(I), I~l,!lRI
202 FO~'AT(lHO,2X,4HZ = ,E10.3,J~,SBZZ = , El0. 3/1H
1 l1H R~O ,1111 R:1 ,11H F=2 ,
2 118 R=J ,11H &=4 ,1111 R=5 )
203 FOBIlAT (18 ,68CR(1)=,6El1.3)
204 fOR!lAT (1l! ,6RTR(I}=,6E11.J)
ICOUIIT ~ 0
GO TO 2
•
C
\ THE CALL ro Rl(I) IR CALCULATING F(I,l) INITIATES THE ITERATIVE
C
C CALCUL1TIOII OF THE CATALYST SURFACE CONCENTRATIOII AND TEftPERATURE,
C CSI 1IID TSI
C
5 WRlrE(6,202) Z, zz
IIRITE(6,203) (:::R III ,I=l, IIR)
IlRITE(6,ZOIl) (TR(I) ,1:1,118)
STOP
END
C
FIG. 5-19 The RDMOT2 computer pLOglam for the design of a NINAF reactor
for the oxidation of naphthalene to phthalic anhydride (continued) .
144
•
•
fUBCTIOK RUHG~ (I,T,',Z,m
IlIf EGER BU ICE •
DII1BIISIOII PHI (50) ,SA'lr:t(50) ,T(II) ,F(R)
•
DATA 11/0/
c
11;11+1
•
GO TO (1,2,3,4,5), 11
C PASS 1
1 RUNGE = 1
RETURII
C PASS 2
2 DO 22 J=l,N
SAYEl (JI =1 (J)
PHI (JI;1' (JI
22 T(J)=SlVEl(J) +0.5 • H. F(JI
z = z + 0.5 H*
ROIIGE ; 1
RETURB
C PASS 3
] DO 3] J=l,1I
PHI CJI = PBI (J) • 2.0 * f' (J)
33 T (JI = SAY El (3) + O. 5 * H • F (JI
Rll!!GE .. 1
BBTDall
C PASS ~
" DO 44 J=l,N
PHI (J) = PHI (JI + 2.0 * F(JI
44 T(J) .. Sl'lET(J) + H • F(J)
Z = Z + 0.5 • H
ROIGE '" 1
BETURI
C PASS 5
5 DO 55 J ; 1,.
55 T IJ) = SUET (J) + (PHI (J) + l' (Jl). H/6.0
11=0
RIJ'GI'! .. 0
RETIJII
!ID
C
FD.cn O. a1 (11
C
BElL 1t1 •
C THE FOLLOWIIIG STlrEIIENT Wl. LL ITERATIVELI CALCULAT & CSI UD TSI,
C 'lIA THI'! CALL TO CS (I)
CSI=CS (I)
R1 = E1'F1 (I)*K1(1) *CSI
RETURN
ElID
C
FUlIC1'IO!l R2 (I)
c
ilEAL 1t2
a2 = E1"F2 (I) *K2 (1) *CB(I)
RETURN
EIID
FIG: 5-19 The RDMOT2 computer program for the design of a NINAF reactor
for the oxidation of napht}!aJene to phthalic anhydride (continued) •
••
145
•
C
YUICTION EYY1!I) •
C •
PHI " PRIl (1)
ilff1 = TUR (PHII /PRI
RE'J'URt! •
ElIll
C
FO NCT 1011 ~F1'2 (I)
C
PHI " PHI2 (1)
El'F2 " TANH(PBI)/PHI
R1WJRK
END
C
FONcnON PHll (1)
C
REA L r; 1
CO""CM A,Al,A2.BI~.CO.D.DBDA,DR1#nh2~DP.E1#E2,ffTC,XG,RG.TO,
1 CSI,TSI,CR,TR
llI!ElISI~H CR(61, TR(6)
PHI1 = llP /6. *SQRT (lt1 (I) Ill)
C SET PRI1 ro A IIIHIIIU! VALOE TO AVOID A NUI!ERICAL PROBLEII IN
C COIIPUTIN;; EFl", SPlIIP!'! .
IF(PHI1.LT.1.0E-10) PHI1 " 1.0E-l0
IlETUllll
END
C
F!JlICTIOII PRI2 (1)
-- RElL 1':2
COl!lIOll I, A " 12, BI~, CO, 0, DB 01., OH' ,DR2,DP, El, E2 ,aTe.!,(G ,RG. TO. •
•
1 CSI.TSI,CR,TR
DIIIEIISIOll CR(6), rR(6)
PRI2 '" OP/6.*SQRT(1'(2 (I) Ill)
IF(PHI2.LT.l.0E-10) PRI2 " 1.0E-l0
RETURlI
EIID
C
REAL l'OliCTIOII 1t1 (l)
C
C NOTE - 1(1 IS 1I0W BASED Oll THE CATALYST S(JBl'ACI! TI!!lPERAT(JRI!, TSI
C •
COft!OH 1.1',12,BIII,CO,D,DBDA,DH1,DR2,DP,E',E2,HTC,r;C,RG,TO.
, . eSI,1sI,CR,TR
DIIIElISIOR CR(6). TR(6)
•
1(1 = 11*EIP(-ElI(RG*TSI))
RETUIlll
EIID •
FIG. 5-19 The RDMOT2'computer program for th~ design of a NINAF reactor
for the oxidation of naphthalene to phthalic anhydride (continued).
146
•
C
RBAL PURCTIOR ~2(~
C
C. ROTE - ~2 IS IOW BASED 01 THE CATALYST SURFACE TEftPER1TDRE, TSI •
C
COftftOR a,Al,A2,815.CO,D,DBDA.DH1,DH2,DP,El,E2,8TC,~G,RG,TO,
1 CSI, TSI,CR, Tl! .
D1ftfRS10I CB(6J, TR(61
K2 ; l2*ElP(-E2/(RG*TS111
RETURN
ERD
C
PUNCTIO~ CS (I)
C
C CS IS THE ClTALYST SURFACE CONCENTRATION OF KEY REACTANT
C COBPU:ED VIA BASS AND HEAT TRAHSFER COEFFICIERTS
C CSI AND rSI ARE ClLCULATFO ITERATIVELY VIA EQUATIONS
C CSI ; CO*CR/(1.0+(Effl*tO/(KG*A)I J (~\
C ISI = TO*TR+DHR/{RTC*'l (S)
C
COI!I!CII I, A1, A2, BIII,CO, D, DBDA, OH', DR2,DP,E 1 ,E2 ,HTC ,KG, RG ,TO,
1 CSI,TSI,CR,T'
DIIIENSIOR 0::2(61, TR(61
REAL tt1,~:;
C SET TBE NlJftSEB Of' ITER1TI)NS, HITER
IHTER = 3
C SET THE INITIAL VALUES OF CSl AND TS1 TO THE BULK GAS
C CONCENTRATION AND TE~PERATURE,
CSI = CO*cR(I)
TS1 = TO-TB (1)
C CCIIPUTE CSI UD TS1 VH EQIJATIOns A AND B
C
DO 1 L= " HITER
CSI = CO*CR(II/(l.+{Eff' (I)*1C1(I)/(ICG*A»))
1 TSI = TO*TR (I) +(DBR (11 / (IITC.AI)
CS ; CSI
RETURl!
EIID
• C
•
FUNCTIOI! CB(I)
C
C CB IS tHE CATALYST SURFACE CONCENTRATIOR OF THE PRODUCT OF
C RElCnOI 1
C
CO~ftOI A,Al,A2,81ft.:O,D.DBDA,DH1,DH2,DP,E1,£2,HTC,ICG,RG.TO,
1 CSI,TSI,CR,TR
DIKENSIOR CRCE), IR(6)
REAL IC " tt2
RK1K2 = IC1 (I)/I(2 (IJ
S = Sl!ftPII (11
C ROTE - :B IS ROi BASED OR CSI
CSCO = CSI/CO
CB = CO. ( (S- DBDA) I (S-1.) ) * (RK 11\'2/ (RIC 1tt2*DBDA -1.) ) * ( (CS CO" S) -CSC 0)
If(CB. LT. D.) C8=0.
BETURII
EIID •
FIG. 5-19 The RDMOT2 computer program for the design of a NIN AF reactor
for the oxidation of naphtlralene to phthalic anhydride (continued).
..
147
•
c
FUlIcnOIl SIIIIPII (rl •
c •
c SIIIIPII IS THE PACTOB 5 POB THE IIACBO-IIICRO PORE ftODEt
c
COIIIIOII 1.11,12,8I",=O,D,D8Dl,DH1,OH2,OP,El,E2.HTC,~G,RG,TO,
1 CSI.TSI.CR,TA·
OIII!1I51011 CR (6), TR (6)
RElL 11111,11112
SIIIIPII=D8Dl*!!1I1 (I). (PBI2 (11 "2j.EFF2 (II /
1 (11112 (1)* (PHI 1 (11 "2)-.eFFl (1))
RETORI
ERD
C
RElL FUIiCTIOII 11111 (I)
c
C 11111 IS 1 PACTOR OS!D III '.!'RE C1LCULATIOI OF 5 FOR THE RACRO-RICRD
C poa E 1I01)!",
COIIIICII t,11,12.8I~.CO,D,D8DA,DR1.0R2,DP,El,E2,BTC,KG,RG.TO,
1 CSI,TSI,CR,TR
DIIIERSIOH CB(6), TB(6)
PHI = PHI1 (I)
~1I1= 1 • • (PHI.TANH(PHI)/BI")
EET{lRR
END
C
REAL FUICTION 11112(11
C
C 11112 IS 1 FACTOR ijSED IN THE CALCULATION OF S FOR THE IIlCRO-IIICRO
C PORe IIODEL
COII!!!'R A, A " A2, BIll, CO, D. DBDl. DH 1 ,DH2,DP,E 1 ,E2 ,HTC, KG, RG, TO.
1 CSI,TSI,CR,TR
DI!lERSION Cl! (6). rR (6)
PHI = PHI2 (I)
RII2= 1 •• (PHI-TUH (PHI) /BIII)
RETUR'i
END •
c
FtlllCTION DRR (1)
C •
C DRR IS THE Stlll OF TRE PRODUCTS OF THE HEATS OP REACTIOR AND

C R1T!S OF REACTION
COIIIIOll A,Al,12.BI~,CO,D.DBDA.DH1,DH2,DP,E1,E2,HTC,~G,RG,TO.
1 CSI,TSI.CR,TR
DI~~!!SIO!! CR (6), TR (6)
RElL It 1
c COIIPUTE Bl 11 Dlll*R1 + DH2*S2 LOCALLY TO "DID A RECORSI'! CALL
C TO FOlICTIOII CS (CSI IS USED III PLACE OF cs (1) )
RH = EFF1 (l) -It 1 (I) .CSI
DHR - DH1-R1I • DH2-R2(I)
RETtlRlI •
ERD
FIG. 5-19 The RDMOT2 computer progtam for the design of a NINAF reactor
for the oxidation of naphthalene to phthalic anhydride (continued).
•
1 DESIGI Ol' UUI' GAS REACTOR
o AIB OXID1TIOI Ol' IlPHrB1LEIE ro PHTHALIC AIHYDRIDE
o ro= 643.2 K 0= 8.000 ft/s TBftlX= 2.000 A= 1200.0 1/ft
"
tOs 0.250B-02 CP=30.334 KJ/KftOL ftll=128.174 ftI2=26.860 PEft=10.000
El= 0.159E+06 Al=0.5809E+14 Dr= 0.050 ft R=0.100 PER= 7.000
E2= 0.8378+05 12=0.22228+06 OBOl t O.930 TI=0.983 OP=0.001"
8II=0.920£+02 "VIS=0.2908-04 PAS 081=0.180£+07 KJ/KftOL
Le= 0.3952-04 KJ/S.ft.K BG=9.316 KJ/KftOL.K 082=0.1922+07 U/KIIOL
D= 0.100 E-04 11**2/5 D 111=0. 205!!-04 11**2/5
o Z = 0.250£+02 ZZ = 0.2502-01
8;0 R=1 R=2 R=l R=q R=5
C8 (11 = 0.9768+00 0.976&+00 0.976£+00 0.976 £+00 0.977£+00 O.986E.00
Ta (I) = 0.101£+01 0.101E+01 0.101&+01 0.101E+Ol 0.100£+ 0 1 0.983E+00
o Z = 0.500£+02 ZZ = 0.500E-Ol
8=0 R= 1 8=2 8=3 R=4 R=5
CB (I) = 0.947£+00 0.947E+00 0.J47£+0~ 0.9461':+00 0.953£+00 J.970&'00
TR(I)= 0.101&+01 0.101E+0: 0.101&+01 0.101E+0· O.I~I1':.Ol O. './83 £+00
0 7 ~-- 0.750&+02 ZZ = 0.750l-01
8=0 B=1 8=2 R=J R=4 R=5
CR{I) = 0.913&+00 0.913£+00 0.91'"£+00 J.9171'+00 0.929 E+OO 0.953E+OO
TR(l)- 0.102£+01 0.102&+01 O. i02E+Ol 0.1021':t01 0.10lEtOl 0.9831':tOO
o z = 0.100R+03 ZZ = 0.100&+00
8=0 8=1 B=2 R=J R=" P=5
CB(I) = 0.871£+00 0.871£+00 0.873£+00 0.880 E+OO 0.902E+00 0.934E+00
TR(I)= 0.1032+01 0.1032+01 0.1032+J1 0.102E+Ol O.101E+Ol 0.983E.00
o z = 0.125£+03 ZZ = 0.125£+00
B=O B=1 8=2 B=3 !I=4 R-5
CR (I) = 0.817&+00 0.8178+00 0.821&+00 0.836 £+00 0.873E+OO 0.915E+00
TB (I) = 0.104£+01 0.104£+01 0.104£+01 0.103E+Ol O.lOlE+Ol 0.983£+00
o z ~ 0.150£+03 ZZ = 0.150£+00
8=0 8=1 R=2 8=3 R='I R=5
CB (I) = 0.740£+00 0.742£+00 0.752£+00 0.782£+00 0.8111£+00 0.893E+00
TB(I) = 0.106£+01 0.106E+Ol 0.106E+01 0.10';E+Ol 0.102£+ 01 0.983£+00
o z = 0.175&+03 ZZ = 0.175E+00 .
8=0 B=1 8=2 B=3 B=4 !!=5
cau) = 0.617£+00 0.623£+00 0.649£+00 0.711E+00 0.804E+00 0.869£+00
TR(I) = 0.109£+01 0.109£+01 0.108£+01 0.106E+Ol 0.103E+01 0.983£+00
o z = 0.200E+03 ZZ = 0.200£+00
8=0 8=1 R=2 P. =3 R=4 R=5
CII (I) = 0.411£+00 0.425£+00 0.490£+00 0.607£+00 0.759E+00 0.643E+00
Ta(I) = 0.114£+01 0.114£+01 0.112£+01 0.106£+01 0.103£+01 0.983£+00
o z = 0.225E+03 ZZ = 0.225£+00
8=0 B=l 11=2 B=3 1l=4 R=5
CB(I) = 0.206£+00 0.219£+00 0.275£+00 0.447£+00 0.701E+OO 0.812E+00
T8(I) = 0.120£+01 0.119£+01 0.117£+01 0.112E+Ol 0.105£+01 0.983E+00
o z = 0.250£+03 ZZ = 0.250E+00
,. B=O 8=1 B=2 B=3 8=4 B=5
•
CR (X) = 0.913£-01 0.995£-01 0.137&+00 0.269£+00 0.621&+00 0.775£+00
TR(I)= 0.123E+Ol 0.122£+01 0.121£+01 0.117£+01 0.106£+01 0.983E+00
o Z = 0.275&+03 ZZ = 0.275£+00
a=o B=l 1=2 11=3 R=4 B=5
CII (I) = 0.392£-01 0.439£-01 0.660£-01 0.153 E+OO O.515E+00 0.729&+00
TB(I) = 0.124£+01 0.124E+Ol 0.123£+01 0.119£+01 0.10BE+Ol 0.983E+00
o z = 0.300£+03 Z~ = O.JOOE+OO
a=o 8=1 R=2 R=3 11=4 R=5
CR (I) = 0.168£-01 0.194£-01 0.326£-01 0.920E-Ol 0.336£+00 0.669E+00
TB (1) = 0.125£+01 0.125E+01 0.124£+01 0.121£+01 0.1111\+ 01 0.984 &+00
o Z = 0.325&+03 ZZ = 0.325£+00
B=O R=l R=2 B=3 R=II 8=5
CR (X) = 0.727£-02 0.881E-02 0.170B-Ol 0.576£-01 0.262£+00 0.598£+00
TB (I) = 0.125£+01 0.125£+01 0.124£+01 0.121£+01 O. 114E+ 01 0.964 E+OO
o Z = 0.350£+03 ZZ = 0.350B+00
R=O R=l B=2 R=3 R=4 8=5
CR (I) = 0.323£-02 0.416E-02 0.944E-02 0.367E-Ol O.17I1E+OO 0.522E+00
TB [Il = 0.125£+01 0.125E+Ol 0.124£+01 0.121£+01 0.115£+ 01 0.9811E+00
o z = 0.374£+0] ZZ = 0.374E+00
R=O B=l g=2 B=3 B=4 R=5
CR (I) = 0.149£-02 0.207£-02 0.553£-02 0.241£-01 0.122&+00 0.447&+00
TB (1) = 0.125£+01 0.125£+01 0.124£+01 0.121&+01 0.115£+01 0.9811 !+OO
o Z = 0.388R+03 ZZ = • ~0.388E+00
B=O 11=1 R=2 B:3 B=4 8=5
CB (L) = O. 998E' OJ 0.146E-02 0.42'1£-02 0.195£-01 0.104£+00 0.410£+00
TB(l)= 0.125E+Ol 0.125£+01 0.124&+01 0.121E+Ol 0.115£+01 0.984£+00
FIG. 5-20 Printout of RDMOT2 computer run.
149
•
- The computation of CB, the concentration of the product of reaction

1 (phthalic anhydride) on the catalyst surface, was carried out according
to themacromicropore 1flOd.f'/17 by the expression:
Si - (D B ID,4) kl/k z C
~, . C
CB = Co --
Si - 1 (k/k~)(DBID/\) - 1
o
DIl ml If't 11~
where - o
DA 1112 If'i 111
ml - 1 + «1f'1 tanh 1f'1)/Bim )

lnz = 1 + [(If'z tanh If'z)/Bi m ]
DA and DB = micropore (Knudsen) diffusivities of naphthalene
and phthalic anhydride, resp~ctively
CBO = initial concentration of phthalic anhydlide at reactor
If'I and If'z = Thiele moduli for macropores
111 and 112 = macropore effectiveness factors
The derivation of this kinetic relationship will not be treated in this

book. It can be found in !Jart in a paper by Carberry.li In our example
CBO = O. Other quantities were taken from Carberry's paper.
In this example we will calculate the design of a single reactor tube.
A number of these tubes will have to be grouped together into a heat-
exchanger bundle in order to meet a desired production capacity.
. , The feed to the reactor is determined by the mole fract:Jn Ju of
naphthalene in air and by the fluid velocity u in the bed. Naphthalene
contents of 0.25 to 1.0% in air have been used, corresponding to Yo
values of 0.0025 to 0.01. At higher concentrations the mixture becomes
explosive and the excess of oxygen is depleted.
Various quantities must be calculated by the computer before the call
for CS(J).
Co = (Yo/22.414)(273.2/To) = 12.189 YolTo
The average molecular weight of the reacting mixture is:

•
The dimensionless reactor radius is RU' = DY/2dp- The gas density P is

calculated at the inlet and, later, in the bed by -
Po = 273.2 Mo/(22.414 To) - 12.189 Mo/To

•
pr~OCESS DESIGN OF FIXED-BED GAS REACTORS 151
•
The various dimensionless groups must now be calculated:
Re = (Mo/22.414){273.2ITo)(u/~) = 12.189 Mo uf(TolL)
Pr = CpIL/Ac;
Se = IL/P D I.,
tl5 1J
k/i = 1.15 uRe- Sc-
It = I. 15 u Re - 05 P ("Pr - '"
Bi m = k/'1'a
ill' = Rj5
Some of these calculations must be repeated inside the DO loop which
calculates the derivatives F{I,I) and F{L2) because the expressions con-
tain the variable I.
Figure 5-18 lists definitions of symbols used in the source program
RDMOT2. The complete RDl\fOT2 source program and its output
printout are given in Figs. 5-19 and 5-20, respectively.
NOMENCLATURE
A Frequency factor
. . .)
A, Cross-sectional area of reactor bed, m-

.,
C Molar concentration of reactant or product, kmol/m"'
3
Molar concentration of toluene, kmollm
3
CB Molar concentration of hydrogen, kmol/m , or molar concen-
3
tration of phthalic anhydride, kmol/rn
Cpi Molar heat capacity of each i reacting species, kJ/(kmol· K)
E Activation energy, kJ/kmol
F Molar flow, kmolls
mi Molar flow of each i reacting species, kmol/s
N N umber of moles passing from the reactor per unit time
p Partial pressure of reactant or product, bars
P Total pressure, bars
•
l', Reaction rate, mole converted per unit time per unit surface
area of catalyst,. kmol/(s'm2)
T,_ Intrinsic reactiort
..
r:'ote, kmol/(s'm3)
Reaction rate expressed as partial pressure converted per second
3
per unit volume, p/(s·m )
•
•
•
Intrinsic reaction rate, moles converted per unit time per unit
weight of catalyst, kmol/(s'kg)
•
R Gas constant = 8.3l4 kJ/(kmol'K)
R Gas constant = 0.08314 (ms·bar)/(kmol·K)
.,
<Jl Apparent reaction rate or global reaction rate, kmol!(m ·s) 3
SI{ Catalyst surface area. or unit catalyst surface area per unit weight,
2
m /kg
Maximum tolerable temperature in fixed bed
v Volume of reactor bed. m 3
x Conversicn, dimensionless
Initial mole fraction of key reactant, dimensionless
z Reactor height, m
(X,f3 Reaction order, dimensionless
AH Heat of reaction, kJ/kmol
Void fraction. dimension less
Intraphase effecti\'ene:.s factor, dimensionless
PR Bulk density of catalyst, kg/m'
Subscripts
, A Ethylene
o Inlet
T Total
REFERENCES
1. R. Winkoop and R. H. Wilhelm, "Kinetics of Tubular Flow Reactors Hy-
drogenation of Ethvlene on Cu-MgO Catalyst," Chem. Eng. Prog. 46:300-
310 (1950).
2. M. Orhan Tarhan and WilIiam E. Schiesser, "Computer-Aided De~!gn of
Nonisothermal Nonadiabatic Fixed-Bed (NINAF) Gas Reactors," paper pre-
~emed at the 74th Am. Inst. Chem. Engrs. National Meeting, New Orleans,
March 11-15, 1973. _
3. Charles N. Satterfield and Peter F. Way, "The Role of the Liquid Phase in
the Performance of a Trickle-Bed Reactor," AlChE J. 18:305-311 (1972).
4. Peter F. Way,
, "The Performance of Trickle-Bed Reactors," Ph.D. thesis,
MIT, Cambridge, 1971.
•
PROCESS DESlGN OFAXED-BED GAS REACTORS 153
•
5. M. Ochan Tarhan and Louis H. Windsor. "Coke Ovens Yield High Quality
Benzene," Chem. Eng. Progr.. 6%(2):67-72 (1966).
6. Alvin H. Weiss and L. Friedman, "Development of Houdry Detol Process,"
Ind. Eng. Chem. Process Design DeveWp. 2:163-168 (1963).
7. Alvin H. Weiss,j. B. Maerker, and R. Newirth, "rloudry Detol Process Shows
Good Results at Crown Central Refinery," Oil Gas]. 60, Jan. 22, 1962, pp.
64-71.
8. F. D. Rossini et aI., Selected Val«l., of Ph)'Sical and The17l"}dY7w;,,ic Properties of
H.\'drocarbons and Relo.ted Compoullds, API Research rroject 44, Carnegie Press.
1953.
9. M. Orhan Tarhan and Louis H. Windsor. "The Catalvtic
•
Route to Benzene
from Coke-Oven Oil," Chem. Ellg. 96-98 Mar. 28. 1966.
10. C. R. Wilke, "A Viscosity Equation for Gas Mixtures,"]' Chem. Phys. 18(4):517-
519 (1950).
11. J. \1. Smith, Chemical EngilIteling Kinetics, McGra\"-Hill, New York, 1956.
12. J. M. Smith, Chemical Engiwerillg Kinetics, 2d ed., McGraw-Hill, New York,
1970.
13. James J. Carberry, "Heat and Mass Diffusional Intrusions in Catalytic Re-
actor Behavior," Catalysis Rro. 3(1):61-91 (1969).
14. James J. Carberry and Donald White, "On the Role of Transport Phewlfilena
in Catalytic Reactor Behavior Digital Simulation of Naphthalene Oxidation
over V20"," Ind. Eng. Chem. 61(7):27-35 (1969).
15. James J. Carberry and M. Wendel, "Computer Model of the Fixed Bed
Catalytic Reactor The Adiabatic and Quasiadiabatic Cases," AlChE J. 9: 129-
133 (1963).
16. Gilbert F. Froment, "Analysis and Design of Fixed-Bed Catalytic Reactors,"
in Chemical Reactor Engineering, Advances in Chemistry Series 109, American
Chemical Society, 1972, pp. 1-34.
17. J ames J. Carberry, "Mass Diffusion and Isothermal Catalytic Selectivity,"
Chem. Eng. Sci. 17:675-681 (1962).
18. F. DeMaria,j. E. Longfield, and G. Butler, "Catalytic Reactor Design," Ind.
Eng. Chem. 53(4):259-266 (1961).
19. K. R. Westerterp, "Maximum Allowable Temperature in Chemical Reac-
tors," Clum. Eng. Sci. 17:423-433 (1962).
20. L. M Elkin, "Phthalic Anhydride," Stanford Research Institute Report No. 34,
1968, Chap. 7, p. 73 .
•
21. D. j. Coleman and G. Pilcher, "Heats of Combustion of Biphenyl,
]\;aphthalene, Anthracene, and Phenanthrene," TrailS. Faraday Soc. 62(4):821-
827 (1966).
22. George S. Parks, John R. Morley, and Peter V. Peterson, Jr., "Heats of
Combustion and Formation of Some Organic Compounds Containing Ox-
ygen,"]' Chem. Phys. 18:152-153 (1950),
•
ID·PHASE
Chapter
OF REACTORS
6.1
DEFINITIONS CI.ASSIFICATION
OF GAS-LIQUID-PHASE REACTORS
A gas-liquid-phase reactor is a reactor in which the gas and the liquid
phases coexist during the catalytic reaction., It is possible to react:
· A gas with a liquid
· Two gases dissolved in a liquid
· Two liquids stirred by a gas
•
-, . The two major types of gas-liquid phase reactors using heterogeneous

catalysts are:
•
· Gas-liquid fixed-bed reactors

· Suspended-bed reactors
The latter class includes:
· Continuous stirred-tank reactors (CSTRs)
· Slurn' reactors
•
· Ebullated-bed reactors
· Three-phase transport reactors (3PTR)
In this chapter we will study only gas-liquid fixed-bed reactors.
Before going into the.. process design of each major type of reactor,
we must study their flow dynamics. heat transfer, and mass transfer
behavior because transport phenomena play a much greater role in gas-
liquid reactor types than in gas reactors. In most gas-liquid reactors, the
•
f56 ,CATALYllC . REACTOR. DESIGN
•
main problem is the definition of the exact ccnditions in the respective

gas-liquid systems. With the exception of gas-liquid fixed-bed reactors,
once the exact conditions have been defined, the design equations are .
usually very simple and in most cases can be solved analytically unless
the reaction kinetics presents some complexities.
In fixed-bed gas reactors it does not matter in what position or di-
rection the reactor is and whether the gas flows upward or downward,
although usually the flow is vertical. In gas-liquid fixed-bed reactors the
direction of flow becomes very important and leads to a number of ne\\
reactor types: the gas and liquid streams may separately flow upward
or downward; hence concurrent or countercurrent flow mav• occur. In
•
addition to these varieties, some of the reactants may change phase

during the reaction. Also one of the phases may be continuous and the
other disperse, and this condition may be reversed. Thus a great variety
of gas-liquid-phase fixed-bed reactors are possible.
Le;: us represent these various types of the theoretically pol>sible fixed
beds in Fig. 6-1 in the form of elongated rectangles. Let us divide the
a:-ea of these rectangles proportionately to the molar flow per unit cross-
sectional area, with the light areas representing the gas phase and the
dark areas representing the liquid phase. Types I to IV ha\'e no appre-
ciable net change of molar flow between the phases, although consid-
erable rrass transfer may occur between the gas and liquid phases. This
meam. that there is no substantial diminution or increase of any phase
through gas formation or condensation. All the other types V to X show
a nel change of molar flow between the gas and liquid phases.
Let us now examine each of these reactor types, consider their ap-
\
plications, and give examples, if such examples are known.
The down flow concurrent reactor (type I, Fig. 6-1) is the most com-
monly used of all gas-liquid fixed-bed reactors. It is commonly called
the trickle-bed reactor. Here, both the gas and the liquid flow downward.
The gas is the continuous phase and the liquid is the disperse phase.
The hydrodesulfurization of petroleum oils and tar oils and many other
reactions can be carried out in trickle-bed reactors. If the hydrocracking
reaction becomes prominent at elevated temperatures, the same oils
produce considerable gas at the expense of the liquid. Thus we have a
trickle-bed reactor of type V. On the other hand, the hydrogenation of
hydrocarbon oils at relatively low .temperatures an~ high pressures de- .
pletes the gas phase, and consequently is performed in type VI trickle-
bed reactors. •
Trickle-bed reactors. may also be countercurrent, as in type Ill, IX,
and X reactors. In these reactor types, the continuous gas phase flows
l
upwards, countercurrently to the downward flowing disperse liquid phase.
As we will see further below, countercurrent fixed-bed reactors are lim-
•
GAS-lIQUID N IASE AXED-BED REACTORS 157
•
I ]I 1II III IX
l G •
l G l G l G
•
l G l L G l G lG
Downtlow Upflow Countercurrent Countercurrent
concurrent concurrent flow vaporizotion
y :TI Jlll vIII :x:
l G l G LG l G lG
L G L G l G LG G
Down flow Oownllow Upllow Upflow Countercurrent
concurrent concurrent concurrent concurrent flow
vaporization condensation vaporization condensation condensation
, fiG. 6-1 Various kinds of fixed-bed leactors.
• ; ,
ited in use to very low flows and are not common in the industry. The
limitation is imposed by the occurrence of flooding. Actually, for given
flow rates of gas and liquid, concurrent-flow fixed-bed reactors have the
advantages of dissipating less power as fluid friction and of achieving
higher values of gas absorption coefficient and gas-liquid interfacial area
without flooding the column. On the other hand, the main advantage
of the countercurrent fixed-bed reactors is their ability to attain consid-
erably more th~n one equilibrium stage for gas-liquid contacting. 2
The type IV reactor is not feasible.

In the upflow concurrent reactors, types II, VII, and VIII, both the
continuous liquid phase and the disperse gas phase flow upward. The
catalyst is fully submerged in the continuous liquid phase and the gas
moves in the form of bubbles. For this reason these reactor types are
sometimes called fixed-bed bubble reactors.
•
•
At very high· flow rates of gas and liquid, it is possible to operate

concurrent fixed-bed reactors with a dispersed liquid phase and a con-
tinuous gas phase. More will be said about such reactors later in this
chapter.
Likewise, countercurrent gas-liquid reactors (types Ill, IX and X) may
be conceivably operated in flooded condition by restricting the liquid
outlet flow. Although the author cannot think of any reason for using
such reactors in preference to upflow concurrent bubble reactors, this
possibility is mentioned here simply for reasons of completeness. In the
resulting types of reactors, which may be designated as types IIIF, IXF.
and XF, the liquid phase would be the continuous phase and the gas
phase the disperse phase.
3
Tarhan has discussed a particular type of concurrent downflow re-
actor in which a cold liquid and a hot gas are mixed at the top of a
reactor bed in the presence of a catalyst. The liquid is simultaneously
evaporated .lOd reacted. Thus, the reactor begins as a type V vaporizing
reactor and ends up as a gas-phase reactor.
A tYI~e VIII reactor may conceivably be used in the alkylation of
i
benzene with ethylene over a zeolite catalyst since the reaction occurs
in the liquid phase and the gas phase is consumed.
The remaining part of the present chapter covers only the transport
phenomena of all gas-liquid fixed-bed reactor types in which the gas
phase is the LOntinuous phase, e.g., the trickle-bed reactors. The process
design of these same reactors will be discussed in Chap. 7.
Fixed-bed reactors in which the liquid phase is the continuous phase,
e.g., the fixed-bed bubble reactors (FBBR), will be discussed in Chap.
.. .
8, which covers both related transport phenomena and process design.
Finally the entire class of suspended-bed reactors, including both
related tI ansport phenomena and process design, will be discussed in
Chap. 9.
6.2
TRANSPORT PHENOMENA IN TRICKI.E-BED REACTORS
Two-phase flow through fixed beds of catalyst has not yet been suffi-
ciently studied. Most of the knowledge on gas-liquid flow dynamics in
packed beds is based on work done with absorption-desorption packings,
such as Raschig rings,2.5--15 spheres, 16.li or glass bedds. 1<.19 Very few papers
exist on the flow dynamics of heds packed with common porous catalyst
2o 21
shapes. • The reactor d~signer must have an accurate idea of the flow
regime in the catalyst bed and must be able to calculate the pressure
drop across the bed. This accurate idea should include knowledge of
any axial or radial dispersion in the gas and liquid phases and the texture
of the liquid flowing through the bed.
•
GAS-lIQUID-PHASE FIXED-BED REACTORS 159
In orGer to understand the various flow regimes encountered in a

gas-liquid-phase fixed-bed reactor, let us refer to Fig. 6-2, which shows
an upflow concurrent reactor. Let us assume that the catalyst bed consists
of commercial 3-mm extrusions of some catalyst. Let us establish a liquid
3 2
upflow of 6 m /(h . m ) through the bed (this corresponds to a linear
hourly space \'elocity (LHSV) of about I for a 3-m-diameter by 6-m-high
catalyst bed). At first, the liquid will flow upward without Jisturbing
the packed bed. The catalyst particles will Je completely wetted by the
liquid. Kow, let us start a modest gas upflow in addition to the liquid
upflow and let us increase the gas flow step'''ise at constant liquid flow
rate. First, at IOK gas rates the gas flows through the packing in the form
of bubbles at slightly higher velocity than the liquid phase. The liquid
phase is the continuous phase and the ga<: phase is the dispersed phase.
This flow regime is called bubble flow, and reactors operating y:ith thi"
regime can be called'jixed-bed bubble reacto1"S (FBBR). As the gas rate is
increased at constant liquid rate, one of two things can happen: (1) If
. the catalyst bed is not limited on top by a hold-down screen or by a bed
limiter, at some point the packing will start to become fluidized, beginning
from the top of the bed. (2) If the catalyst is fixed by a bed l;miter, then
new flow regimes may be observed without losing the fixed-bed concept.
22
The first one of these regimes is termed slug flow or pulsing flow. 2:; This
regime is characterized by a periodic fluctuation of the density of the
composite fluid (gas-liquid mixture) flowing through the bed between
the gas density and the liquid density. This alternate variation between
mostly gas flow and mostly liquid flow constitutes a sort of pulsing. The
frequency of the pulsing increases both with increasing liquid rate and
,•
• with increasing gas rate. With still further increase of gas flow rate, the
density difference between the alternate slugs disappear entirely, pro-
ducing a third flow regime, spray flow. This is a regime in which the gas
Gas +Iiquid effluent
3.2-mm (1/8-in)
extrusions
Zr: 6 m
3 m dia .
•
G -
o ...J2.:;.- ~
-'
Gos
L
FIG. 6-2 Schematic representation of an upflow gas-liquid reactor.
•
160 . CATALYTIC REACTOR DESIGN
•
phase is the continuous phase. The liquid phase becomes disperse and
is carried through the column as a heavy mist in the gas stream. At this
point the packing surface is covered by a thick layer of liquid, which
becomes progressively thinner with increasing gas rate. Finally all the
liquirl is transported away as a mist or spray.
No unsteady flow regime has been used intentionally to design any
reactor in the past. It was thought that unstead y flow would require
e:aremely strong- mechanical design and the kinetics under these con-
ditions would be difficult to predict. However, recent experience with
fluidized-bed reactors suggests that the unsteadiness of the pulsing flow
does not have to be a disadvantage. It is perfectly possible to operate a
fixed-bed reactor with an intense gas-liquid flow that pulses. With even
faster flows, the spray regime might be used. as demonstrated in pilot
. stage by the upflow srray re!!ime fixed-bed reactor of the Synthoil proc-
ess,2~-28 a process developed by the V.S. Bureau of Mines to liquefy coal
by hydrogenation in a fixed-bed reactor. Although the Synthoil process
involves a coal slurry rather than a pure liquid, coal particles are almost
completely dissolved by the time they reach the Synthoil reactor, and
besides it may be argued that any flow regime that works with gas and
slurry will most certainly work with gas and liquid. Incidentally, the
Synthoil process turned out to be coal hydrogenation catalyzed by coal
ash under turbulent hydrogen supply and has been abandoned for all
practical purposes. The pulse flow and the spray flow may have some
applications in the taming of exothermic reactions.
22
Turpin and Huntington showed these three flow regimes in 1967
by plotting the ratios of gas-liquid velocities against gas mass velocity, as •
seen in Fig. 6-3. They state that the lines drawn on this figure "to separate
the three flow regimes are actually transition regions rather than points
1000 - - - - - - - - -
--.. Bubble
>-
.-
- >- flow
(,,) ~
-
0",
0 100'-
'" -
>.., I
",>
"'", • Slug flow
0", I
Eo I
10
",E
":;
0- 0
.-
.."
""
I
---
--Spray flow
...J
1 " - - -- - - - '-----'
10 100 1000 10000
Gas moss velocity. lfl/ff 2• h
FIG. 6-3 Various flow regimes in vertical flow tblough gas-liquid-phase fixed
2
beds. [1 lb/(if· h) = 0.001356 kg/(m . s), 1 kg/(m2 . s) = 737.3 Ib/(fe . h)] (From
22
Turpin and Huntington by pennission from the American Institute of Chemical
Engineers.)
•
GAS-LlQUI FIXED-BED REACTORS 16i
•
•
Air-water system
900 f- 73.5° F
800 r-
700 -
-
"'"• 600 c:<:>
--
~
..... 500
.-
..,
0-
.-
~
~
Pulsing
<:>
400 - '"
g
•
regIon
-
.0
'"
<:>
.;, 300 -....
co
.-
co
<:>
200 - , Tronsition
'"'"
100 <!> -- -----
'-_ region
o ~
o 5000 10,000 15,000 20,000
z
GL,lb HzOt{f1 'hl
FIG. 6-4 Flow legimes for concurrent air-water flow through fixed beds.
(From Weekman and Myerl~ by pet mission from the Amel'ican Institute o/Chemical
Engineers.)
of abrupt change from one flow type to another.·' Their experiments

were made with the practical air-water system. Other systems have yet
to be investigated.
Another diagram has been prepai'ed by Weekman and Myerl3 by
plotting s1 1perficial velocities of gas versus liquid, as seen in Fig. 6-4.
The above experiment may be repeated with a downflow fixed-bed
reactor. At the start the system behaves as a trickle-bed reactor in which
the gas phase is the continuous phase and the liquid phase is the disperse
phase. If the liquid flow rate is kept constaryt and the gas flow rate is
\ increased, the flow regime goes over to spray flo\\' without going through
the pulsating regime, since at all times the gas phase remains as the
disperse phase. However, if the gas flow is kept low and constant and
the liquid flow is progressively increased, the packed bed may be brought
to a pulsating flow regime, since the increasing liquid flow is bound to
reach the flooding point.
The most common downflow concurrent regime is the trickle flow
regime, in which moderate flow rates of liquid and gas are used and the
gas phase is the continuous phase. Trickle flow is probably the best
studied among gas-liquid systems, although it has not yet been studied
quite sufficiently. The texture of the liquid phase appears to be a mixture
of films, rivulets, and droplets flowing on the surface of the catalyst
particles. 2,6.21.29 •
Gas-liquid fixed-bed reactors may also be operated countercurrently

either in trickle flow or in bubble flow, Hmve\'er, the range of flow rates
for this regime is too narrow for catalyst-packed beds to be of any in-
dustrial importance.
•
•
Pressure Drop across Concurrent Trickle-Bed Reactors
At least two methods for computing the pressure drop across a concur-
rent trickle-bed reactor have been published. The one is by D. E. Sweeney31J
22
and the other is by Turpin and Huntingwn. These methods will be
discussed I::~low.
Sweeney proposed a simple relationship:
+ = 1 (6-1)
where (IlP) = pressure drop per unit length, Palm

p = fluid censity, kg/m3
Subscripts G denotes gas-phase

L denotes liquid-phase
LG denotes two-phase
F denotes frictional
T denotes total
The single-phase pressure drop figures (ilPk and (~P)I can be cal-
ll
culated by the equation proposed by Ergun and Orning· :
(6-2)
. .
where E = fractional void volume, dimensionless
= viscosity of fluid, Pa . s = kg/Cm . s)
2 3
a = specific surface of solid particle, m /m
u = superficial velocity, based on empty reactor cylinder, m/s
Pc - gas density, kg/m3
= dimensionless constant
gc = force-to-mass conversion factor = "
1.0 kg . m/(I\ . s-)
A list of j3 values was given by Ergun and Orhing. These values vary
between 1.1 and 5.6 for gases and various materials. Equation (6-2) can
•
also be used for (aP)L if Pc is replaced by PLo The same authors also
discuss a simple method-for determining the exact 13 coefficient for the •
fluids and the packing shapes used.

22
The method of Turpin and Huntington is considerably more com-
plicated. These workers proposed a correlation applicable to vertical
•
GAS-LlQUID-PHASE FIXED-BED REACTORS 163
high-pressure reactors operated in concurrent upflow or down flow

•
regimes: •
(6-3)
where Z = height of packed section in reactor, m

P = pressure; PI = inlet pressure; P~ = outlet pre,mre
H' = weight f)0w rate
-
.4 = average area
u - linear velocity
Cl = MW/RT, a constant
C 2 = CIP,
C:\ = Clk,
/I., = constant depending on variation of pressure \,'jth the lon-

gitudinal coordinate = (PI - P 2 )/Z
Subscripts G '-= gas
L = liquid
The use of Eq. (6-3) requires the evaluation of the two-phase frictional
pressure drop (M)cu-, AL (and thus Ac), and the pressure loss due to
the acceleration of the fluids. The pressure drop (1iP/(,lf can be expressed
in terms of a two-phase friction factor feu- which is defined as:
fCLF = (lJ..PIZ)cl..F})rgr dimension less (6-4)

2 Pco Ucs
where ucs is the velocity which the gas would have if it were flowing in
single-phase flow through the unpacked conduit (or reactor) at the en-
tering density PCt).
The factor fGLF has been correlated with the gas-phase and liquid-
phase Reynolds numbers separately for upflow and downflow. These
correlations are:
,
Infcl..F = 8.0 - 1.12 B - 0.0769 B2 + 0.0152 B' (6-5)

•
where B = In(ReiI6i/R~7.,i6;) for upflow with
Re 1.167 ~
0.3 :s ~T :s 500
ReL' I I
InJcLF = 7.96 - 1.34 B + 0.0021 B2 + 0.0078 E'

•
•
•
Re l. 167
for downflow with 0.2 :5 R ~.767 :5 500 (6-6)
eL
An equivalent diameter D, is defined by

D, = 4 RfI (6-7)
where RH is the hydraulic radius. To determine RH the bed is assumed
to consist of a number of parallel channels, the total \'olume of which is
the volume of voids V" in the bed and the total surface of which is the
total surface area of the solids. With these assumptions, RH is then the
ratio of the rotal volume of voids to the total area of solids. Thus:
total volume of voids
D, = 4 RH = 4 --------- = (6-8)
total area of solids
Since we can write:
Total volume of voids V,. E
- -- - (6-9)
Total volume of particles Vp 1 -
Vv = VI> E/(l - E) substituting this value of V,. in Eq. (6-8):

4 Vp E
D = ----'-- (6-10)
t (1 - E)Sp
-
In order to determine AL in Eq. (6-3), Turpin et al. determined what
they call the liquid saturation or the fraction of the voids fIlled with liquid
er/£. The m-:>ss velocity G, based on the total cross-sectional area of the
unpacked reactor, was correlated with EdE as follows:
For upflow (6-11)
24
For downflow EL = -0.017 + 0.132(Gr/Gd (6-12)
with 1.0 :5 (GdGc)°·24 :5 6.0 for both equations, which are said to be only
±25% accurate.
The pressure loss due to the acceleration of the liquid does not have
to be considered for operating pressures below 3.4 atm gauge (3.36 bars
gauge). Above this pressure, the acceleration terms can be calculated
from inlet and outlet quantities.
A trial-and-error procedure must be used in the solution of Eq.
(6-3). Tlie frictional pressure drop (AP)GLF can be obtained directly from
Eq. (6-4) and Eq. (6-5) or (6-6). However, a trial-and-error solution is
, ...
• • •
GAS-UQUID-PHASE FIXED-BED REACTORS 165
•
.
•
required to obtain the total pressure drop - (P 2 - PI)' The procecure
is to assume an average column pressure, which in effect fixes P 2 • Then
This quantity is used in Eq. (6-3) and the procedure is repeated until
the calculated average column pressure is sufficiently close to the as-
sumed average colUlnn pressure.
Turpin's correlations were made with the well-known water-air sys-
tem. For other gases, the viscosity was not expected to change appre-
ciably, but for liquids other than water a viscosity correction factor
9
(J.LuiJ.Ldo. was used. Here subscripts wand L denote water and other
liquid, respectively. This factor is used to multiply the Re~167/Re~;67 term
in Eqs. (6-5) and (6-6).
Pressure drop in packed beds in COUIltercurrent flow is determined
by means of the generalized pressure drop correlation first established
by Sherwood et al.,32 which can be found in its improyed present form
33
in a brochure by ~he Norton CO. Unless extremely large particles of
catalyst are used, the design of countercurrent gas-liquid fixed-bed re-
actors does not make much sense, since with the usual sizes of catalysts •
the packing factor F would be very high and flooding would occur at
quite low rates of gas and liqllid flow. Thus, industrial-size countercur-
rent gas-liquid fixed-bed rClctors are not practical.
Axial Dispersion and Hoidup in Trickle-Bed Reactors

"
In contrast to fixed-bed gas reactors, axial dispersion in gas-liquid-phase
fixed-bed reactors is not insignificant. In studies made with laboratory
and pilot-plant reactors an app':"~ciable amount of liquid holdup was
measured in the porous catalyst bed. Even the gas flow appeared to have
some axial dispersion. However, in large industrial trickle-bed reactors
both the liquid and the gas flow were found to be plug flow.
The studies of Lapidus,21 Schiesser and Lapidus,16 Hochman and
21l
Effron,19 Sater and Levenspiei,34 and Glaser and Lichtenstein are of
great interest in this field. These workers used various tracers in gas
and liquid phases to detect and measure the residence time distribution of
the fluid in laboratory-scale packed beds. They did this by two methods:
•
1. The step function input: In this method the tracer is fed at tull con-
centration during a sufficiently long period of time to reach a steady
concentration in the c;ffluent equal to that in the input. Then the
tracer addition is suddenly discontinued and the decrease in tracer
concentration in the effluent was measured (Fig. 6-5).
•
166 CATALYT1C REACTOR DESIGN
r====:::-----
•
1.0
O.S •
~Porous
S 0.6 spheres
...... Nonporous
u 0.4
spheres--
0.2
o'-- --'-- --'-- -:::::: =-
o 10 20 30 40
Time,s
FIG. 6-5 Comparison of the step response for porous and nonporous pack-
ings. C :=: tracer concentration in effluent; Co :=: tracer concentration at inlet.
(From Schiesser and Lapidus, 16 by from the American Institute of Chem-
ical Engineers.)
.
2. The pulse function input: In this method the packing is hrought into
equilibrium with a tracer-free flow. Then suddenly, a tracer conc:en-
tration is added to the inlet of the packing, maintained constant for
a short time, and then again suddenly discontinued. Again the tracer
wncentration in the effluent is monitored (Fig. 6-6).
21
Figure 6-7 shows three types of time-of-contact curves obtainable by
a step function input. If there is absolutely no backmixing in the reactor,
the response' would be a steplike line labeled A plug flow. If there is
complete backmixing, as in a CSTR, curve B would be obtained. In real-
21
life cases, type C curves are obtained. Lapidus found that in concurrent
flow over nonporous packing the time-of-coT1tact or residence-time curve
approached the plug-flow regime and that the effects of minor deviations
from plug flow would •
not be important unless chemical conversions of
'. 95% or greater were 8:esired. By contrast, residence time experiments
with porous packing produced distorted curves, the distortion being a
consequence of mass transfer of tracer into and from the internal voids,
or pores, of the packing. Pulse-type input curves are affected only to a
minor degree by this inass transfer and thus produce results almost
21
identical to those of a nonporous packing. Lapidus and Schiesser and
Lapidus 16 separated the contributions of pore diffusion and backmixing
16
in bulk voids. As can be seen from the plot of Schiesser and Lapidus
in Fig. 6-8, diffusion of liquids into pores adds a long tail to the step
response curve. Lapidus found that only 40 to 50% of the pore \'olume
is filled with liquid. A corresponding fraction of the packing is thus
•
unavailable for liquid-phase catalytic reaction, which indicates poor over-
all liquid-catalyst conta~ting. The reactor moJel which emerges from all
this is one in which a r~actant molecule enters a catalyst bed either in
the gas phaSe Oi' the liquid phase, moves along with the bulk flow to a
particular catalyst particle, diffuses into a catalyst pore to an active site,
•
•
GA5-UQUID-PHASE RXED-BED REACTORS 167
•
•
becomes adsorbed at the site. and reacts with another adsorbed molecule
or all by itself (depending upon the particular chemical reaction). The
reaction product another molecule becomes desorbed and diffuses
all the \vay back to the bulk flow. By that time the bulk flow may have
moved, say. some 20 min downstream and the produ"Ct molecule coming
out of the pore joins fresh reactant molecules in the main bulk flow with
this much delay. This is the essence of axial dispersion and its net effect
is a decrease in overall conversion.
The task of expressing this axial dispersion in a manner useful for
design purposes has been carried out by DeMaria and White/ Hochman
and Effron.19 Sater and Levenspiel,34 and others. The axial dispersion
term in the chemical reaction equation has been expressed as a Peck,
number, as discussed in Sec. 4.3. The Peelet numbers proposed by various
workers are listed below:
1. In the gas phase of a two-phase syster1:
34
Sater and Levenspiel PeG = (udplDak = 3.4 Rec067
(6-13)
DeMaria and White' (6-14)

Hochman and Effron 19 PeG = 1.8 Re,~o., 10 -fUN)S RCL
(6-15)
with (j = +40%
2. In the liyuid phase of a two-phase system:
34 3 711
Sater and Levenspiel PeL = 7.58 10- ReZ :l (6-16)
•
'- , Hochman and Effron 19 PeL = 0.034 Re~'s 10'U)()$ ReG
(6-17)
0.100 alumina
-,'" spheres
o -
U 0.050 rous alumina
::> spheres
OO~
10 20 30 40 50
Time, S
FIG. 6-6 Comparison elf pulse respor.se for porous and nonporous packing.
C = tracer concentration.. in effluent; V = volumetric flow rate of liquid;
..
Q = moles tIacer injected in pulse input. (From Schiesser and Lapidus,t6 by
pennission from the American Institute of Chemical Engineers.)
•
•
•
...
-- •I "\ •
-.-'"'" ,
I
t
\
\
\
\
A
Plug flow
-e
o
.-'" •t \
\
-c.,u: t
I
t
\
\
Perfect
,,
• •
c:
o •,t mIXing
u
\
B
I
,• '..,.-C
" Intermediate
o 8
Time t
FIG. 6-7 Thlee types of experimental time-of-contact curves. (From Leon
Lapidus, «Flow Distribution and Diffusion in Fixed-Bed Two-Phase Reactors, Ind.
Eng. Chem., 49:1001 (1957), by pe/mission from the American Chemical Society.)
I ' ,
where u = axial velocity, m/s
2
Da = axial dispersion coefficient, m /s
dp = nominal catalyst particle diameter (diameter of a sphere
having the same surface area as the actual particle)
Subscripts Land G denote liquid phase and gas phase,
respectively.
The fact that these workers came out with such a variety of results is
quite disconcerting and confusing to the designer. It seems that everyone
has been missing something important. Fortunately for the reactor de-
signer, most design problems encountered involve industrial-size reac-
tors, which are of the plug-flow type. In the case of laboratory or pilot-
scale reactors, the designer can act conservatively without committing a
significant economic sin. He can simply select the Peelet number cor-
relation which gives the highest backmixing (the poorest yield), hence
the smallest Pe. If the actual pilot plant then produces a higher yield,
no one will complain.
35
Mears has proposed a minimum reactor length z required for free-
dom from significant axial dispersion effects in trickle-bed reactors. For
less than 90% conversion 'lnd first-order reactions, Mears' condition is
expressed as:
•
Z 200: Co
- > 1n ---"- (6-18)
d, Bo CJ
•
GAS-llQUID-PHASE FIXED-BED REACTORS 169
,
•
where 0: = reaction order
Z = length of reactor bed, m
, d, = equivalent sph~rical diameter of catalyst particle, m
= (dp Lp + tfpI2)0.5
dp = diameter of catalyst particle. m
Lp = length ('f ~talyst particle. m
Bo = Bodenste;n number = ri, uliJ"n dimensionless
u = superficial vebcily. :11/s
2
Da, = axial eddy diffusivity, m /s
3
C = concentration of reactant, kmoL'm
Subscripts: 0 = initial value; f = final value
The Bodenstein number is a Peelet number based on the particle di-

ameter d, instead of dp. Mears used the correlations of Hochman and
l9
Effron to calculate it.
1.0 = - - - - - - - - -
0,8
0,6
OA
0.2
1.0 0
u
, , 0.8
"-
u 0.1
,
, 0.08
0.06
<.)
o 0.6
......
<.)
0.Q4
0.4
0.02
0.2
o _ - - 1 ._ _ _--.:::
0.01
50 100 150 200 250 300 350300 500 100
Time,s Time.s
(01 {b I
FIG. 6-8 Comparison of the step and integt ated pulse I esponses for porous
pacKing: (a) arithmetic plot and (b) semilogaritbmic plot. Curve 1: integrated
pulse response, porous spheres. Curve 2: saturation step response, porous
spheres. Curve 3: elution step response, porous spheres. Curve 4: nonporous
spheres (From Schiesser a1Jd LaPidus,16 by pet mission from the Ame, ican Institute
of Chemical Engineel'S.)
• •
The koldup of a trickle-bed reactor is important information that a

reactor designer must have in order to calculate gas and liquid flow rates
and also to estimate conversion rates.
36
Three kinds of liquid holdup in the catalyst bed can be defined : the
total holdup eL is the total liquid in the packing under operating condi-
tions; the static koldup Ss is the liquid in the packing which does not drain
from the packing when the liquid supply to the column is discontinued;
and the operating koldup eo is the difference between the totai and stat:c
holdups. All three types of holdup are expressed as cubic meter~ of
36 37 37
liquid per cubic meter of packed bed. . D. L. ROSS showed that holdup
of any type is exponential with liquid superficial mass velocity G, that
is, if holdup and G are plotted on double logarithmic paper, the data
points fit a straight line. Holdup may be determined experimentally in
either pilot reactors or existing commercial reactors. In case this is not
possible, holdup may be estimated from the following correlation by
38
Stltterfield et a1. :
Gd v, d3g p2 -It,
EL = 9.9 2 (6-19)
f.L f.L
2
where G = superficial mass velocity, kg/(s . m )
d = characteristic diameter of catalyst particle, m

f.L = dynamic viscosity, kg/{m' s)
2
g = gravitational constant, m1s
p = liquid density, kg/m3
\
--- ,
The dimensionless group (Gdlf.L) is the Reynolds number and the group
d3gp2/f.L2.~ made up from the ratio of the Reynolds number squared to
2 2
the Froude number Fr = (G /p dg) and is known as the Galileo number
39
Ga.
This equation neglects the additional dimensionless term (adt' in
Davidson's holdup correlation,40 where a is the area per unit volume.
Others have correlated experimental holdup data for trickle beds with
the dimensionless groups proposed by Davidson and Satterfield. These
correlations are listed in Table 6-1.
It appears that there is not much agreement {)n the correlation. All
except Otake and Okada agree that Davidson's term plays no role. All
except Satterfield agree on wand find twice the value found by the
latter. In the absence of a higher certainty, the designer is advised to
use Eq. (6-17).
The holdup affects many parameters in the trickle bed. As the holdup
•
•
GAS-UQUID-PHASE FIXED-BED REACTORS .7.
•
TABLE 6-.
Correlation of Holdup Data for Trickle-Bed Reactors
EL = k . (Gdlp.)'" . (d'gp2/p.l . (ad)' .
w y % Authors References
0.676 -0.44 1.0 Otake and Okada 41

0.76 o o Hochman ami Effro:. 19
0.75 -0.5 o Mohunta and Laddha 42
0.333 -0.333 o Satterfield 38
ELincreases, and the volume fraction Ep occupied by ::.0lid catalyst remains

constant, the relationship
.
EL + Ep + E(; = 1 (6-20)
indicates that EC; has to decrease. The pressure drop will also be thereby
affected.
39
Henry and Gilben base the local reaction rate constant on the volume
of liquid, hence holdup, rather than on the bulk volume of catalyst when
deriving kinetic relationships in their reactor element. Thus, holdup
becomes part of their rate expression, as we will see further below. RossJ,
shows that the logarithm of conversion in trickle beds is inversely pro-
portional to the residence time of the reactants in the holdup in the bed.
9
Henry and Gilbere report on a more complicated relationship between
43
conversion and hold up. Satterfield states that, all other things being
equal, the reaction rate is proportional to liquid holdup.
Generally speaking, the liquid distribution over the catalyst bed can
be very nonuniform at the low liquid space velocities occurring in I-m-
tall reactors as compared with full scale, 15- to 20-m-tall reactors. As
liquid velocities increase, distribution uniformity improves. but does not
37 H
become perfect even in full-scale reactors. .
Radial Dispersion in Trickle-Bed Reactors

Radial dispersion in trickle-bed reactors is less important than axial dis-
persion. from the viewpcint of the reactor. l\lost of the studies on radial
dispersion in packed beds have been made with common tower packings,
which are used for absorption-de~orption purposes. Of course, with the
large packings there is a lo.rge increase in the void volume near the wall
and the ratio of this volume to the total packed volume is not negligible.
In contrast, with catalyst particles of the order of magnitude dp = 0.003
•
•
m, or 3 mm, the increase in void volume at the reactor wall is practically

negligible. .
Axial dispersion actually means a delay in part of the fluid stream
reaching the end of the reactor bed, the practical result of which is a
decrease in yield. T~e effect of radial dispersion is not a delay but a
variation in the gaslliquid ratio €C/EL' The random packing of catalyst
pellets ca'lses a variation of this ratio from point to point, but the extent
of the vanation :.hould not adversely affect the reaction kinetics.
LiquiJ distribution :n packed columns and trickle-bed reactors has
been made the sub~~ct of a mode! study by G. J. Jameson. In this model
IO
"the liquid is assumed to spread from one packing piece to another at

the common point of contact. By the use of a mechanistic approach a
mathematical cescription of the flow process was synthesized." Then,
"predictions from the model were co.nparerl with experimental results
from the literature and they were found to agree quite well."
There is another type of radial disoersion which may become very
significant and even dangerous. If the catalyst contains or forms fines
mixed with regular particles at one particular point of the catalyst bed,
or if the catalyst bed is stepped ou while being filled into the tower and
thus compressed and compacted, the flow of fluid will be curtailed through
the dust-loaded or compacted region and will be diverted to the more
open regions of the bed. If the reaction is an exothermic one, the com-
pacted region might turn into a hot bed and trigger really serious trouble
because low flow rates or longer residence times mean a poorer ability
to remove the generated heat. If the reaction is endothellllic, the com-
pacted region would be cooled and practically excluded from the reactor
'.
• capacity. All these considerations are really not under the direct control
of the designer. However, the designer must be aware of such possibilities
and prescribe proper and detailed procedures for charging the catalyst
and for operating the catalyst bed. Also, the designer must provide for
proper gas and liquid distribution to prevent radial dispersion. The
persons who should be responsible for preventing radial dispersion are
those supervising the filling of the reactor with catalyst. That job must
be done with utmost care.
Heat Transfer in Trickle-Bed Reactors

Heat transfer relationships in trickle-bed reactors were first studied by
1i
Weekman and Meyers .45 in an air-water system. Actually most common
trickle-bed processes are run in adiabatic reactors, with interbed heat
exchange if necessary. For this reason, standard heat transfer infor-
mation is fully adequate. Only in the case of strongly exothermic reac-
tions did Weekman and Meyers suggest the use of sidewall-cooled re-
actors, in fact, gas-liquid-phase NINAF reactors. They developed
•
GAS-llQUID-PHASE FIXED-8ED REACTORS 173
•
•
experimental data for such reactors and found that a change from gas-
continuous (trickle-bed) to pl,llsing flow results in very large improve-
ments in radial two-phase heat transfer. In some cases this improvement
reached 400%. The addition of a gas-phase flow to the liquid flow in-
creases the effective thermal conductivity over that measured for single-
phase liquid flow. Lumped heat transfer coefficients at the wall were
quite high, e.g.,
2
h = 0.6241 kJ/(s . m • K)
2
observed at CL = 33.91 kg/(s . m )
2
and Gc == 0.610 kg/(s . m )
The concept of the overall effective thermal conductivity K, lumps all

the conductivities in the gas, liquid, and catalyst phases in one parameter
and assumes the temperatures in these three phases to be the same.
An equivalent heat transfer coefficient ho is defined as:
ho = Q (6-21 )
21Troz At/m
where Q = heat-transfer rate, kJls •
ro = radius of the reactOl- tube, m

z = axial distance, m
At/m = the log mean temperature difference
(tu. - to) - (tU' - tb )
•
In (tu' - to)/(tu' - tb)
tu. = wall temperature, QC
to = inlet bulk temperature, QC
tb = outlet mixing cup temperature, °C
li
Weekman and Meyers calculate !to as :
2.892 0.183 •
ho = Kt + (GLCp; + GcCpc) (6-22)
ro z
where K, = overall effective thermal conductivity, kJl(s . m . K)

C = mass velocity based on emp~y tube area, kg/(s . m 2
)
Cp = specific heat, kJl(kg . K)

c·p -- specific heat-of saturated air, kJl(kg . K)
-
Subscripts: G denotes gas
L denotes liquid
•
174. CATALYTIC REACTOR DESIGN
In SI units ko will have the dimensions of kilojoules per second per square'
meter per kelvin.
It was found that even at the highest gas rates and lowest liquid rates
the air was saturated with water vapor. Thus where \'aporization takes
place, as in the air-water system, the correct heat balance can be achieved
by using C~ = AHcl!:lte instead of Cp<; where !:lH(; = enthalpy increase
of moist air and !:lte = to - lh'
The transition from ~a:,-contil~UOUS to pulse flow strongly influences
heat transfer. Generally, both K, and h" increase \"ith increasing gas and
liquid rates. The transition regime imposes certain bends and inflections
-
on the K, versus Gc curve~,"
A radial transport model has been developed b\' assuming that the var-
ious heat-transfer mechanisms can be lumped into two lerms.4{; Accord-
ing to this model, all the heat transferred by eddy difhsion in the radial
direction would be included in one term ana the molecular conduction
in the stagnant bed would be included in the other term, This concept
led to the development of the following relationship:
K, (K,)" I
A = " + ),ReLPrL + 13("(; "L)Re(;Pr(, (6-23 )
I. I.
where AL = molecular conductivity of liquid. kJl(s ' m' K)

Ae - molecular conductivity of gas, kJ/(s . 111 • h)
(K,L - contribution to overall effective thermal conductivity
due to molecular conduction in stagnant bed,
kJ/(s . m . K)
\,
; ,
),,13 = radial fractions of liquid and gas mass velocity.
The constants (Kt) .. )" and f3 were determined from experimental datA
in the pulsing region and are given in Table 6-2 in both CS Customary
System (USCS) and SI units.
TABLE 6-2
Values of (K.)o, )" and f3 in uses and SI Units
BtuI(h . ft' . OF) kJ/(s . m' . K)
•
(K,)o 7,71 4,37 x 10-'
.
'Y 1.74 X 10-3 0.987 X 10-"

0.172 0.976 x 10~
13
•
GAS-LIQUID-PHASE RXED-BED REACTORS 175
•
G G G
L •
"." -
(0 ) ( b)
G G+L
,..----
••
Cold
L
L
G+L G+L •
, (c) (d) ( eJ
FIG. 6-9 Various ways of cooling an adiabatic gas-liquid reactor.
Trickle-bed NINAF reactors might be applicable to highly exothermic

reactions. However, most industrial trickle-bed processes are not that
exothermic and some sort of interbed cooling is sufficient to tame the
heat evolved.
The interbed cooling or heating of gas-liquid fixed-bed reactors is
considerably more complicated than that of adiabatic fixed-bed gas re-
actors. The mere addition of the liquid phase to a gas reactor creates a
host of new problems. Some of the cooling methods of gas-liquid reactors
are shown in Fig. 6·9. In Fig. 6·9a both phases are cooled in a joint
indirect cooler, the cooleo gas and liquid are separated, and the gas is
further piped while the liguid is pumped up to the top of the second
bed. Obviously gas and liquid cannot be pumped together. In Fig. 6-9b
both phases are first separated and then only the liquid phase is cooled
after being pumped up to the next bed. This scheme is based on the
•
176 CATALYTIC REACTOR DE~GN
•
•
knowledge that cooling of liquids is more efficient and economical than
cooling of gases. In fact, the liquid may be cooled low enough so that
by mixing it with the gas the desired temperature for both phases is
obtained. The scheme of Fig. 6-9c can be either concurrent or counter-
current. In any case, the liquid is downflow. Here again, the liquid phase
is separated and cooled and redistributed on top of the next bed. In Fig.
6-9d we have an upflow concurrent reactor. Above the lower bed, gas
bubbles continue to ascend and pass through the valve tray into the
upper bed. The continuous liquid phase can be cooled by withdrawing
liquid from the side and pumping it through a heat exchanger; the
cooled liquid is returned to the reactor at the bottom of the upper bed
just above the valve tray. Above the upper bed, the two phases separate
and can be withdrawn separately. In Fig. 6-ge we have another upflow
concurrent reactor, but here the interbed cooling is done by direct in-
jection of additional cold liquid or wld gas. Probably, other methods of
cooling liquid phase reactors are also available, e.g., Fig. 7-2.
Mass Transfer in Trickle-Bed Reactors

Extensive work has been done on mass transfer in trickle-bed reactors.
29 47
The reader is especially directed to the publications of C. N. SatterfieId •
of MIT, J. J. Carberry 48 of the University of Notre Dame, and J. Hanika
4
in Prague. 9-5!
The addition of the liquid phase to the simple gas-phase catalytic
system introduces entirely new problems in reaction kinetics and mass
transfer. Figure 6-lO represents the mass-U ansfer phenomena around
\ a catalyst particle in a trickle-bed reactor. It i,:,; k:1own that 40 to 50% of
the pore volume is filled with liquid. For truly liquid-phase reactions, it
can then be safely assumed that catalytic reactions will take place in the
liquid phase or at liquid-covered surface sites. Consequently, a gaseous
reactant molecule will have to be absorbed in a liquid droplet, diffuse
inside the droplet through the pore to the catalyst site, become adsorbed
on the site, and react there with an adsorbed liquid molecule. That liquid
droplet comes there first by bulk. transport as a droplet, after which part
of it intrudes by capillary force into the catalyst pore. The reaction
product will have to diffuse through the liquid out of the pore and if it
stays in the liquid phase, it will move further with the outside part of.
the droplet, which might fall further below in the catalyst bed. If the
reaction product is a.gas, it will have to be desorbed from the liquid
droplet once outside the pore.
29
Studies of Satterfield .43 and others S1.1ggest thut the practical result
of mass transfer in gas-liquid reactors is a lower value for the effective-
ness factor Tt. The effectiveness factor of O'.-methylstyrene hydrogenation
•
•
GAS-UQUID-PHASE FIXED-BED I<EACTORS 111
•
Gas phase
Oesarption
. Absorption
Calalyst pellet
Liquid
~op(
OiffuSiO~,......
I
Liquid
•
/
(a )
Gas I Liquid
.
/ pore
I "I
I
I
I ./
I
r
I
I
(b)
FIG. 6-10 Mass-tIansfer phenomena around a catalyst particle in a trickIe-

bed reactor.
..
over a Ptlalumina cd'[a1':st

, was found to be as low as 0.07
. to 0.13 for 3.2
52 53
by 1.3 mm (Ifs in by Y20 in) pellets. On the other hand, Cecil et al. in
..
trickle-bed hydrodesulfurization studies have found effectiveness factors
as high as 0.8, i.e., of the same order of magnitude as effectiveness factors
of gas reactions. If both gas-phase and liquid-phase reactions occur in
a trickle bed, the overall effectiyeness factor can be quite high, i.e., close
to ·1.0. However, in purely liquid-phase reactions 11 is expected to be
typically low. Why Cecil's value is as high as it is is not quite clear.
Peter F. Way 54 in his Ph.D. thesis at MIT made a thorough review of
the literature on trickle-bed reactors and discussed the mass transfer of
gas-liquid reactions in trickle-bed reactors under certain limiting con-
• ditions such as isothermality, first-order kinetics, plug flow, yolume con-
stancy, and gas-liquid equilibrium. Way's ev.perimental strategy is of
interest: he first ran his heterogeneous catalytic reaction (isomerization
of cyclopropa ne. to propyr~ne over a silica-alumina cracking catalyst) in·
the gas phase and made measurements. He then ran the same reaction
over the same catalyst in the presence of a liquid which is a solvent for
•
178 CATAl'(TIC REACTOR DESIGN
•
the feedstock, operating the reactor as a trickle bed, and again made
measurements. The rates of the gas reaction and the liquid-gas reaction
are expressed as follows:
. 3
Gas-phase rate = - k 11 C, kmolJ(s . m') (6-24)
where all the terms can be separately determined or calculated.
3
Two-phase rate = - k l)' 11 C, kmol/(s . m ) (6-25)
Two types of two-phase reaction rate constants are c0nsidered: krr,

the two-phase reaction rate constant, based on concentration in the liquid
phase; and k~, the two-phase reaction rate constant, based on concen-
tration in the' gas phase.
A factor for the external mass-transfer resistance is defined:
-y=C
I
where C j is the concentration in the liquid at the gas-liquid interface.

The relationships between the bulk gas concentration C, C" Cj , and C*
are diagrammatically represented in Fig, 6-11. C* being the concentra-
tion in the gas phase that would be in equilibrium with the liquid at the
cataly:,t interface C,.
Vapor-liquid equilibrium is maintained at all points of the reactor:
)' =
- Kx
where K is the vapor-liquid equilibrium constant. This is one of the
original assumptions and means that C (bulk) is in equilibrium with C"
It follows that:
C* = 'Y C
If Arrhenius expressions are written for krl' and kt~, their activation
•
energies EI1' and E!~, respectively, would be related as follows:
•
(6-26)
where Ek = 12,500 kJ/kmol for the solvents Isopar I and Nujol.

We may obtain some insight into the nature of two-phase kinetics by
comparing the rate expressions
Gas phase; • In Cl = k 11 \I(

(6-27)
Co- F
Two-phase (liquid concentration units):
(6-28)
•
GAS-UQUID-PHASE FIXED-BED REACTORS 179
•
Bulk gos
C
Equilibrium
Gos
-- -. Cj -
-
- -
Cs Cs: rCj
Ca1alyst
particle
r:IG. 6-11 Relationships among C, C" Ci , and C* in mass transfer bulk
gas and catalyst surface across the gas-liquid interface.
Two-phase (gas concentration units):
(6-29)
3
where Cl> C2 = molar concentrations of feed and product, kmol/m
3
Vc = volume of catalyst particle, m
F = feed rate of gas at reactor temperature and pressure,
3
m /s
FL = feed ratel)f liquid at reaction temperature and pres-
3
~- , sure, m /s
3
VG = gas molar volume, m Ikmol
3
VL = liquid molar volume, m /kmol
The terms in the brackets can be considered as "effective" feed rates in

the two-phase equations. The quantities -y and 1'] can be evaluated and
hence, the intrinsic rate constants can be calculated:
'Y = 1 - + (FLI2F r ) In(X/X2 )]

•
(6-30)
•
where KLS = overall m(l£s-transfer coefficient from gas-liquid interface
•
to the catalyst surface

•
dp - diameter of pellet = length of pellet, III
X = mole fr:lction in liquid phase

•
•
•
•
•
For spheres and cylinders KLS can be calculated as

•
6D(1 - E)
KLS = ---'----'- (6-31)
£oLd"
where D is the diffusivity in liquid phase and EL is the extelllal liquid
holdup. With the value of "I obtained from Eq. (6-30), KerTJ'Y and Kr,TJ'Y
can be calculated from the following re l 3.tionships:
1 +"1
Krr'YTJ = V (6-32)
o 2
1 1 + "I
Kr, 'YTJ = V +F (6-33)
(
2
where y is the mole fraction in the gas phase.
Finally, the value of TJ is obtained gr.... phically by the method of
29
Satterfield after calculating 4> for the two-phase system:
<!> = R2 (h.rrTJ)'· (6-34)

D E
where <!> is the tortuosity factor. .

The above formulas were all based on volume constancy during the
reaction. In case the volume changes during the :'eaction, it is still possible
to compute t!'le rate of the reaction. In most cases the volume change
in the liquid phase and concentration chang-:s of the reactant in both
, .
phases can be neglected. With concentration being constant, the tel Il1
\.
. '
KerTJ'Y can be readily calculated from the expression for Kef:
(6-35)
where Cs = "I Ci and

1 + F de
- KrrTJ'Y = C (6-36)
I dVc
Also, in case the gas volume change can be measured, a simple rate
53
equation can be used.
In addition to the foregoing studies made in the United States, some
very interesting work has been done by J. Hanika et a1. 9-51 in Prague.
4
.
These workers attempted a fundamental approach by using a vertical
49
flat plate as an oversin'Iplified model. They distinguished among three
flat models: plug flow, -the linear velocity profile, and the parabolic
velocity profile. The first was solved by the Fourier method. For laminar
flow, the diffusion equation was solved by the finite difference method.
It was found that the conversion is affected very little by the transverse
•
GAS-LIQUID-PHASE FIXED-BED REACTORS 181
,
velocity profile in the flowing liquid film and thai. the effect on conversion
of diffusive mass transfer in. the direction of flow is also very small.
Basically, three regions were observed in the reactor during operations:
,
At Sh > 10, the diffusion region

1
At 10- < Sh < 10, the transition region
1
At Sh < 10- , the kinetic region
This model was checked experimentally for catalytic hydrogenation of
cydohexene in methanol and I-propanol as solvent in presence of a Pt
51
black catalyst.
A more realistic model of a vertical column of spheres was developed 50
by the same authors. This mathematical model is very similar to the
38
experimental model of Satterfield et al.
The foregoing information on mass-transfer relationships in trickle-
bee: reactors should enlighten the reader in general terms. In specific
terms, mass transfer will have to be expressed by means of an effective-
ness factor for the particular liquid-phase reaction. That effectiveness
factor is used in the design equations. How this factor is calculated will
be discussed in detail in the next chapter.
NOMENCLATURE
a Catalyst particle surface-area/volume ratio, m-I
- 9
A Average area, m- [Eq. (6-3)]
Bo Bodenstein number = d,ulD a , dimensionless
3
C Molar concentration of reactant, kmoVm
C* ~oncentration in the gas phase that would be in equilibrium
3
with the liquid at the catalyst interface, kmoVm
Cl C 2 C3 Constants of Eq. (6-3)
Cj Molar concentration in the liquid at the gas-liquid interface,
3
kmol/m
Cp Specific heat, kJ/(kg . K)
C; Specific heat of saturated air, kJ/(kg . K)
Cs Molar concentration oii. the c;;.~alysL surface, kmoVm 3
dp Catalyst panicle diameter, m

d, Equivalent spherical diameter of catalyst particle, m
D Diffusivity in liquid phase, m%
2
Do Axial dispersion coefficient for mass, m /s
•
•
Axial eddy diffusivity, m%

•
Equivalent diameter of reactor, m

Activation energy for the group Kvdvc
Activation energy of gas-liquid reaction based on gas-phase
concentrations, kJ7kmol
Err Activation energy of gas-liquid reaction based on liquid-
phase concentrations, kJ/kmol
f Frictional factor, dimensionless
F Feed rate of gas at reaction temperature and pressure,
3
m /s
Fr Froude number, dim~nsionless
g Gravitational constant, m!S2
Force-to-mass conversion factor =
:Mass flow rate in gas phase, J.: g/(m2 . s)

Mass flow rate in liquid phase, kg/(m2 . s)
Gallileo number, dimensionless
2
Equivalent heat transfer coefficient, kJ/(s . m . K)
Gas-phase reaction rate constant
Two-phase reaction rate constant based on concentration
in the gas phase
•
. . Two-phase reaction rate constant based on concentration
in the liquid phase
•
Constant of Eq. (6-3), depending on variation of pressure

with the longitudinal coordinate
K Vapor-liquid equilibrium constant
K, Overall effective thermal conductivity, kJl(s . m . K)
KLS Overall mass-transfer coefficient from gas-liquid interface
to [he catalyst surface
Lp Length of catalyst particle, m

P Pressure: PI = inlet pressure and P 2 = outlet pressure
Pe Peelet number, dimensionless
- Q Heat transfer rate, kJ/s
TO Radius of reactor tube, m
Hydraulic radius of reactor, m
•
•
GAS-UQUIO-PHASE FlXED-BED REACTORS 183
•
2
Sp Total area of solids or catalysts, m
t Temperature, DC
tb Outlet mixing cup temperature, DC
u Superficial velocity based on empty reactor cylinder, mls
v Molar volume
3
Vc Volume of single catalyst particle, m
3
Vp Total volume of catalyst particles, m
3
V" Total volume of voids in the catalyst bed, m
W Weight flow rate
x Conversion, dimensionless
y Mole fraction in gas phase, dimensionless
z Axial coordinate, m
Z Reactor length, m
a Reaction order
Dimensionless constant in the equation of Ergun and Orn-
•
mgor
R?dial fraction of gas mass velocity
External mass transfer resistance factor = C/C; or
Radial fraction of liquid mass velocity
(tlP) Pressure drop per unit length. Palm
I1tlm Log mean temperature difference, DC
.
Fractional void volume, dimensionless

Ec Gas-phase fraction. dimensionless
EL Liquid-phase fraction or liquid holdup, dimensionless
Eo Operating holdup, dimensionless
tp Catalyst-particle-phase fraction, dimensionless
Es Static holdup. dimensionless
Effectiveness factor. dimensic:1kss
Molecular conductivity of gas. kJl(s . m . K)
•
Molecular copductivity of liquid. kJl(s . m . K)
Viscosity.
, . Pa . s
Viscosity of water, Pa . s
•
CATAlVfIC REACTOR DESIGN
•
•
p Fl~id density, kg/ms
.
(J' Standard deviation

•
,. Empirical factor to correct for ":ortuosity" and for non-

uniformity of catalyst pore cross section
Subscripts
f Final
F Frictional
G Gas phase
L Liquid phase
LG Two-phase
o Initial or inlet
T Total
w Wall
REFERENCES
1. J. Klassen and R. S. Kirk, "Kinetics of the Liquid-Phase Oxidation of Ethanol,"
AIChE J. 1:488 195 (1955). (Cited as example of countercurrent trickle-bed
process.)
2. L. Philip Reiss, "Cocurrent Gas Liquid Contacting in Packed Columns," Ind.
Eng. Chem. Process Design DeveWp. 6:486 199 (1967).
, 3. M. Orhan Tarhan, Vaporizing and Pretreating Aromatic Hydrocarbons
Feedstocks without Polymerization, U .S. Patent 3,448,039, 1969.
4. Paul B. Venuto and P. S. Landis, "Organic Catalysis over Crystalline Alu-
minosilicates," Advan. Catalysis 18:259-371 (1968) .
•
5. J. C. Charpentier, C. Post, and P. LeGoff, "Ecoulement ruisselant de liquide
dans une colonne it garnissage. Determination des vitesses et de- debits
relatifs des films, des filets et des gouttes," Chim. llld. Genie Chim.
100(5):653-4)65 (1968).
6. J. C. Charpentier, C. Post, W. Van Swaaij, and P. LeGoff, "Etude de la
retention de Iiquide dans une colon ne it garnissage arrose it co-courant et
a contre-courant de gaz-liquide. Representation de sa texture par un modele
de film~, filet~, et gouttes," Chim. lnd. Genie Chim. 99(6):803-826 (1968).
7. F. DeMaria and R. R. White, "Transient Response Study of Gas Flowing
through Irrigated Packing," AIChE J. 6:473 181 (1960).
8.
-
E. Dutkai and E. Ruckenstein, "Liquid Distribution in Packed Columns,"
Chem. Eng. Sei. 23:1365-1373 (1968).
9. C. J. Hoohendoorn and J. Lips, "Axial Mixing of Liquids in Gas-Liquid
Flow through Packed Beds," Can.]. Chem. Eng. 125-131 (June 1965).
•
GAS-UQUI FIXED-BED REACTORS 185
•
•
10. G. J. Jameson, "A Model for Liquid Distribution in Packed Columns and
Trickle-Bed Reactors," Trq.ns. Inst. Chem. Engr. 44:TI98-T206 (1~6).
11. L. Musil, C. Prost, and P. LeGoff, "Hydrodynamique des colonnes noyees.
a' garnissage avec contre-courant de gaz-liquide. Comparaison avec les co-
lonnes arosees," Chim. Ind. Genie Chim. 100(5):674-682 (1968).
12. K. E. Porter, "Liquid Flow in Packed Columns. Part I: The Rivulet Model,"
Tran<.Inst. Chem. Engrs. 46:T69-'1'73 (1968) .
•
12a. l{ E. Porter, V. D. Barpett, ard J. J. Templeman, "Liquid Flow in Packed

COlUmns. Part Il; The Spread of Liquid over Random Packings," Trans.
Inst. Chrm. Enb" 46:T74-T85 (1968).
13. K. E. Porter and J. J. Templeman, "Liquid Flow in Packed Columns. Part
Ill; Wall Flow," Trans. Inst. Cite7/!. Engr. 46:T86-T94 (1968).
14. J. J. Templeman and K. E. Porter, "Experimental Determination of Wall
Flow in Packed Columns," Clum. Eng. Sri. ~a:1139-1140 (1965).
IS. W. P. M. van Swaaij,J. C. Charpentier, and]. Villermeaux, "Residence Time
Distribution in The Liquid Phase ofTlickle Flow in Packed Columns," Chem.
Eng. Sci. 24:1083-1095 (1969).
16. William E. Schiesser and Leon lapidus, "Further Studies of Fluid Flow and
Mass Transfer in Trickle Beds," AIChE]. 7:163-171 (1961).
17. Vern W. Weekman, Jr. and John E. Myers, "Heat Transfer Characteristics
of Concurrent Gas-Liquid Flow in Packed Beds," AIChE]. 11:13-17 U965).
(Special copyright permission from the American Institute of Chemical
Engineers.)
18. S. F. Chung and C. Y. Wen, "Longitudinal Dispersion of Liquid Flowing
through Fixed and Fiuidized Beds," AIChE]. 14:857-866 (1968).
,
•
'-. ., 19. J. M.Hochman and E. Effron, "Two-Phase Cocurrent Downflow in Packed
Beds," Ind. Eng. Cltem. Fundamentals S:64-71 (1969).
20. M. B. Glaser and I. Lichtenstein, "Interrelation of Packing and Mixed Phase
Flow Parameters \\;th Liquid Residence Time Distribution," AIChE]. 9:30-34
(1963).
21. Leon Lapidus, "Flow Distributioll and Diffusion in Fixed-Bed Two-Phase
Reactors," lnd. Eng. Chem. 49:1000-1006 (1957).
22. Jim L Turpin and R. L Huntington, "Prediction of Pressure Drop for Two-
Phase, Two-Component Concurrent Flow in Packed Beds," AIChE ].
13:1196-1202 (1967).
23. Vern W. Weekman, Jr. and John E. Myers, "Fluid Flow Characteristics of
Concurrent Gas-Liquid Flow in Packed Beds," AlChE J. 10:951-958 (1964) .
•
24. Sayeed Akhtar, Sam Friedman, and Paul M. Vavorsky, "Low SulfurFuel
Oil from Coal," C.S. ~ureau of Mines Coal Desulfurization Program, Tech.
Progr. Rep. 35 (July 1971).
25. Sayeed Akhta~, Sam Friedman, and Paul M. Yavorsky, "Process for Hydro-
desulfurization of Coal in a Turbulent Flow Fixed-Bed Reactor," paper
•
186 . CATAlYTIC REACTOR DESIGN
,
•
presented at the 71st Am. Inst. Chem. Engrs. National Meeting, Dallas, Feb.
20-23, 1972. .
•
26. Sayeed Akhtar, Sam Friedman, and Paul M. Yavorsky. "Low-Sulfur LiC!uid
Fuels From Coal," paper presented at the Am. Chem. Soc. Symposium on
Quality of Synthetic Fuels, Boston, Mass., April 9-14. 1972.
27. Sayeed Akhtar,Jamesj. Lacey, M. Weintraub, Alan A. Reznik, and Paul M.
Yavorsky, "The Synthoil . Balance and Thernlal Effi-
ciency," paper presented at the 67th Am. lnst. Chem. Engrs. Nz.tl Meeting,
Washington, Dec. 1-5, 1974.
28. Paul M. Yavorsky, Sayeed Akhtar, and Sam Friedman, "Convertip':, t.::cal
into Non-Polluting Fuel Oil," Glum. Eng. Prog;r. 69(3);51-52 (1973).
29. Charles N. Satterfield, Mass Transfer in Heterogenous Catalysis, MIT Press,
Cambridge, 1970, pp. 86-88.
30. D. E. Sweeney, "A Correlation for Pressure Drop in Two-Phase Co-Current
Flow in Packed Beds," AlChE j. 13:663-669 (1967).
31. Sabri Ergun and A. A. Orning, "Fluid Flow through Randomly Packed
Columns and Fluidized Beds, Ind. Eng. Chem. 41:1179-1184 (1949).
32. Thomas K. Sherwood, G. H. Shipley, and F. A. L Holloway, "Flooding
Velocities in Packed Columns," Ind. Eng. Chem. 30:765--769 (1938).
33. Ralph Strigle, Jr., Frank Rukovena, and Leonard Rollison, "Generalized
Pressure Drop Correlation," Sheet Gr-I09 R6 Norton Chemical Process
Products Division, Akron, Ohio .
.
34. V. E. Sater and Octave Levenspiel, "Two-Phase Flow in Packed Beds," Ind.
Eng. Chem. Fundamentals 5:86-92 (1966).
" 35. David E. Mears, "The Role of Axial Dispersion in Trickle-Flow Laboratory
Reactors," Chem. Eng. Sci. 26:1361-1366 (1971).
36 .. H. L Shulman, C. F. Ullrich and N. Wells, "Performance of Packed Columns:
Total, Static, and Operating Holdups," AlChEj. 1:247-253 (1955).
37. Leon D. Ross, "Performance of Trickle-Bed Reactors:' Chem. Ellg. Pmgr.
61(10):77-82 (1965).
38. Charles N. Satterfield, A. A. Pelosof, and Thomas K. Sherwood, "Mass
Transfer Limitations in a Trickle-Bed Reactor," AIChEf- 15:226-234 (1969).
39. H. Clarke Henry and John B. Gilbert, "Scale-up of Pilot Plant Data for
Catalytic Hydroprocessing," Ind. Eng. Chem. Process Design Develop. 12:328-334
(1973 ).
40. J. F. Davidson, "The Hold-Up and Liquid Film Coefficient of Packed Towers.
Part II: Statistical Models of the Random Packing," TrailS. Inst. Chem. Ellgr.
37:131 (1959). ..
41. T. Otake and K. Okada, "Liquid Holdup in Packed Towers: Operating
Holdup without Gas£1ow," Chem. Eng. (japan) 17:176-184 (1953).
•
GAS-UQUI FIXED-BED REACTORS f87
•
42. D. M. Mohunta and G. S. Laddha. "Prediction of Liquid-Phase Holdup in

Random Packed Beds," Chem. Eng. Sci. 20:1069-1072 (1965).
43. Charles N. Satterfield, "Contacting Effectiveness in Tdckle-Bed Reactors,"
Chem. Reaction Eng. Reviews, Intern. Symp.. 1974, .4dvan. Chem. SeT.
I !8:50-74 (1975).
44. Arnold A. Bondi, "Handling Kinetics in Trickle-Phase Reactol's," Chem-Tech.
1:185-188 (1971).
45. Vem W. ·vVeeklllan,Jr., "Heat Transfer and Fluid Flow for Concurrent Gas-
Liquid Flow in Packed Beds," Ph.D. thesis, Purdue University,
•
1963 .
46. Sakae Yagi and Daizo Kunii. "Studies on EffeniYe Thermal Conductivities
in Packed Beds," AIChEj. 3:373-381 (1957).
47. Charles N. Satterfield anci Peter F. Way, "The Role of the Liquid Phase in
the Performance of a Trickle-Bed Reactor:' A1ChE j. 18:305-311 (1972).
(Special copyright permission from the American Institute of Chemical
Engineers.)
48. James J. Carberry, "Heat and Mass Diffusional Intrusions in Catalytic Re-
actor Behavior," Calal),sis Rev. 3(1):61-91 (1969).
49. J.Hanika, K. Sporka, ;!nd V. Ruzicka, "Investigation of Hydrogenation in
Liquid Phase. XVI. Theoretical Models of H\'drogenation in Liquid Film.
Flat Plate," Collection Czech. Chem. Commull. 35:2 J 11-2123 (I970).
50. J.Hanika, K. Sporka, and V. Ruzicka, "Investigation of Hydrogenation in
Liquid Phase. XVII. Theoretical Model of Hvdrogenation in Liquid Film
on a Vertical Column of Spheres," Collectiun Czech. Clum. C01l!lllun.
36:1358--1369 (1971).
5L J. Hanika, K. Sporka, and V. Ruzicka, "lm'estig;uion of Hydrogenation in
Liquid Phase. XVIII. Experimental Verification of a Theoretical Model of
a Trickle-Bed Reactor," CollectUm Czech. rlmn. Commun. 36:2903-2913 (1971).
52. Charles N. Satterfield, Yi Hua Ma, and Thomas 1\.. Sherwood, "The Effec-
tiveness Factor in Liquid-Filled Porous Catalyst:' in Inst. Chem. Ellgs. Sym-
posium SeT. No. 28, Tnstitution of Chemical Engineers, London, 1968, pp.
22-29.
53. R. R. Cecil, F. X. Mayer, and E. N. Can, Jr.. "Fuel Oil Hydrodesulfurization
Studies in Pilot Plant Reactors," paper presented at AIChE Meeting, Los
Angeles, December 1968.
54. Peter F. Way, "The Performance of Trickle·Bed Reactors," Ph.D. thesis,
M1T, Cambridge, 1971.
•
••
•
Chapter
PROCESS DESIGN OF
TRICKLE-BED REACTORS
The design of trickle-bed reactors is considerably more complicated than

that of fixed-bed gas reactor'>. There are no standard published methods.
Many oil cO!llpanies have developed and are using their own proprietary
design procedures. In the following we will attempt to develop a pro-
cedure based on the present-day best published knowledge of trickle-
bed reactor design.
7.1
GENERAL PROCEDURE
•
The first thing the designer should do is study the reacting system with
all its kinetic and mass-transfer peculiarities, because this infOllIlation
will determine the kind of design model selected. There is a choice
between a plug-flow and a partially backmixed reactor. In either case
the reactor will be concurrent downflow and adiabatic. The use of criteria
discussed in Sec. 6.2 will determine whether the reactor is plug-flow or
not. We will select a process and design one reactor of each type in this
book.
A hydrocarbon oil desulJurization reactor is selected as the example. The
following assumptions can be made:
· The reaction occurs between the liquid phase and the catalyst surface.
· The reaction is adiabatic.
•
• The key reactants are sulfur compounds dissolved in the oil feed and
a hydrogen-containi~g gas.
· The liquid volume in the reactor remains constant.
•
f90 'CATALYnC REACTOR DESIGN
•
Although OUt main purpose is to design a reactor for the conversion of

sulfur compounds, we must take account of all the side reactions oc-
cUlling• in the reactor because they all contribute to heat evolution and
make up the composition of the reacting mass. Because the number of
individual reactions is too large, it is customary to lu~p them into groups
of reactions. We may write one equation for each of the following lumped
•
reactIon groups:
· Hydrodesulfurization
· Hydrodeoxygenation
· Hydrodenitrogenation
· Hydrocracking
· Saturative hydrogenation
Because economics dictates the recycling of the unused hydrogen, the
recycled gases normally contain certain impurities. Hydrogen sulfide,
the product of hydrodesulfurization, can be easily removed from the
recycle gas.] Thus the major impurity will be methane, a product of the
hydrocracking side reaction. It is customary to remove at least part ef
2
this methane from the effluent gas and to produce hydrogen from it.
Other impurities are water and ammonia. Ammonia is normally removf'd
together with the hydrogen sulfide in a monoethanolamine absorber,
and water vapor is removed from the desulfurized gas in a molecular
sieve or equivalent dryer.
In order to develop the design equation, reference is made to Fig.
,
,
" '
7-1, which represents a cylindrical packed bed of catalyst. In this bed a
Gas in{C (0) =Co

T(O)=T v
Liquid in
r z=O
2
Area 'If 0 T /4
~' •Z
f, Z - • V.L ,•
,
• Z + f,z
Pa eked bed of ealalysl ,... ZT

•
C{z) Cdzl}
T{z) TL(z) V • z=z T
Gas out
, •
LIQ UI d out
FIG. 7-1 Schematic representation of a typical downflow gas-liquid fixed-bed
reactor.
•
•
PROCESS DESIGN OF TRICKLE-BED REACTORS 191
differential height !:!.Z is considered for which a materials balance and a

heat balance ",ill be obtained. The design will be determined for the
liquid-phase reaction, and gas concentrations will be calculated from the
liquid-phase reaction at all points.
Let us desip"nate:
~
3
CH = molar hydrogen cOf'centration in bulk phase, kmol/m
CL = molar conu'ntrarion of key reactant in liquid phase or molar
concensation of hydrocarbons containing an atom of sulfur,
3
km:JUm
., .)
A, = cross-sectional area of the catalyst bed = 71'DT/4, m-

z = axial coordinate in the reactor
ZT -.: total reactor :ength, m
Let us introduce the concept ..lf phase fraction, which is the fraction of
the reactor bed volume occupied by anyone phase. The total volume V
of the packed catalyst beds consists of the volume taken by the catalyst
particles Fp (which includes both the volume of the solids and that of
the pores). the gas volume Vc, and the liquid volume V L • The following •
equations can be written:
Fp
and I V +
Ifweset
,
•
Vp - VL F(;
cp - CL and - cc
F V V
it follows that
(7-1)
where cc = gas-phase fraction

CL = liquid-phase fraction or liquid holdup
cp = catalyst particle phase fraction
also c = void fraction = Cc + CL
While tp and hence £ are constant along the bed length, lOG and tL
may vary somewhat in s()me cases and appreciably in others. \Ve will
compute CL according to Satterfield's Eq. (6-19):
(6-19)
•
,
•
Plug-Flow Trickle-Bed Reactor
The case of the plug-flow industrial size reactor will be considered first.
Let us ,make a materials balance for the liquid phase of the differential
reactor volume increment:
(Molar inflow axially) - (molar outflow axially)
- (molar disappearance by reaction) = °
Let us calculate the value of each set of parentheses in general terms:
Molar inflow axially = 2 I

4' DT UL EL CL =
1T
Molar outflow axially = ~ D~ UL EL CJ-.l=

'iT 2
Molar disappearance by reaction = -E
L -
4 DT az: <R
•
where DT is the reactor diameter in meters and· UL is the superficial

velocity of the liquid phase in meters per second. Using these expressions
in the materials balance equation and dividing both sides of the resulting
equation by (1T/4)D~ UL az EL gives:
Cd, - Cd,+.l= _ !:RI = °

az UL
where !:RI is the rate of the hydrodesulfurization reaction in kilo moles

per cubic meter per second. This equation cm be rearranged to
CLlzHZ - Cd, - !RI
-
6.z
When 6.z ) 0, the left-hand side of this equation tends toward dCddz
and
- - (7-3)
dz: UL
Equation (7-3) can be converted to a dimensionless fOlIIl by substitution:
and
Thus we obtain:
de, -- -
dZ (7-4)
where CLO is the initial value of CL'

•
PROCESS DESIGN OF TRICKlE-BED REACTORS 193
,
•
An analogous set of equations can be developed for the heat balance.
Referring to Fig. 7-1, we can write for the differential volume:
(Heat inflow axially) - (heat outflow axially)
+ (heat generated by reaction) = 0
The various heat flows to substitute in the equation are:
Heat inflow axially in liquid phase = TI, ~ D} UL PL CpL EL
'IT
Heat outflow axially in liquid phase = TI<+.1< '4 D} UL PL CpL EL
Heat generated by reactions = 2: [( - LlH)9l]('IT/4)D} Llz. EL
Heat inflow axially in gas phase = TL ~ iJ} up (p lOG
Heat outflow axially on gas phase = 11,+60. ~ D} up Cp tG
"V 'IT
+ L.. [9l( - LlH)] "4 Dj- LlZEL
?
=- 0 (7-5)
Equation (7-5) can be divided by (1Ti4)D}(upc p tG + UL PL CpL EL)Llz. and

rearranged:
,
,
,,
•
"
When Llz ) 0,
and
dz
Again, dimensionless variables can be substituted into Eq. (7-6):

Tr = TITo
•
and after simplification we will have:
*
dT
dZ = 2: [(-LlH)~K] dpcjTo(EG P cpu + CL Pi.. CpL UL) (7-7)
Because the reaction occurs in the catalyst particle, the exothermic

heat is released right inside the particle and is propagated across the
•
•
exterior surface of the particle to the bulk liquid and from there to the
gas flow. Consequently, there should be a temperature gradient between
the inside of the particle and its outside surface. However, because of.
the high thermal conductivity of solid catalysts, it is reasonable to assume
that, for moderately exothermic reactions, the temperature inside the
particle is constant. (A similar assumption was made in the case ofNINAF
reactors.) Then the continuously liquid-washed catalyst particles would
be substantially at the temperature of the bulk fluid streams.
Let us now define the lumped chemical reactions we will consider:
Sulfur-containing hydrocarbons:
Hydrocarbon S;- 2 H2 ) hydrocarbon=H2 + H 2 S (7-8)
Oxygenated hydrocarbons, e.g., phenols:
Hydrocarbon OH + H2 ) hydrocarbonl-H + H 20 (7-9)
Hydrogenated hydrocrackable hydrocarbons:
Hydrocarbon CH 3 + H2 ) hydrocarbon H + CH 4 (7-10)
Nitrogenated hydrocarbons, e.g., pyridines, quinolines:
Hyd + 3 H2 ) hydrocarbon H3 + NHs (7-11)
Unsaturated hydrocarbons with double bonds:
Hydrocarbon + H2 ) hydrocarbon=H 2 (7 -12)
Literature values for the kinetic constants of the above reactions fall •
in a very wide range. It is obviously possible to develop a: cobalt molyb-

date-on-alumina catalyst that would work according to any of the kinetic
data published. Consequently, while some of the kinetic data in this book
are taken from the literature, others were simply assumed from the
general range of the published data. The reactor designer should of
course obtain new data that must correspond to the particular catalyst
to be used.
The following kinetic expressions will be used in this book:
8
9{1 = Tjl( - dCddt) = Tjl 1.008 X 10 exp( - S2,060IRT) CL (7 -13)
8
9{2 = Tj2( - dCoJdt) = Tj2 3.6 x 10 exp( - 50,208/RT) Cox (7-14) .
• 6
9{3 = Tj3( - dCNldt) = Tj3 6.48 x 10 exp( - 72,060IRT) CN (7 -15)
• 18
9{4 = Tj4( - dCh/dt)
.
= Tj4
- 9.0 x lO
6
exp( - 243,500IRT) Ch, (7-16)
9{s = Tjs (-dCh!dt) = Tjs 3.6 X 10 exp( -46,860fRT) C hc (7 -17)
where Cox = molar concentration of compounds each containing one

atom of oxygen
•
PROCESS DESIGN OF TRICKlE-BED REACTORS 195
•
C:\molar concentration of compounds each containing one

=
atom of nitrogen.
C hy = molar concentration of hydrocrackable hydrocarbons. i.e .• •
the entire unreacted feed stock

CIK = molar concentration of unreacted unsaturated or saturable
aromatic hydrocarbons
TJ = effectiveness factors of various reactions
The reaction rate constants of Eqs. (7-13) to (7-17) are all expressed
in l~r-I.
Sulfur compounds can be lumped into aliphatic sulfur and thiophenic
sulfur. The lalter react more slowly and require more severe conditions
i 4
for hvdrodesulfurization.
•
R. A. Flinn et al.: and R. R. Cecil et al. use
the following expression for the two kinds of sulfu:':
(7-18)
where S = sulfur content of the product
S? = initial ..:ontent of type 1 (aliphatic) sulfur
S~ = initial content of type 2 (thiophenic) sulfur
k j = reaction rate constant for type I sulfur
. k2 = reaction rate constant for type 2 sulfur
e = lILHSV, where LHSV is the liquid hourly space velocity.
3
Flinn et al. showed that this relationship does not quite represent the
experimental data. Rather, the reaction appears to follow the rate qm-
stant kl up to a certain temperature, above which there is a bend in the
correspondiri5 rurve and the reaction then proceeds according to k 2 •
Although hI and k2 values were given, no E" E 2 , Ab and A2 values were
published. Consequently, in the absence of data for sui fur types, this
book uses total sulfur data. Thus, CL represents the molar concentration
of both type 1 and type 2 sulfur or total sulfur. i.e., the molar concen-
tration of compounds each containing one atom of suIfur, and Cr is the
reduced molar total sulfur concentration.
Similarly, the other molar concentrations. Cox. C:-;. Ch" and C hc can
also be expressed in reduced forms:
•
where C oxo , C:-;o, C hvO , and C HCO are initial "alues for Cox. C:-;, Ch" and C ho
respectively. •
Design equations similar to Eq. (7-4) can be deyeloped for Crux> Cr :-;,
CrhY' a!1d ..C rhc : -
dp ~R2
-- (7-19)
Cox(l llL
•
•
•
dCrN - dp !K3
- (7-20)
·dZ C NO UL
•
•
dCrby _ dp 9l. 4
- (7-21)
dZ ChyO UL
dCrbc
- dp ~R5
(7-22)
dZ ChcO UL
Because the major reactant feed components are rather high-boiling

liquids, there is no reason to be concerned with the mass transfer of
these components from one phase to the other. However, ifit is necessary
to calculate the mass transfer of H2 from the gas phase to the liquid
phase and the mass transfer of reaction products such as H 2 S, CH 4 , H 20,
and NH:\ from the liquirl phase to the gas phase, the following equations
can be written:
kKHa (CUB - CLH ) = L (H 2-consuming reactions) (7-23)
kKH?S a(CLH,s - CuH,s) =:0 !RI (7-24)
kt;<:H, a(CU :H • - CUCH.) = !R.4 (7-25)
kKHP a(CI.Hp - CuH,p) = !R.2 (7-26)
kK:-;H, a(CL:-;H, - Cu:-;H,) = !R.3 (7-27)
where subscript H denotes hydrogen, L denotes liquid phase, and Le

denotes liquid phase in equilibrium with gas phase.· The heat transfer
•
from the catalyst to the liquid and to the gas is assumed to have very
little resistance since catalysts, liquids, and the bulk gas are all the same
remperature..
To summarize, the relationships that can be used to describe the plug-
flow trickle-bed reactor system are Eqs. (7-4), (7-19) to (7-22), (7-13) to
(7 -17), and (7-7). After substituting the values of ~Ri in the six first-order
ODEs, Eqs. (7-4), (7-7), and (7-19) to (7-22), these equations can be solved
numerically and simultaneously as initial-value ODEs. The initial values
can be written as follows:
Inlet Z = 0 C, = 1.0 c'ox = 1.0
C,hc = 1.0 -.
'T'
r
_
- 1.0
The numerical values Qf the various heats of reaction are:
- t:.H, = 251,0()0 kJ/kmol for hydrodesulfurization
-t:.Ho=
- 68,200 kJ/kmol for hydrodeoxygenation
-t:.H 3 = 64,850 kJlkmol for hydrodenitrogenation
,
•
PROCESS DESIGN OF TRICKlE-BED REACTORS t97
•
-!l.H4 = 41,000 kJlkmol for hydrocracking
-!l.H5 = 125,520 kJlkmol for hydrosaturation
Equations (7-13) to (7-17) can also be expressed in ki!Jmoles per
square meter per second and the concentration terms can be replaced
by products of reduced concentrations by initial concentrations:
4 (7-28)
fKI = 111 2.8 X 10 exp( - 82,060/RT)C CL" T
5
~R2 = TJ2 1.0 X 10 exp( - 50,200/RT)ClOX Coxo (7-29)
~Rs = TJs 1.8 x 10 exp( -72,060/RT)Cr~ C:\o
3
(7-30)
•
fR4 = TJ4 2.5 X 10 exp( - 243,500/RT)Crll~' C"yCJ

15
(7 -31)
3 (7-32)
HI.5 = TJ; 1.0 X 10 exp( - 46,860iRT)Cmc C hd1
Trickle-Bed Reactor with Axial Dispersion

Small trickle-bed reactors such as those used in laboratories and pilot
plants have some axial dispersion. Let us write the material balance for
the liquid phase of the differential reactor volume increment in Fig.
7-1.
(Molar inflow axially) - (molar outflow axially)
+ (molar inflow by axial dispersion)
- (molar outflow by axial dispersion)
- (molar disappearance by reaction) = 0 (7-33)
• • dz •
•
11.{ I
1>' 0 ar
fl b . I d' . 7r
out ow y aXla Isperslon = -4 Dj-
q
£1. -
D del.
d
\Z
where - D(dCJdz) is the flux in axial direction according to Fick's law
and D is the diffusivity of the reacting molecules in the liquid phase.
Using these expressions in the balance equation, Eq. (7-33), dividing by
(1T/4)D~ UL !l.z fL, and rearranging gives:
(I)
• \ I
--
Ur
When LlZ ) 0, the difference expressions ir. the foregoing equation tend
to become differentials a.nd we obtain
- (7-34)
•
198 CATALVllC REACTOR
• •
Equation (7-34) can he converted to a dimensionless fOllll by substituting
.
C. = CdC LO and Z = zldp
dC D ,fcT 9t 1 dp
•
---.: - T
. 2
- (7-35)
dZ - UL dp dZ
Here, the term uLdplD is the Peelet number Pemai for mass and axial
dispersion in liquid phase.
Similar equations can be written for all the other lumped reactions
occurring in the process. Also, an analogous heat balance equation can
be developed:
(Heat inflow axially - heat outflow axially)
+ (heat inflow by axial dispersion - heat outflow by axial dispersion)
+ (heat generated by reactions) = 0 (7-36)
The axial heat flows are:
Liquid phase Gas phase
Inflow
Outflow
The heat flux by axial dispersion across a cross-sectional area Ac is given

• 5
•
by Fourier's law :
dT .
-Ka Ac dz (7-37)
where Ko is the axial thermal diffusivity in packed beds in square meters

per second. Thus the heat flows by axial dispersion are:
Liquid phase Gas phase
'IT 9 dT
Influx - '4Dr EL PL CpL KaL dz z
•
'IT 9 dT
Outflux - -Dj- EL tlL CpL K al• d
4 Z z+6z
•
PROCESS DESIGN Of TRICKlE-SED REACTORS 199
The heat balance equation must inelude both the gas phase and the
liquid phase. as well as all the reactions. This gives a very long expression,
which after simplification. rearrangement, and conversion of differences
to differentials gives:
dT d'lT
---,,-
ECP cp Ka + EL PL CpL kaL
- 9
dz dz-
which can also be written in dimensionless form:

dT,
-
1 ECP c p Ka + EL PL CpL K.L
dZ ECP Cp U + EL PI. CpL UL
d
+ 2: URiC - ilH);]
To
p
We may defiue a Peclet number for heat for two-phase axial dispersion:
Pe,.,," =
dp(Ec P cp U + EL PL CpL ud
-.!...;.-:..~-!-----=-~--!.=-~ {7-38)
- Ec P cpKa + EL PI. Cpl. KaI.
with which the heat balance equation becomes:
. (7-39)
,,
.
--.
.
> In Eq. (7-39) everything except the Peelet number is relatively easily
o~tainable. The Peelet number Peha2 is a function of gas-phase and liquid-
phase axial dispersion coefficients, which have to be determined.
The reactions, which take place in the catalyst partide. release the
exothermic heat right inside the particle. This heat is propagated across
the exterior surface of the particle to the bulk liquid and from there to
the gas stream. As in the case of the NINAF reactors, the temperature
inside the particle is assumed to be constant.
Now let us summarize the relationships that can be used to describe
the trickle-bed reactor system with axial dispersion:
The five reaction rates given by Eqs. (7-28) to (7-32) are of course
the same as in the plug-flow case. The design equations are Eq. (7-39)
as the heat baiance equation and
- (7-40)
dZ
,
.
•
•
dC,ox - I d2Crox dp 9(2
- 2 - 0 • (7-41)
dZ 'Pe"",1 dZ UL Coxo
dC T.'X - 1 ~CTN - dp ~R3

2
0 (7-42)
dZ Pern.... dZ Ut. CNO
dC m, I " my _ d" ~R4

d-C o
-- 2
(7-43)
rlZ Pe"",l dZ Ut. C hvO .
•
'1
dC me I d-C me d" !K"
-- 0
1Z2
- (7-44)
d7. Pc "",I ill. C hd •
The following boundary conditions must be written:

Inlet z=o CT = 1.0 Crox -- 1.0 C,N -- 1.0
Crln = l.U
. C"IL = Le T T = 1.0
dC T - dTT -
Outlet Z = ZT - 0.0 - 0.0
• dZ dZ
It is not possible to write boundary conditions for each ODE. One
can design a reactor for the conversion of a specific fraction of the suI fur ,
L the oxygen, or the nitrogen or for a certain amount of hydrocracking
or saturation, but not for all these specific conversious at the same time.
If it is decided to design for su!fur conversion, one has to accept whatever
one obtains from the other reactions.
".
7.2
DESIGN EXAMPLES FOR
PETROLEUM HYDRODESULFURIZATION
Let us now calculate two specific examples for the petroleum oil hydro-
desulfurization reactor that was discussed generally in the previous sec-
tion. Selected design parameters related to both examples are listed
below:
o Desired final fractional sulfur conversion Xv = 0.65
· Feedstock boiling in the 260 to 365°C range and containing 4% sulfur,
no oxygen, 0.35% nitrogen, and olefins corresponding to a bromine
number of 5.0
· Temperature 375°C = 648.2 K
•
o Pressure = 55.0 bars *
3
o H2/oil ratio = 0.5 m H 2 (NTP)/kg oil
· Catalyst: cobalt molybdate on alumina, 5-mm square cylinder pellets
of PE = 950 kg/m3
•
PROCESS DESIGN OF TRICKLE-BED REACTORS
•
· Kinetics: key reaction is first-order, kinetic data are given in Eqs. (7-28)
to (7-32); 111 = 0.4; weight .hourly space velocity (WHSV) = 2000
3
kg/(m 'h)
· Void space in catalyst bed E = 0.36
· Oil density at ambient temperature, PLO, is given as 35.3° API or 141/
(35.5 + 131 5) = 843.3 kg/m3
· Thermal expansion of the oil, 1.49 at 375°C, ~iyes density at reaction
~emperature PL = (843.3/1.49) = 569.3 kg/m'
- CpL = 3.3095 kJl(kg' K)
Most industrial-s:ze reactors are of the plug-flow type. The general de-
sign contiguration of such a trickle-bed reactor is shown in Fig. 7-2. The
reacting gas G enters the reactor vessel from the top. The reacting liquid
L also enters from the top but is distributed by means of a liquid dis-
tributor over the catalyst bed As will be seen further below, the reactor
will need twc catalyst beds with a gas quench in between as a means of
interbed cooling. The effluent gas leaves the vessel at the bottom. The
reacted liquid accumulates at the bottom and is rt:leased from the reactor
by means of a leyel controller.
Design parameters specific to the plug-flow reactor are given below:
The plant capacity is 250,000 tlyr.
The approximate reactor volume can be calculated from the weight
,
...r--Bed 1
Quench
v-Bed 2
•
G•
- - -- - - - ,Le
,,
-- -
,
L
FIG. 7-2 Trickle-bed reactor with interbed quenching.
•
,
hourly space velocity. Assuming an on-stream time of 310 days/yr, the
hourly capacity is '
,
,
250,000 kg/yr = 33 602 k /h = 9.33393 kg/s
(310 days/yr)(24 h/day) , g
Then the approximate reactor volume is
33,602 kg/h, = 16.801 m''\

2000 kg/(h'm")
In order to determine the reactor's hr:/Sitt1diallleta mlio, we must assure
that the reactor will indeed operate as a trickle-bed reactor. For this, we
may refer to Fig. 6-4 and calculate the gas/liquid ratio as follows. We
note that 0.5 Nm Hikg oil is equivalent tu (0.5)(2.016)/(22.4 m~/kmol)
3
which equals 0.045 kg H2/kg oil. Then, sillce 5000 lb oiU(h·ft2) appears
to be safely in the gas-continuous region up to 250 Ib gas/(h'ft~), the
hydrogen rate, assuming pure hydrogen is used, is [5000 Ib/(h·[(2)] .
(0.0451bllb) = 225 lb H 2 /(h·fe). Indeed, 225 Ib/(h'fe) is in a safe region
in Fig. 6-4 and the process is certain to be trickle-bed. The minimum
reactor cross-sectional area is:
9 9
(33,602 kg/h) . (0.0929 m-/fe) = 1.3782 m 2
[5000 lb/(h'fe)] . (0.453 kgnb)
Since we already know the volume, the reactor height will be l6.80 1
3 2
m /1.3782 m = 12.19 m and the reactor diameter 1.324 m, which are
quite reasonable values. A lower height/diameter ratio would also be per-
• • missible since the process would then be slower.
An economic study should be made of the cost of the reactor at
different height/diameter ratios. At large diameters and high pressures,
the reactor wall must be thicker and hence more expensive. On the other
hand, the cost of the reactor is also a function of it:> external surface
area, which for perfect cylinders is given by the relationship:
Surface area 4 H
-----= + 0.5
Volume H D
where H is height and D is diameter. This relationship gives a minimum
.surface/volume ratio for H = D. Because in this example we do not want
to go into cost problems, we will simply select a somewhat larger di-
ameter, namely Dr= 1'.5 m. The corresponding cross-sectional area A,
2
is 1.7671 m and the approximate reactor height is 9.5 m.
The sulfur content of the feedstock is gi,'en as 4.0 wt% of sulfur. This
corresponds to 4.0/(32.064)(100 kg) = 0.12475 kg-atoms SOIIOO kg of
SO-containing material.
•
-
When designing a reactor that is actually going to be built, the designer
should use actual molecular weight data obtained in a reliable laboratory
on properly sampled representative feedstocks. However. for the pur-
po~e of this book we can look up the molecular weight of oil from page
6
21 of Maxwell's book from which we obtain a value of 670 for an oil
with a mean boiling point of 594°F (322.2°C) and API gravity of 35.3°.
Then 100 kg of oil contu.ins 100/670 = 0.14925 kmol. Thus the mole
:ractio'l of S-containing oil is:
0.12475 mol SIlOO kg 0
_ = .8358 = •)'"
0.1492;) mol/lOO kg
This means that 83.58% of all molecules contain one atom of sulfur.
Lf't us calculate C /.!,:
= 14.0) (569.3 kg1m:{) = 0.7102 kmol S/m:!

(32.064)(100 kg)
Also, 0, ,,·t 'k oxygen = 0)16 kmolll 00 kg of oxygen-containing
material. The gas oil selected contains no oxygen. However, for rea-
sons of completeness, equations for oxygenated compounds will still be
developed:
Co,,, == __O-"'-,P..:c'-_ kmol/m:1

(16) (lOO)
The content of is best expressed as a bromine number. A
11llsaturaies
bromine numbc" uf 1.0 means that 1.0 g of bromine is added to the double
\ bonds contained in 100 g of feed stock. The molar concentration of dou-
ble bonds in the feed can be expressed as follows:
-
Br. - no. PL (0.001) :l

ChcO = k = 0.1781 kmol unsaturates/m
(159.832)(0.1 g)
The contt'lIt of h.• drocrackable compounds is difficult to define. Only the
reaction results show the extent of hydrocracking. The basis of feed
concentration is the entire feed:
569.3 k g / m : ' ,
== 670 = 0.8497 kmol/m
The nitrorzclI
,. colI(t'lltratioll is 0.35 wt % N in feed. The molar c0ncen-
tration of nitrogen-conpining compounds is:
\0.35) I'L ,~
C,," = k /k = 0.14224 kmol N compounds/m-
(100)(14.008 'g g-atom)
The molar COllfelltration of suIfuT in liquid phase will then be
•
•
s
GLO = (4.0)(569.3)/(100)(32.064) = 0.7102 kmollm initially and GL =
0.7102(1 - x) at any point. in the reactor after that. Since the liquid
volume is assumed to remain constant throughout the reactor, conver-'
si on x may be defined in tenus of concentrations:
Similarly
Xj = 1 - erN
X~ = 1 - Grhy
X; = I - Grhe
One kilo mole of gaseous process mixture at 375°C and 55 bar occupies
the volume of
3
(22.414 m NTP)(648.2 R)( 1.0] 325 bar) = 0.97972 m3
(55 bar)(273.2 K) .
S
Furthermore, 1 m of reactor void space will contain at reaction con-
3
ditions 110.97972 = 1.0207 kmollm , which is also the initial hydrogen
concentration GHO '
The Hloil mol£ ratio can be calculated from the H/oil ratio:
S
(0.5 m H 2 )(670 kg/kmol). = 14.946 kmol H 2/kmol oil
3
(22.414 m NTP/kmol) (1 kg od)
For simplicity's sake in calculations, the reactor is a~svmed to use pure
'- -',
3
hydrogen, although this is not common. Thus GHO = 1.0342 kmol/m •
The densit), of oil is given as 35.3° API. This corresponds to 141.5/(35.3
3 s
+ 131.5) = 0.8483 g/cm or 848.3 kg/m . The thermal expansion of this
6
oil is 1.49 at 375°C according to page 143 of Maxwel!'s data book. Thus
the density at reaction temperature is 848.3/1.49 = 569.3 kg/ms = PLo
This figure may be used as a constant because it does not vary signifi-
cantly in the temperature range of the reactor. Howeyer the gas demit)·
does vary with conversion and should be expressed by the function:
p = (273.2 P122.711 T)(2.016(1. - Q1X 1 - Q2X2 - QgXg -Q4X4 - Q;x;)

+ 34.032 QIXl + 18.016 Q2X2 +
•
16.043 Q.~X3 + 5.6773 Q4x.d
where •
QI = (4.0% S/IOO)(670·kg oillkmol)/(32.066 kg .s/kmol).

(14.946 kmol H2 available/kmol oil)
If all the sulfur would react, it would involve QI fraction of the initial
. ---,-.
.
~---~>----~
'>,.--'-
"" _.. .
PROCESS DESIGN OF TRICKLE-BED REACTORS 205 .
•
• •
•
H 2 • Similarly. if all oxygen in the oil would react with H 2 • it would involve .
Q2 fraction of the initial H 2 , ete.
Q2 = (% 0:/100)(670 kg oillkmol)(l.O kmol H:/katom 0)/(16.0 kg ~
O/katom)( 14.946 kmol H2 ayailable/kmol oil)
Q:l = (0.35 % 1\;/100)(670 kg oil/kmol)( 1.5 kmol H 2/katom f\)/( 14.0 11 kg
N/katom)(l4.946 kmol H2 available/kmol oil)
We will assume that every hydrocarbon mole is hydrocrackable.
l
Q4 = (kmol H:/kmol oil)(22.4l4 m:l/kmol)/(0.5 m: H/kg oil)(670 kg/kmol)
= 0.0669
Q'> = Br no.l159.832)(0.01)(670 kg/mol)(22A14 m:' /kmol)/(14.946 kmol
H2 available/kmol oil)
Reynolds m'mbers are calculated as follows:
and
Here dp is the diameter of a sphere that has the same outside surface as
the catalyst pellet we use. The surface of the square cylinder pellet is
271"1"2 + (21")(271"1") = 671"1"2. When r = 0.0025 m, the surface area is
•
0.00011781 m "'hich equals the surface of the sphere, 471"r~. Then r., =
2
(0.000117811471")0.5 = 0.0030618, and thus dj, = 0.00612 m.

Viscosity of hydrogen at 375°C = 0.015 cp = 0.000 IS g/(cm's) = 0.000015
kg/(m·s). (See Chemical Engineers' Handbook/ Fp. 3-21.)
Viscosity of oil = 0.0021 g/(cm's) = 0.00021 g/(m·s). (See page 163 of
6
MaxweIl's book. ) •
~,~
, ~
= =
, ~
2
GL (9.3339 kg oills)/( l. 767 m ) 5.2819 kg/(m2·s)
G = (S.2819 kg/m2·s)(0.045 kg H2/kg oil) = 0.2377 kg/(m2·s) •
Rec = (0.00612 m)(0.2377 kg/m2·s)/[0.00001S kg/(m's)] = 96.98

ReL = (0.00612 m)(S.2819 kg/m2·s)/[0.00021 kg/Cm's)] = 153.93
In order to calculate the linear velocities u(; and UL in the reactor, we
must first calculate the phase fractions E(; and El.'
3
Liquid flow = (9.3339 kg/s)/(569.3 kg/m:l) = 0.016395 m /s
3
Gas flow = (9.3339 kg/s)(O.S m /kg)(648.2 K)(1.01325 bars)/
•
273.2 K . S5.0 bars = 0.20399 m%
The void fraction is ·assumed to be E = 0.36. Thus EL + Ec = 0.36.
Equation (6-16) is used to estimate El.'
-
-1/3
.
•
206 .CATALYTIC REACTOR DESIGN
,
where Re = 153.93
d = dp = 0.00612 m
J.LL = 0.00021 kg/(m's)
PL = 569.3 kg/ms
2
g = 9.807 m/s
EL = O. ~0833 = 0.208
Thus Eo = 0.36 - 0.208 = 0.152
Now we can calculate UG and UL at the inlet:

3
0.20399 m /s ="'_ /
UG = (1.767 m 2)(0.152) 0./;)95 m s
3
_ 0.016395 m /s _ 00 6 /
UL - (1.767 m2)(O.208) - . 44 m s
We can also calculate the residence times of the gas and the IUfuid in the
bed:
3 •
= (16.801 m )(0.152) = 12. 19 s •
OG 0.20399 m3/s 5
3
e = (16.801 m )(0.208) = 213 15 = 3.5525 .
L 0.016395 m3/s . s mm
The specifu; heat of the oil is assumed to be constant and equal to 3.3095 •
kJ/(kg· K). However, the specific heat of the gas is a function of gas com-
position and will change with conversion. We need numerical values of
the specific heats of water, H 2 , H 2S, NHs, and CH 4 :
cp (H 2 0) = 34.401 + 0.000628 T + 1.34 X 10-<1 T2
c/H 2 ) = 27.698 + 0.003389 T
cp(H 2S) = 30.1248 + 0.01506 T
cp(KH 3 ) == 28.0328 + 0.02636 T
cpCCH 4 ) = 22.343 + 0.04812 T
•
where T is absolute temperature in kelvins and other dimensions are

given in kilojoules per"kilomole per Kelvin.
cp = cp(H 2 ) (1. - QIXI - (bX2 - Qsxs - Q4X4 - Q;xs) + cp(H 2S)Qlx I/2 .
+ cp(H 20) (bX2 + cp(NHs)( 1I3)Qs x s + cp(CH 4 )Q4 X 4
•
PROCESS DESIGN OF TRICKLE-BED REACTORS
•
There are several ways of computing the effectiveness factor of the
trickle-bed reactor, none of w4ich appears to be rigorous and fully con-
vincing. In view of this uncertainty, several methods will be used to
compute 1] and results will be compared.
The value 1] = 0.4 was assumed for Cecil et al.'s' catalyst with E =
41,000 kcaIlkmol, or 171,544 kJ/kmol.
One method of calculating 1] can be derived from the method of
8
Henry and Gilbert. For a first-order reaction, one can write the follow-
ing expression for the apparent rate constant:
LHSV I - Xl.O
kapp = In
Er
- I - XLF
where the sUbscript LF means the final value of the liquid-phase reaction
and the subscript app means apparent.
From the definitiqn
(7-45)
one can calculate
1] = LHSV In 1 - XLO
(7-46)
EL k 1- XLF
where XLF = 0.65 and XLO = 0 .

The liquid hourly space velocity (LHSV) can be calculated from the
WHSV, 2000 kg/(m3 . h), and the oil density at ambient temperature,
3
PLO = 843.3 kg/m :
LHSV = (2000 kg/m3 . h)/(848.3 kg/m3) = 2.3577 h- 1

I
= 2.358 h- In 1 _ 11.901
1] 0.208 k 1 - 0.65 - k
Here we must use the hourly k value
15
k = 1.99 X 10 exp[·-I71,500/(8.314 x 648.2)] = 29.7841
•
Thus
- (11.901129.7841) = 0.3996
•
,
,
Another method of calculating the effectiveness factor in trickle-bed

reactors, which uses the Th~e1e modulus 'Plb has been proposed by Sat-
9
terfield, Ma, and Sherwood as follows:
tanh 'PH I k Pp CL
7]= 'PH = - (7-47)
'PH a D lleff 3600
where D~leff = effective diffusion coefficient = D" e'lT, rm /s 2
J
k = intrinsic reaction rate constant = 29.7841 h-
Pp - particle density, g/cm 3
e' = porosity of catalyst == 0.60, dimensionless
'T = tortuositv• factor = 3.9, dimensionless
CL - molar concentration of reactant in liqu:d phase
= c· Cw = 0.7102 C .
a - ratio of external surface area of catalyst particle to
volume = 12.0
2
DH = molecular diffusion coefficient for hydrogen, cm /s
The calculation of 7] must be made in the cgs system in order to avoid

excessively large numbers in computing tanh 'fJ1I' '
The particle density can be calculated from the relation:
3 3
Pp = PB/(l - e) = 0.95 g/cm /(1 - 0.36) = 1.484 g/cm
'O
For estimating
•
DH Wilke and Chang have proposed:
"-, .
T(XM ) v·,
DH = 7.4 x 10- 10
o~ - cm /s 2
(7-48)
fJ.. Vb '.
where T == absolute reaction temperature = 648.2 K

X = an empirical "association parameter" of the liquid, taken
as 1.0 for petroleum oils
AIL = molecular ,,'eight of the oil = 670
= viscosity of the liquid at reaction temperature = 0.0021
•
pOise
3
, Vb = molar volume of diffusing solute, 3.7 cm /(g-mol) [ob-
tained. from Kopp', law (p. 16, Satterfield's bookll)]
DH = 7.4 X IO-H~ (648.2)(670)'"/(0.0021)(3.7°. ) == 0.002697 cm /s
6 2
q 'J
D Heff = (0.002697 cm-/s)(0.6)/3.9 = 0.0004149 cm-Is
•
•
1 (29.7841)(1.484)(0.7102 C,) V2 ~ r;;-
<PH = - = 1.5281 vC,
3 (0.0004.149)(3600)
•
The value C = 1.0 can be assumed at the start of the reaction, i.e., at
T
the inlet.
tanh <PH - 0.91

TJ= - = 0.595
1.5281
Now we can compare the three numbers we have:
According to Cecil et al.
TJ = 0.4
According to Henry and Gilbert
TJ = 0.3996
According to Satterfield et al.
TJ = 0.595
We will use TJ = 0.4.
The Computer Program RDMOT4

The computer prograI'n RDMOT4, which was developed to solve the
plug-flow trickle-bed problem will now be explained. Figure 7-3 shows
a block diagram of the RDMOT4 program and Fig. 7-4 lists the defi-
nitions of symbols used in pr?grams RDMOT4 and RDMOT3.
Figure 7-5 isa listing of the RDMOT4 Fortran program. Like RDMOTI,
RDMOT4 is designed for a multibed reactor with intermediate gas quench.
The integration of the ODEs is stopped when the temperature exceeds
a preset value TRMAX; the amount of hydrogen gas needed to quench
the reaction fluids from TRMAX to the inlet temperature is calculated;
this amount of hydrogen is added to the reaction mix; and the integration
of ODEs is continued for a second bed. Variables such as Z, YI, Y2, are
saved at the end of each bed in form of dummy variables called SAVEZ,
SAVEY1, SAVEY2, and reconvened to the actual v;lriables at the staj't
of the new bed, A DO loop (labeled 5) repeats bed calculations up to a
bed number of IBED. -It turned out that onlv, two beds were needed.
An equit1aleuce statement establishes convertibility between variables
of the main program and those of the FUNCTION RUl\GE. Input data
•
•
•
DIMENSION
Y(5). F(5) L.. WRITE TABLE
HEADINGS
7 :3 - ICOUNT =ICOUNT + I
CALCULATE 11.T YES<TR>TRMA

INITIALIZE
QUENCH WRITE ZZ
SAVE1 Y(I) •...• YI4).T CALCULATE
SAVEYI • T ZZ
SAVEY2 / \
SAVEY:3
SAVEY4 >YES
SAVEY5 K=RUNGE 2} >4983
REAL. .. >
COUNT
I YES<
IFREQ
EQUIVALENCE Y(4~ES Y(4)'O~
(y (1) .CR)
(Y(2).CRN)
(Y{3I,CRHY) 'f
<K/l
YES
WRITE ZZ
(Y(4).CRHC)
(Y (5) TR) ICOUNT=OJ
/REAO INPUT7
CR<O.OOI >YES -
6
CALCULATE CALCULATE •
DATA NOT F( I )•...• F(5)
FUNCTION OF WRITE 11
CR.CRN •...•TR
.
.
WRITE TITLE WRITE 11 4 WRITE END

TO OUTPUT OF REACTOR
STATEMENT
LWRITE-NAMEUST 7 ~WRIT~8EO
END H AOING
7 TITLE
CALCULATE
,. CALCULATE GAS
GAS COMPOSITION COMPOSITION
00 5 J-i.18EO + QUENCH
/WRITEBE07 /WRITE QUENCH ~WRITE GAS

COMPOSITION
7
TlTlf L..WRITE GAS 7
INITIALIZE Z. COMPOSITION /
Y{II,Y(2) •...Y{51 END
I COUNT SAVE Z. Y(I J•...•Y(5J ./
,. CALCULATE
I • •
.
CONTINUE
"-
,\5
COEFFICIENTS
FUNCTION OF
CR •...• TR
L
FIG. 7-3 Block diagram of the RDMOT4 computer program for designing
commercial trickle-bed reactors.
are read in and a number of quantities are computed that are inde-
pendent of concentrations and temperature.
The titles of the output are printed, and the input data are printed
as a name list.
Concentration and temperature variables are then initialized and'
quantities that are functions of these variables are computed. Values at .
the inlet of the bed are printed, and FUr-.-CTIO:\ RUNGE is then called
to simultaneously integrate the ODEs for mass and heat. A number of
safety statements are used for each variable. For example, no concen-
tration is permit\.ed to exceed unity, and the concentration is set to zero
•
DEfINITION Of SY8DOLS fOR PROGRA8S RDsaT] AND RDBOT4
A CATALYST 8ASS-TRANSFER SORPACE AREA/OHIT YOL08E, l/B •

AA SOBDIAGONAL ARRAY IN SUBROUTINE TIIDAG
AC CROSS-SECTIONAL AREA OF REAC~OR, 8**2
All ABBOHIA "OL FRlCTICN IN'CAS PHASE, DIBENSIORLESS
A/lIIF ftOLlR FLOW OF AftftONLl, K80L/5
Al fREQUENCY FACTOR OF BElCTIOlll
A3 fREQUENCY fACTOR OF REACTICiN 3
&4 FREQUENC! fACTOR OF REACTICN 4
A5 fREQUENCY FACTOF OF REACTION 5
B DIAGONAL ARiAf IN SU5ROOTIHE TRlDAG
Bl, 83, B4, B5 D~ftftY YARIABLES IH RDftOT3
BET! YARIABLE IN SUBRCUTINE TRltAG
BBNO BROIIINE N~IIBER OF "EED
C SUPERDIAGONAL ABRAl IN SUBROUTINE TRIDAG
Cl1, e121, C122, e123, e124, C125, e13, e21, C22, C23, C24
COEFFICIENTS IN TRIDIAGONAL SYSTEft, IN RDlle!)
CC1, CC3, CC4, CCS DUIIIIY YARIABLES IN RD80T]
CHC 1I0LA11 CONCENTRATIC,N OF UIISATiJRATED HYDROCUilONS,KIIOL/~."3
CHCS CRC ON CATALYST SURFACE, KftOL/ft .... 3
CSCO INLET VALUE OF CHC, KNOL/N •• )
CRIS IIOLAR CONCENTRATION Of BYDROCRACKABLE HYD50CARBONS
ON CATALY3T SURFACE, KIIOl/II •• 3
CRYO INLET YhLUE OF CHY, KSOL/S*.)
CHQ IIETP.ANE 80L FRAC~ICN IN GAS PHASE, DlftENSICSLESS
CHllftl' ftOLAB FLOW 01' ~ETHANE, K~OL/S
CLO IIiLET CONCEIITRlTION Of SULPUR IN LIQU1& PHASE, "!lOL/II** 3
CNS CN ON CATALYST SURfACE, K"OL/ft •• )
CNO INLET VALUE OF CN , KSOL/ft**3
CP SPECIPIC HEAT OP GAS, ItJ/KG.K
CPCH4 SPECIFIC HEAT OP !lETHAME, KJ/KG.K
CP H2 S PECIrIC HEAT 0 F 82 , KJ/KG. K
CPH2S SPECIFIC HEAT OF H2S, KJ/KG.K
CPL SPECIFIC BEAT OF LIQUID, KJ/KG.K
CPNH3 SPECI.I'IC HEAT OF RH3, IJ/KG. It
CR REDUCED eOL CONCENTRATION OF SULFUB 1ft LltUIO PHASE
CSHC REDOCED 80L.COIICN.OF ~NSATURATED HYDROCARIICfiS
CRAY REDUCED IIOL.CONCN.OF HYDROCR~CKABLE HYDROCARBONS
CRN REDOCED 80L.COIICN.OF CO!lPDS. CONTG. EACH CNE ATOI! OF N
CS CONCENTRATION Of SULFOR ON CATALYST SORfACE, KIIOL//I •• 3
D RIGHT-HAND SIDE ARRAY IN SUBROUTINE TRItAG
DAB DAIIIOEHLEB NU!BER POR HEAT, DI~ENSIOBLESS
DAl!l,DAI!3,DAft4,DAII5 DAIIKOEHLER jU8BER poa "ASS, POR REACTIOIS
1, 3, 4, AND 5, RESPECTIVELY, DlftENSIC5LESS
DELTAZ LONGITUDINAL INCRE!!ENT OR STEPSIZE = ZT/ (DP.") (RDIIOT))
OPTS DERIVATIVE OF MS IN NEIITOR-RAPHSOR ITERATION
OH TOTAL REACTION BEAT, KJ/K"OL
DHl HEAT OF REACTION 1, KJ/K80L
DH3 HEAT OP REACTION 3. KJ/KftOL
DHII HEAT OF REACTION 11, KJ/K80L
OHS HEAT OF REAeTIOH 5, KJ/K80L
DP CATALYST PARTICLE DIlftETER. 8
DT INTERNAL DIA8ETER OF REACTOR, "
EPFl EFFECTIVENESS FACTCR OF RIACTIOS 1
EPS VOID FRACTION, DlftEKSIOHLESS
EPSG GAS PHISE FRACTION, DlftEBSIONLESS
EPSL LIQUID PHASE FRACTION , DlftENSIOJLESS
El ACTIVATION ENERGY Fo.a REACTION 1, KJ/KliOL
E3 ACTIVATION ENERGY FOR REACTION 3, KJ/K8CL
Ell ACTIVATION ENERGY fOR REACTION 4, KJ/K~OL
ES ACTIVATION ENERGY FOR REACTION 5, KJ/KecL
F DERIVATIVE IN RDIIOT/!
PEED OIL PEED, KG/S
FTS FUNCTION OF TSI IN NEWTON-RUHSOR ITERATION
GAM/IA VARIABLE IN SUBROU1INE TRIDAG
Ci- /lASS FLOW RATE, ~G OIL/S.8 •• 2
H STEPSIZE IN PLUG-PLOW REACTOR (RDftOTII)
BI!f 80LAR PLOY OF HYQBOGEH, KIIOL/S
FIG. 7·4 Definition of symbols for the programs RDMOT3 and RDMOT4.
211
•
HaIL HYDROGEl-Ta-OIL BA1Z0,ft**3CITP)/IG
BTe HEAT TRAISFEB COEFFrCXEIT. KJ/B**2.S.1 •
HYD HYDROGEN BOL F8ACTIOI ra GAS PHASE, DIBERSIOHLESS
82S BOL l'IACTIOII OP IIID£OGEI SULFl:DE XII GAS PHlSE •
H2SftP BOLAR FLOW OP HYDROGEN SULPIDE, KBOL/S
I SUBSCRIPT = LORGITUDtRAL IUBBER OP IRCREftEIT DELTAZ
ICOUNT COUlTER fOR PUHCTrOI BUNGE (RD8014)
IF HUft8BR OF EOUAT10IS IH SUBROUTINE TRIDlG
IBED . HUBBER OF BEDS la BDaOT4
IFRE~ PREQUERC! OP PRIITIIG IN ROBOT4
IPPl DUftft! VARIlBLE la SUBROUTINE TRIUlG
ITER TEST FOR TRID1G ITEl!lTIOII = TRUE all fALSE
KC ftASS TRAIISPER COEPPICIEHT PROft LIQ. TO CAT. SURFACE,a/s
Kl. K3, K4. K5 RATE CONSTAITS OP REACTIONS 1. 3. 4. AHD 5, RESP.
L LAST EQUATION 11 SUBROUTINE lBIDAG
LAST VARIABLE IR SUBROUT1RE TRIDIG
B WftllER OP STEPS 1:1 BDftOT3
"WL ftOLECULAB WEIGHT OF OIL fEED
aITRO ~ OF HITBOGEK BY aEIGHT III FEED
HalTER IIUftBER OF TRIDAG ITERATICNS, COUNTER,DIBENSIOHLESS
P PRESSURE, BAR
PEHA2 PECLET KUBBER FOB 2-PHASE HEAT TRANSFER, AXIAL DISPERSIO"
PEIIU PECLEr HUIIBER FOil IIASS , AXIAL DISP1':RSIOII. LIQ. PRASE
PHI DUftftY VARIABLE III FUHCTICR RUSGE IN RO~OT4
Q1 FRACTIOII OF R2 COHSUBEO AT COIIPLETE REACTICN OF SULPUR
Q3 FRACTION OF 82 COHSUftfD IT COIIPLETE REACTION OF HITROGEN
04 FRACTION OF 82 CONSURED AT COl!2LETE B!DBOCRACKING REACTION
Q5 FRACTIO" OF H2 coaSUIIED AT CO~2LETE SATURATIOII REACTION
RG GAS CONSTANT = 8.314 KJ/KftOL.K
RHO DENSITY OF GAS PHASE, KG/II •• 3
RBOL DENSrry OF LIQUID PHASE. KG/M*.3
RIIU VISCOSITY OF LIQUID. PAS
Bl RATE OF BEACTIOH 1, KIIOL/S.II •• 3
B3 RATE OP REACTION 3, KIIOL/S.II*.3
B4 RATE OF BEACTION 4, KRO!./S_ft U 3
B5 RATE OF BEACTION 5, K!!OL/S. ft**3
S WEIGHT " 01' SUL FUR IN PEED
SAVEf1,SA VEY3 ,SA VEIII ,SAn;Y5,SAVEZ DUlliiY v ARIA ELES IN RDflOTII
SIG"A DUII"Y VARIABLE
.
18 PLUG-FLOW
- REACTOR -IH CALCULATIONG
HEAT BALANCE ODE
SIGIIAl DUIIIIY VARIABLE III NEWTON-RAPHSCN ITERATION IN LAB REACTOR
SIGMA2 DOIIIIY VARIABLE IH BEiTOH-RAPHSON ITERATION IN LAB REACTOR
SIGBA3 DUII~Y VARIABLE lH CALCULATING tA8(1) IH LAB REACTOR
SIGIIAD DURRY VARIABLE 11 CALCULATING F(5) IN LAB REACTOR
SOli SUII OF Gis 1I0LlR FLOiS. KIIOL/S
T ABSOLOTE TEIIPERATUBE, K
.
• .
•
TB REDUCED ABSOLUTE BULK TEIIPERATUBE =T/TO ,DIIIEIISICHLESS
TRX UNK"OiR REDUCED ABSOLUTE BULK TE~PEBATURE.DlftEHSIONLESS
TS ABSOLUTE CATALYST SURFACE TEftPERATURE. K
TSI _ DUIIIIY VARUBLE FOR TS (I)
TO ABSOLUTE TEnPEIIATUIlE AT INLE'!, K
U SUPERFICIAL GAS VELOCITY, ft/S
UL SUPERFICIAL LIQUID VELOCITI, "IS
V SOLUTION VECTOR IN SUBROUTINE TRIDAG,
Yl,Y3,Y4,YS INPUT VARIABLES IN FUNCTION RUNGE
Z REDUCED LONGITUDIIAL COORDINATE = ZZ/DP .DI~EHSIOHtESS
ZZ LOKGITUDIII AL COOIRDI"ATE. a
•
FIG. 7-4 Definition of symbols for the programs RDMOT3 and RDMOT4
•
(continued).
when it becomes less than 0.00001 in order to prevent so-called under-

flows, which would terminate computer executions. Similar safety state-
ments are used for deri.rratives. Integration calculations are ended when
the reduced sulfur concentration is decreased below 0.001. For each
reduced concentration the derivative function F(N) is computed; safety
statements are used to prevent these derivatives from becoming positive.
212
•
C
C PROCESS DESIGH OF TRICKLE-BED REACTOR
C FOR •
C PETROLEU~ OIL HIDRODESULFURIZATIOJ
C
C •••• PLUG-FLOil INDUSTRIAL BIACTOB _...
•
C ..... CS = C •• TS = ~ ;I. .......
C
DIIIENSIOJ 1(5) ,F(5)
DATA QUENCH,SAVEZ,SAVEfl,SAVEY2,SAVEY3,SAVEY4,SlVEI5/0.,O.,1.,1.,
1 1.,1 •• 1./
INTEGER RURG E
REAL Kl.K3,K4,K5,3WL,HIT~0,Ql,Q3,Q4,Q5
IQUIVALEHCE (1 P),CR), (1 (2) ,CRN), (1(3) ,CRRt),
1 (Y (") ,ClIHC), (1 (5) ,TR)
C
C •••• DEFINE COEFFICI~N~S WHIC3 ARE NOT FUNCTIONS OF CR OB TH ••••
READ(5,100)1,11.A3,A",A5,BFNO,CPL,DH:,DHJ,£H4,CH5,CP,DT,El,E3,E4,
1 E5,EFF1,EPS.PEED,H,HOIl,H1C,lIWL,NITRO,P,RG,RHCL,BIIU,S,T0,
2 TRlIAX,IBED,lFREQ
1:)0 FOB/UT (n10.3 / 1E10.3 I 7<:10.3/7E10.3;4:;10.3;12,16)
CLO = S * RHOL/3206.4
AC = 3.1"'6 *(Dr/2.)**2
GL = FEED/lC
FPSL = 9.9 • (GL*DP/NIIU) "O.3~3/
1 (DP •• ] " 9.B066 "RROL*"2/(RlIU •• 2»*"O.J33
EISG = EPS - EPSL
UL = GLI (RlIOt • E1'5L)
CNO = 8I1aO*RHOL/1"00.8
ClieO = BIiNO*RHOL/15983.2
CHYO = RHOL/1I11L
NAIIELI STj"JATA/A, A1 ,.\],1.4, AS, AC. BF NO, CLO, CNO, CIIYO ,CBCO ,CPL. DH1,DoD.
1 DH",DH5,DP,DT,E1,E3,Eij,f5,E~f1,EPS,EPSG,EPSL,FEED.H,HOIL,HTC,
2 IBED.IFREQ,~WL,NITP.O,P,RG.RHOL,RIIU,S,SAVEZ,SAVEY1.SAVEY2,SAVEYJ,
3 SAVE14,SAvEr5,TO,TRlIAX,OL
IIRITE(6,1S0)
150 FOR!! AT (1H I, "6X, 2911DESIGN OF TRICKLE-BED REACTOR)
:.IRITE (6, 151)
151 FOR~AI(1~J,55X,11~I~?UT DAT~I
WRITE (6, DATA)
C
DO 5 1=1, IBED
WRITE (6, ~91 I
99 FOR 11 AT (1H1, 20X, 10!lFIXl'~ BE;) , 12)
C
C ..... INITIALIZE Z, r(1), 1(2), YP), Y(41. Y(5), AND ICOUNT ••••
Z = SAVEZ
Y (1) = SAVEYl
Y (2) = SA VEY2
Y (3) = SAVEY]
Y (4) = SAVEY,.
Y (5) = SA VEY5
ICOUNT = 0
C •• _. CALCULATE COEFFICIENTS THAT ARE FU~CTICNS OF CBN AND CRHC ••••
U = (Gt*TO*1.01325/(273.2*EPSG.P))" (80IL- «CliO*(1.-CRN/3.») +
1 (CBeO* p.-CRHC) I/BHOL)
VRITE(6,152)
152 FOBIIAT(tHO.4X,JHZZ=,6I,3HCR=,7X,"HCRB=,6I,5HCRRT=,5I,5RCRHC=,6X,
1 2HT=/lH .3X,5H~ETER,q4X,8HDEGREE K}
C •••• CALL OH THE FODTRTH-ORDER RUNGE-KOTTA PUHCTIOR. __ _
ZZ = '4 • DP
T = 1'0 .. TH
WRITE (6,2001 ZZ,Y(1),Y(2),t(3),1(4),T
2 K=RUNGE(5,T,F.Z,H)
IF(Y(") .LT.O.O) T(")=O.O
C •••• IF K=l CO~PUTe DERIVATIVE VALOE5 ••••
IF (K.NE.l.0) GO TO 3
C •••• IIATERI4L BALANCE• ODE FOR SULFUR ••••
IF{CR.GT.l.0) CR=1.0 ~
IF(CR.LT.O.001) GO TO 6
Kl=Al*EX~(-El/(RG*TO*TR)
FIG. 7-5 Fortran program RDMOT4 for designing a plug·flow industrial· size
trickle·bed reactor for petroleum oil hydrodesulfurization.
213
• •
f(1,= -EFF1.K1.DP*Ci/UL
IF(F(1).GT.0.) F(1)=0.0
C •••• aATERI~L B1L1RCE ODE YOH RITiOGEN••••
IF(CRS.CT.l.0) CRII=1.0 •
IF (CRN.LT.a.00001, CBR=O.O
KJ=13* EIP (-El/ (RG*TO*TR).,
F(2) = -EFF1*K3*OP*CRN/UL
IF (F(2).GT.0~O) F(2)=0.0
•
c •••• 51TERI1L BALANCE oDe FOR HYDROCF.ACKABLES ••••
IF{CRHY.GT.l.C, C~H!=1.0
IF(CRHY.LT.0.OC001) CRHY=O.O
K4= A4* EIP {- E4/ (RC*TO.TR)}
F (3) = -EfF l*KiI*DP*CilHY/UL
IF (F(J).GT.J.O) P(3)=0.0
C •••• MATERIAL BALAfiCE ODE FOR UNSA!URA1ES ••••
IF(CRHC.G!.1.0) Cl!HC=1.0
IF(CRHC.LT.0.00001) CR!lC=J.O
K5=AS*EI? (-E5/ (HG*TO*TH)
F(4)= -EfPl*K5*OP*CRHC/~L
IF (F (4) .::1.0.0, F(II) =().O
C •••• UEAT BALANCE UDE ••••
E1= EPfl*Kl*CLO*Cn
R3= Effl*K3*CNO*CRN
H4= EfFl*KII*CHYO*CRHY
RS= EFfl*KS*CIlCO*CRHC
SIGil! = PH1*R 1) • (01l3*B)) • (OH4*li4) • (DilS.RS)
C •••• CALC'JLATION OF GAS DENSITY ll~O ••••
Ql = 2.0a6S6E-OSO'SO'r,WL
Q3 = 7.16304E-05*~ITaO.~Iil.
~1I = 22.414/(aOIL*I!WL)
05 = 9.38276E-05*aRNOO'~RL
aHO= 12.02S*P/{TRO'TO)*(2.016*(1.-(C1O'(1.-CR» -
1 (Q3*(1.-CRII») - (Q4*(1.-CRHY) - (Q5*(1.-CRAC)) +
2 (3~.032*Q1O'(1.-CR)) + ('6.Cq)*Q)* (t.-CRN)) +
] (S.6773*Q4* p.-CRHY)
C •••• CALC"LATIO~ OF TUE S?ECIFIC HEAl C~ Of REACTING GAS "IX ••••
CPH2 - 27.6Qa + (;).001J89* T~ * lR)
. C?C12S= JO.124S • (0.01506 * 10 * TB)
CPcaq= 22. )~3 + (0.04812 • TO • !Il)
- -
CPIIH]= 2a.0328 • (0.02636 * TO • IF)
Ct'= ;:PHZ*(1.-Q1O'(1.-CR) -Q3*(1.-CEN)-;!4* (l.-CRH!) -;;5* (t.-CRRC) •
1 (CPIl2S*Ql*(1.-CR)/2.0)' (CfNII3*C3*(1.-CEN)/3.0) +
2 (CPCH~*Q4*(1.-CEHY)
f:S) = SIGI'IA*OP*EPSL/(TJ*«U'SG-liHC-CP*U) • (E?SLO'RHOL*CPL*OL»))
IF(F(S).LT.O.O) F(5)=O.0
GO TO 2
3 ICOUNT = ICOUNT + 1
C •••• IT TR :;REA7E ::-HAII TR~AI, EliD TUE BED ••••
IF (Tli .• GT. TH"AX) GO TO 4
C • ••• .rp ,,~ACTOR L::!1GTH EXCEEas 10 ~ETERS, =:NiJ CUCULATIONS .....
• = '7'0
~ • - -R
•
zz = Z * 1> P
If(Z.GT.Q98J.O) GO TO 0
If (ICOUNT.NE.IFREQ) GO TO 2
WRITE(6,200) ZZ,Y(1),Y(ZJ,Y(3J,I(4J.T
200 fOB:!A! (18 ,lP6El0.3)
ICO O!iT = J
GO TO 2
C • • •• E NJ 0 F BE 0 ......
" WRITE (6,2\)0) 2Z,1(1) ,Y(2) ,1(3) ,1{1I) ,T
WRITE (o,;:Ol) I
201 FOoMA: (lA ,SX,11AilND Of B£ll .12)
C •••• CO~P;)TE GAS C(,WOSITICN AND QUENCH AT !lED OUTLET ••••
EMF =(H~D*O.5/22.4'Q)*(1.-Ql*(1.-CR) - ;)3* {1.-CllNl -
1 Q4*(1.-CRHY) - :)5*(1.-CRHCii
H2SMF - FEE)*S*(1.-CR)/32J6.6
AI!~I' = FEED*N1TliO*(1.-CRN)/1400.8
CH4~F = FEED*(1.-CEHY)/~WL
SU~ = B"F + H2S~f • A~l!f + CH4~1'
QUENCH; (FEED*CPL/~i/L) + (SU!I*CP») * (TR*TO - TO) / (29. 895 *
1 (TO-298.2»
WHTE (6. 202) QUE Nca
202 FOHHT(1HO, 5I,9HQUEIICR = ,1'10.5,78 KIIOL/S)
WRITE (6. 230)
FIG. 7-5 Fortran program RDMOT4 for designing a plug.flow industrial·size
trickle-bed reactor for petroleum oil hydrodesulfurization (continued).
214
•
230 FOBft1T(1aO.1SX.29HGAS CG"PCSITIOR. "OL FBACTIOR/1BO.9X.
1 8HHIDaOGER,SX,lBB2S.7X.lBMHl.7X,3BCHfll
BID = B"F /50"
H2S = B2SIIF/SOII
A" = AII"F /SO"
CHII = CHilli F/StJ"
iRITE{6,2311 HID.82S. All. CHII
231 FOI8AT(1HO, 8I,F8.5,2X,F8.S,2I,F8.S,2X,F8.51
SlYEZ '" Z
SAVEtl: Y(lI
SlYET2= 1(2)
51 VE13= I PI
SAVEIQ= 1(41
S 51 VE IS = 1. 0
C 5 CORTI!IUE
C USE THE TOP -5" IF THE REV BED SHOULD ST1~T AT TB=1.
C USE THE BOTTO" "S" IP THE HEll BED SHOULD SlABT 11 la=IBPtJT VALOE.
C •••• END OF REACTOR ••••
6 IIElTE (6, 200) ZZ, 1(1). 1(2), Y (31, Y (11). T
IlRITE (6, 2031
203 FOBIIAT(1H ,5X.1<IBEHD Of' REACTOR)
C •••• CO:'lP'lTE GAS COIIPOS I::IOH AT REACIO!! ~HO ••••
HH!' = (!'EEO"0.S/22.fl14) "(1.-Q1"(1.-Cll) - ,,3"{1.-CRN) -
1 QfI"(1.-CRHYI - Q5"(1.-CRHC))
H2S~F = FEEO"S"(1.-Clll/3206.6
A~~P = PEED"NITRO"(1.-CR~)/1400.9
. CH411F = FEEO*p.-'::RHY) /I:llr.
SU~ = H~F • H2S~P • A~~F • C3f1HF
HYD = H3 P/SU~
H2S = H2S~f/SUII
All = 1/!!1F/SIJ!I
CHq = CH4'P/SO!l
lIRITE(6, 230)
IIRIT&(6, 231) HYD, 625, AM, Cl14
STOP
END
C
FIIIICTIOH RUHG(; (H. Y. F. Z, ill
lilT EGEB RUNGE
DIIIENSION PRI (50), SAVEY (SO), Y (N), F(N)
I: A'U 11/0/
~ = • 1.
~
GO TO (1.2,3,4,S), ~
C •••• PASS 1 ••••
1 RUIIGE = 1
RETUliN
C •••• PASS 2 ••••
, 2 DO 22 .1 = 1, 11
SAVE!(.1) = Y(.1)
PHI (J) = F (.1)
22 1(.1) = SA VEY (.1) • 0.5 .. H • F (.1)
Z = Z + 0.5 .. H
RUNGE = 1
RETURN
C • " . PASS ) ••••
3 DO 33 .1 = 1, N
PHI(J) = PHI (.1) + 2.0 .. F(J)
33 Y(J) = S1VEY(J). + 0.5 .. H .. F{J)
50llGE = 1
RETORN
c •••• PASS 4 ••••
ij DO 411 .1 = 1, N
PRI(.1) = PRI(.1) • 2.0 .. F(J)
114 Y (JI = SAVEY P) + H .. 1'(.1)
Z = Z + 0.5 .. H
RONGE; = 1
RETORN
C •••• PASS 5 ••••
5 DO 55 .1 = 1, R •
55 1(.1) = SAVE!(.1) • (PHI (J) + I' (.1» .. H/6.0
I! = 0
RIINGE = 0
RETUIl!!
HD
FIG. 7-5 Fortran progtalD RDMOT4 for designing a plug·flow industrial· size
trickle·bed reactor for petroleum oil hydrodesulfuri z 2tion (continued).
215
•
2t6 CATALYTIC REACTOR DESIGN
,
1.200£+03 2.800£+04 1.800£+03 2.500£+15 1.000£+03 5.000£+00 3.310£+00
2.512£+05 6.485£+04 4.100B+04 1.255£+05 0.602£-02 1.5 £+00 8.206£+04
7.206£+04 2.435£+05 4.686£+04 0.4 £+00 0.36 £+00 9.334£+00 0.2 £+00
0.5 B+OO 1.296£+00 ~.7 £+02 0.35 £+00 5.5 £+01 6.314£+00 5.693£+02
0.21 £-.03 11.0 E+OO 6.482E+02 1.C7 £+00
5 500
A= 120(}.0 CHCO=OI780 £4=243500.0 IJ2ED=5 SAVEYI = 1.0

Al =28000.0 CPL=3.3100 E5~46860." IFREQ=500 S..WEY2= 1.0
A3=1800.0 DHI=251200.0 EFFI=OA MWL=670.0 SAVEY3= 1.0
A4=0.25£+16 DH3=64850.0 £PS = 0.360 !\ITRO=0.350 SAVEY4= 1.0
A5= 1000.0 D"',,=4JOOO.il ~PSG=O.14856 P=55.0 SAVEY5 = 1.0
AC = 1. 7671 UH5 = 125500.0 EPSL = 0.2114 RG = 8.3140 TO=648.2
BR:\O=5.0 DP=O.602E-02 FEED=9.3340 RHOL=569.30 TRMAX = 1.07
CLO=O.iI02 DT=1.50 H=0.2 RMU=0.2lOE-03 l'L = 0.439E - 01
C!\O=0.1422 El =82(160.0 HOIL=U.50 S=4.0
CHYO=0.8497 E3 = 72060.0 HTC= 1.2980 SAVEZ=O.O
FIG. 7·6 Input data for computer l'rogram RDMOT4.
In order to integrate the heat ODE, the rates of all reactions and the
density and specific heat of the gas mix are calculated. A safety statement
is used to prevent the heat derivative from becoming negative.
This first part of the DO loop is repeated until the FUNCTION
RUNGE completes its five passes and all the ODEs are integrated. Be-
cause we do not want the results of every integration step to be printed,
a counter named ICOUNT is used. This counter counts the completed
integration steps. When ICOUNT becomes equal to IFREQ, it prints
the results of the last integration step.
The values of T and ZZ are calculated (see Fig. 7·4 for meaning of
symbols). If the total bed length exceeds a predetermined number such
as 30 m, the reactor calculations are ended (if
. thev, have not been ended
before for some other reason). At each bed end the last results are
printed and then bed end titles are printed. Now the QUENCH is corn·
puted and printed and the gas composition at bed end is calculated and
printed. At the end of the reactor the results are printed and gas corn·
position is calculated and printed.
The input data used in the above program are listed in Fig. 7-6 and
the output data are listed in Fig. 7-7. We see that the first bed reaches
TRMAX in 5.799 m of reactor length. At that point CR 0.5161,
CRN 0.7774, CRHY 0.9776, CRHC 0, and T 693.6 (which equals
420A°C). The gas phase contains only 95.463% H 2 •
The second bed is c2tlculated to a total reactor length of 30 m. How-
eyer, the desig-ner should stop the integration calculations for the second
bed at a desirable CR of 0.35 at ZZ 11.2 m. It can be seen that the two
beds are about equal in length. The interbed cooling can be implemented
according to Fig. 7-2. These results are the solution of the plug-flow
trickle-bed reactor problem.
•
•
•
Laboratory Reactor with Backmixing
An experimental trickle-bed 'reactor that meets Mears' condition of a
l2
back-mixed reactor will be considered here. The condition is
•
20 a d, I Cl)
ZT> n- (6-18)
Bo Cl
where a = I = reaction order

3
C = concentration of key reactant, kmollm
ZT -- total length of reactor bed, m
d, - equivalent spherical diam..:ter of catalyst particle, m
2
= [0.005 + (0.005/2)2]0.5 = 0.00612 m
Subscripts f and 0 denote final and initial, respectiyely.
Cr = Co(l - xf)
where xf is also the desired conversion CoIC, = CulC o( I - xf) = If

(l - Af) = l/(l - 0.65) = 2.857 and Bo = Bodenstein number.
The Bodenstein number, Bo, is a Pedet number based on particle diameter
d, in~ ..ead of dp (see Sec. 6.2). Actually, Eq. (6-18) is a condition for plug-
flow regime. Consequently, the condition for a backmixed reactor would
be an inequality with the opposite sign of that of Eq. (6-18). Let us
calculate the ZT value that separates the plug flow and the backmixed
regimes. Then we have to take Eq. (6-18) as an equality, rather than an
, inequality. In Eq. (6-18), Bo is an indirect function of reactor length ZT,
consequently ZT can be calculated by trial and error by starting with an
assumed ZT' Let us assume that ZT = 1.25 m. Assuming the same length!
diameter ratio used in the plug-flow example, the reactor diameter would
be DT = (1.25/6.3333) = 0.19737, and the bed cross section and total
2 3
volume are Ac = 0.030594 m and V = 0.03824 m , respectively.
3
The oil throughput is (2000 kg/m3 . hr)(0.03824 m ) = 76.486 kg/h
2
CL = (76.486 kg/h)/(3600 x 0.030594) = 0.6944 kg/Cs . m )
2
Gc = (0.6944)(0.045 kg H2/kg oil) = 0.03125 kg/Cs . m )
Rec == (0.00612)(0.03125)/(0.000015) = 12.75
ReL = (0.00612)(0.69445)/(0.00021') == 20.24
•
The Bodenstein number. is really a Peclet number based on a particle
diameter, so we can use Eq. (6-17) to calculate it: -
Bo = 0.034 Re2· 5 lOo.003{Re)c = 0.167

ZT (calculated) = (20)(1)(0.00612)(2.857)/(0.167) = 2.09 m
•
FIXED BED 1
ZZ= CH= CfiN= CRIIY= CBBC= T=

IIETER DEGREE f(
·0.0 1.000E+OO I OOOE+OO 1.000E+00 1.000E+00 6.482£+02
6.020E-01 9.592E-01 9.832E-Ol 9.995P'-01 3.111E-01 6.566E+02
1.2 O"E_O 0 9. 135E- 01 9.o43E-Ol 9.938£-01 1.297£-01 6.623f+02
1.805E+00 8.~50E-Ol 9.43UE-0. 9.978E-01 4.151E-02 6.6688+02
2.407E+OO 8.146E-Ol 9.221L-vl 9.%5£-01 1.2'17E-02 6.70n+02
3.008E+00 7.628E-Ol 8.99lE-J1 9.947l:;-01 J.S21f.-OJ 6.749£-02
3.609£+00 7.102E-Ol 3.750E-Ol 9.925E-Ol 9.321E-04 6.790£+02
4.210E-OO 6.56,E-Cl 8.497£-Jl 9.896E-Ol 2.308E-0'l· 6.8301':+02
4.811£+00 6.0cQ'-Ol 8.233E-Ol 9.A59~-01 5 330E-CS 6.870E+02
5.412E_()0 5.502;:-01 7. IS?E- 01 'l.A12E-Ol 1.146E-OS 0.910E+02
S.199E+00 5.161E-01 7.77H-Ol 9.176E-Ol 0.0 6.936£+02
Efl;) Ol' BED 1
QUENCH = 0.01276 K~OL/S
GAS CO~POSIIIO., ~OL fRAC~ION
HYDROGEN H2S HH) CH'I
0.95463 0.03153 0.00)64 O.CC219
FIG. 7·7 Computer output of program RDMOT4 for designing industrial·size

trickle-bed reactors.
We can repeat this calculation by assuming Zr = 1.5 m and find a cal-

culated value of 1.88 m. The limiting value for Eq. (6-18) must be be-
tween 1.50 and 1.88 m. Any number smaller than this limiting number
would correspond to a backmixed reactor. Hence 1.5 m is a good number
for ZT'
The diameter
- .of
- the bed will be 1.5/6.3333 = 0.197 m; or around 0.2
2 3
m; also,A c = 0.0311416 m ; V = (0.0311416)(1.5) = 0.047123 m • The
3
throughput of oil is (0.047123 m )(2000 kg/m3 . h) = 94.248 kg/h, or
0.02618 kg/so
The reaction conditions are the same as those gi\'en for the plug-flow
reactor.
Throughput of gas = (0.02618 kg/s)(0.045 kg H2/kg oil)
- 0.0011781 kg/s
Volume flow of oil = (0.02618 kg/s)/569.3 kg/m3
= 0.000045986 m'l/s
Volume flow of Hry-
l
_ (0.0011781 kg/s)(22.414 m: /kg-mol)(648.2 K)(1.01325 bars)
- -
(2.016 kg/kmoJ)(55 bars)(273.2 K)
3
- 0.00057252 m ts
2 2
Cc = (0.0011781. kg/s)/(0.031 1416 m ) = 0.03783 kg/(s . m )
2
CL - (0.02618 kg/s)/(0.03114 m') = 0.8407 kg/(s' m )
Rec = (0.00612)(0.03783)/(0.000015) = 15.43

ReL - (0.00612)(0.8407)/(0.00021) = 24.50
PROCESS DES!GN OF TRICKLE-BED REACTORS 219
FIXED BED 2
CR: Cl!!!!: CllHC= .,.-

.-
I!::TEll ilEGRf:E K
5.801E~OO 5.161E-01 7.774E-01 9.776E-Ol 0.0 6.48]£+02
6.402E+00 4.969£-01 7.653£-01 9.772E-Ol 0.0 6.<194£+02
7.C03E+CO 4.778E-Ol 7.532£-01 9.768E-Ol 0.0 6.507l!+02
7.604£+00 4.589E-Ol 7.409E-Ol 9.764P.-Ol 0.0 0.5198_02
S.20SE+00 4.403E-Ol 7.285E-Ol 9.760E-Ol 0.0 6.5311!+02
8.806£+00 4.219E-Ol 7.161E-Ol 9.155E-Ol 0.0 6.544E+02
9.4u7E+OC 4.037E-Ol 7.035E-Ol 9.750£-01 0.0 0.556£+02
1.001E+Ol 3.859£-01 6.908E-Ol 9. H4E-Ol 0.0 0.56n+02
'.061E+Ol 3.684£-01 0.781E-Ol 9.738£-01 0.0 6.581[+02
.1.121::+01 3.512E-Ol 6.653£-')1 9.111E-Ol 0.0 6.593E-02
1.181=:+Cl 3.34"E-Ol 6.52~E-Ol 9.724E-Ol 0.0 6.604£+02
1.241E+Ol 3.180P'-01 6.395E-~1 9.71uf,-01 0.0 6.613E+02
1.3J1E+Ol ).021E-Ol 6.267E-Ol Q.7)8E-Ol 0.0 6.623£-02
1.362E+Ol 2.867E-Ol 6.139E-11 0.09.6~9E-01 6.632E+02
1.422f+Cl 2.71Re-Ol 6.011E-Ol Y.ogOE-Ol 0.0 6.64"+02
1.4S2E.Cl 2.574E-Ol 5.883E-Ol 'l.691E-Ol 0.0 (, .650E+02
1.542£+01 2.434E-Ol 5.756£-01 9.670E-Ol 0.0 6.66JE+02
1.602E+Ol 2.)00E-Ol 5.630E-Ol 'l.659E-Ol 0.0 6.669£+02
1.&62<.+012.'70£-01 5.'04E-Ol 3.6<11:;-010.0 6.678£+02
1.122L~01 2.045f-Ol 5.37'lE-J1 9.0SE-Cl a.\) 0.68SE+02
1.762<:+11 1.n6E-Ol 5.255E-01 9.622~-;;10.:) 6.69U+02
1.842F.+01 1.BOE-01 5.131E-Jl 9.609E-01 0.0 6.697£+02
1.<;on.J1 1.705E-Ol 5.012::-J1 9.515E-01 0.0 6.703£+02
1.~63E.Ol '.601E-Ol 4.S92E-11 'L58H:-01 0.0 (; .709E+02
2.023:;+01 1.S03E-vl ~.71SE-)1 9.5660-01 0.0 6_716E+01
2.J83E+31 1 •• I1E-01 4.',58C:-Ol 'l.5sn:-01 0.0 o.122E+02
2.143E+01 1.321E-01 4.54JE-J1 9.S1~o-01 0.0 0.7:<8<+02
2.20JE+Cl 1.237E-01 4.4)OE-Ol 9.S1a::-C1 0.0 6.734£+02
2.263E+Ol 1.15/E-Ol ".318E-:ll 9.501£-01 0.0 0.737E+02
2.323:'+01 1.0b2E-Ol 4.20n-Ol 9.483E-01 0.0 6. 740~~02
2.38J:i:+ll 1.D1lE-Jl ".102E-:11 9.<l66E-Ol 0.0 6.7"3£+02
2."""E+01 9.4531:-02 3.997E-Ol 9."'+~E-C1 0.0 6.746£+02
2.503E+01 8.82aE-Ol 3.894E-01 'l.429E-Ol 0.0 6.7Q9E+02
2.562E+Ol 8.241E-02 3.193E-Ol 9.~10E-Ol 0.0 6.752£+ 02
2.020E+Ol 7.690E-02 3.694E-Ol 9.191£-01 0.0 6.755E+02
2.679E+)1 7.171E-02 3.597Z-01 <).3I2E-Cl 0.0 6.758£+02
2.738E+Ol 6.685E-02 3.502E-01 9.352~-Ol O.V 6.761E+02
2.797E+01 6.228E-02 3.409E-01 9.332E-01 0.0 6.765E+02
\ 2.855E+01 5.o01E-02 3.318E-Ol 9.312E-Ol 0.0 u.768E~02
•
-". , 2.914£+01 5.401f-02 3.229E-01 9.291E-01 0.0 6. 771E~02
2.973E+Ol 5.027E-02 3.1Q2E-Ol 9.270£-01 0.0 6.772E+02
3.000I+01 4.865E-02 3.103E-Ol 9.260E-01 0.0 6.772£+02
END OF REACTO"
GAS COMPOSITION, ~OL FRACTION

HYDROGEN R2S CH4
0.90338 0.07803 0.0'133 0.OC726

FIG. 7-7 Computer output of progr am RDMOT4 for designing industrial.size
trickle·bed reactors (continued).
Let us calculate the Peelet number Pe mn / according to the following

two correlations:
l3
Sater and Le\"enspiel Pe"",/ 7.58 x 10-: Re~~703 = 0.0718
1
Hochman and Effron 14 5 0 00 1

Pe "",I = 0.034 Re2· 10 . : Rc"
.
= 0.1993
As a conservative measure, we will select the correlation that gives the
smallest Peelet number, namely that of Sater and Levenspiel.
Pe mal = 0.0718.
•
,
No correlations are available for the mixed Peel et number Peila2 for
heat and two-phase flow. Heat Peelet numbers may be estimated by
analogy from mass Peelet numbers. We can assume (for the lack of a
better method) that the two-phase Peelet number is made up of the
Peelet numbers of each phase in the same proportion as the phase frac-
tions. We have no proof of this fact, but it seems like a reasonable
assumption that might not be too far from reality. We can use it in this
book until actual experimental data are available.
Thus (7-49)
There are three correlations for Pe"lIIg:

Sater and Levenspiel l3
Pe "'ilK = 3.4 Re(~(1.t;7 10-0.0026 Re, = 0.469-l
l
DeMaria and White ;;
Hochman and .t:ffron H Pe"lII): = 1.8 Re(~O.7 10 -0.005 Rel = 0.20

Again the smallest number is selected, 0.20, and that gives Pehil2 = 0.4993.
The Computer Program RD1-tfOT3

The !Jackmixed trickle-bed reactor problem can be sol\'ed by using the
Fortran program RDMOT3, developed in Chap. 2, Sec. 2.6, as Case 2
with C, ::F C and T, ::F T for first-order reactions. The \'~rsion of this
program for several reactions in parallel is discussed in Sec. 2.8. The
application of this program to the b~ckmixed trickle-bed reactor problem
is explained below. Figure 7-8 shows a block diagram of the RD~IOT3
program, and Fig. 7-9 is a listing of the program.
First, the concentration and temperature variables, both in the bulk
phase and on the catalyst surface, are dimensioned, as are the reaction
rate constants, reaction rates, Damkohler numbers, reactor lengths. and
the variables of the subroutine TRIDAG. The number of integration
steps 11 is then read in: M = 400.
Bulk-phase concentrations and temperature are initialized b\· means
of a DO loop (labeled 7) from step I to ~I 1. Input data are read in and
quantities independent of concentrations and temperature are calcu-
lated. The titles of the output are printed and the input data are printed
in the for'm of a name list. A DO loop (Iabeled 8) prints reactor lengths
ZZ(I) and TRIDAG coefficients independent of reactor length are cal-
culated. A DO loop (labeled 9) initializes catalyst surface concentrations
by equating them to their respective initial bulk-phase concentrations.
Also, surface temperature is equated to bulk temperature.
A counter called NO ITER is used to count the number of TRIDAG
•
•
iterations. A test called ITER is used to terminate TRIDAG iterations.
A DO loop (Iabeled 10) is used to calculate the TRIDAG coefficients for
the sulfur concentration ODE. Here T5(1) is calculated for each reactor
length increment by a r-:ewton-Raphson iteration, and from that result
other quantities are calculated for the same reactor length increment.
Finally, the coefficients of the Subroutine TRIDAG are computed. All
the calculated values are stored in "dimension" storages.
The boundarv• values are set and subroutine TRIDAG is called. The
reduced sulfur concentrations calculated by TRIDAG are printed. We
select for printing 10 values starting with I = 41 and ending with I = 40 I,
thus pri'lting e\'ery f<>rtieth increment. Again safety statements are used
to make cenain that eR is positive and smaller than 1.0. This type of
computation is repeated for the mass ODEs for nitrogen, hydrocrack-
abies, and unsaturates.
The integration of the heat ODE is basically similal-, except that it
includes the calculation of the density, specific heat, and superficial ve-
locity of the gas mixture.
Thus the RDil.10T3 program successively integrate~ all the ODEs for
the entire reactor length, starting from initial conditions, and then re-
peats this procedure in a series of iterations, each time imprm'ing on
the previous calculations, until the results change less than a given test
value. Our test is applied to TR and the test value is 0.00 l. Onr~ this
test is met, the reactor design results are printed. Finally, the composition
of the gas phase is calculated and printed for the la points along the
reactor length for which concentrations and temperatures arc-printed.
Figu~e 7-10 is a listing of the input data for RDMOT3. Figure 7-11
is the output of RDMOT3: first it lists the input data as a name list; then
it lists the reactor lengths, the concentrations and the temperatures for
the 10 selected points along the reactor length for each successive iter-
ation. To meet the test 11 iterations are needed. Then the definiti\'e
reactor design data are printed and the gas compositions for the 10
• •
pomts are gl\·en.
We can see from the output data that 1.20 111 is an excessi,'e length
for the laboraton. reactor. since CR is decreased to 0.00078i at the end
'
of this reactor. Howe\,er, it is all right to build an experimental reactor

somewhat o\'ersized. The desired cOI1\'ersion of 65% or CR = 0.35 is
reached at about 0.28 m. The reduced temperature TR shoots quickly
above 1.07, which was used as TRr-.IAX in RDMOT4 and le\'e!s off at
l.378. In practice, we- would not bother designing this experimental
reactor as a multibed J;eactor with interbed quench but would rather
wai'lt to see \,'hat happens to temperature. If we want an experimental
reactor \\·jth 65s;,: conversion, h'e would simply build a reactor that is
only 0.28 m long,
,
DIMENSION
VARIABLES SET BOUNDARY
I LOGICAL ITER I
I CONDITIONS
•
CALL
LREAD M 7 TRI OAG
NOITER =0
~ WRITE CR(l)
INITIALIZE BULK 00121=2,1.1

VARIABLES ...J
CALCULA E TS J BY
/READ INPUT / NEWTON - RAPHSON
IrE R ATlO",N,,-_ _
CALCULATE
l CONSTANTS l UlA H
PARAMETERS FROM TS(Jl
NAMELlST
CALCULATE TRIOAG
12
CALCULATE Z.ZZ-' r.:::"~~C~O~E~FFICIENTS
SET BOUNDARY VALUES
/ WRITE TJ{LE Z (11 /
I
CALCULATE CALL
CONSTANTS TRIDAG
CI1.CI3. C21.C23
\
INITIALIZE
SURFACE
VARIABLES LWRITE CRN (j 1 /
NOITER = NOITER +1 - 2(l DO 14 1= 2,.1,4
ITER = *FALSE* CALCULATE TS(!) 8'1'

NEWTON -RAPHSON
I 0010 I=2.M~ ITERATION
CALCULATE TSO) BY ITWULA E ~~HER .

NEWTON-RAPHSON PARAMETERS FROM TS( 11
ITERATION
CALCULATE TRIDAG
CALCULATE OTHER 14 COEFFICIENTS
PARAMETERS FROM
•
. . c TS!l) .J
SET BOUNDARY VALUES
CALCULATE TRIDAG
COEFFICIENTS 10
FIG. 7-8 Block diagram of the RDMOT3 program .
•
,
. SET BOUNDARY
CALL \ VALUES
TRIOAG
/ CALL \
\
TRIDAG
/ WRiTE CRHY (1) 7 L. WRITE TRX(I) 7

DO 16 1-2, M 00301-2,1.1
CALCULATE TS( I)
BY NEWTON-RAPHSON
lTER~TlON YES
ITRY (I) - TR( 01 >0.001
CALCULATE OTHER
PARAMETERS FROM
TS(!) ITER' .TRUE.
CALCULATE TRIDAG
16
COEFFICIENTS
I TR(I)-TRX(I)
SET BOUNDARY
VAlfES _J CONTINUE
.
CALL
TRIDAG YES
20 ITER .AND. NOITER<20
L. WRITE .,.CRHC (J) 7 .....,

DO 18 I ' 2, M / WRITE TITLE 7
I
CALCULATE T~EJ. BY WRITE ZZ (I l. CR(l), CRH(I),
NEWTON - RAPHSON CRHY(IJ,CRHC(I), TRX (ll,
ITERATION TS(I), CS(~
CALCULATE OTHER
PARAMETERS FROM
TS '~)
WRiTE TITLE 7
.
CALCULATE TRIDAG
I~
.
COEFFICIENTS FOR
HEAT
•
DO 231 1-41,401,40
CALCULATE GAS
COMPOSITION
WRITE ZZ (I), GAy

COMPOSITION
"
231 CONTINUE
/
END
FIG. 7-8 Block dia~ram o~

•
"
the RDMOT3 program (continued).
•
C
C PROCESS DESIGN OF TRICKLE-BED REACTOR
C FOR •
C PETROLEOft OIL HYDRODESOLFORIZATION
c
C •• _.CS AND TS SUBSTITUTION SCHEeE 2 ••••
C ..... CS 1I0T = C : 'fS H04f ; 'I _ •••
C
DlftENSIOH CR(401j,CRN(401),CRar(401},CRaC(401),TR{401),
1 CS (401), CNS (401) ,caY S (1101) ,cac 5 (1101) ,'IS (401) ,Kl (401) ,
2 K3 (11 01) ,1\11 (liD 1 ) ,1\5 (liD 1) ,111 (401) , B3 (1I0 I) ,RII (1101) ,liS (401) ,
3 DAe1(401),DA~3(4011,DA~II(q01),DA"S(1I01),DAH(II01),Z(401),
11 ZZ(401)
DI1IE1I510N AA (IIOll,I!(401) ,C(401) ,DCII01I,UI(401)
REAL Kl,K3,K4,K5,l\c,e.L,N1TBO,Ql,Q3,~,Q5
LOGICAL ITER
READ (5,99) ~
S9 fOR~AT (I10)
NOITER = 0
C
C •• __ lH1TIAl.rz;;: CB, CBN, CRHY, CRHC, AND TR ••••
!ll = l! • 1
DO 7 1=1, 111
Ca(I) = 1_
= 1_
Cll N (I)
CBHY(I) = 1.
CRHC(I) = 1.
7 TR(l) = 1.
C
C •••• Df.yIN~ COEFFICI~HTS .HICH ARr HOT fUNCTIONS 01' ca OR TB ••••
REAO(5,100) A,CPL,DH1,DP,DT,El,EPS,fEED,H1C,HOIL,KC,P,PEftAL,PEHA2,
1 RG,R~U,S,TO,OELTAZ,RHOL,Al,EFP1.E3,E4,E5,A3,A4,15.DH3,DHII,OR5,
2 NITRO,6RNO,ftWL
1C~ FOR/IAT (71':13.3/ 7El0.1 /7El0.3/7El0.3/6El0.3)
CLO = 5 ,. R;t)L/3200.lI
le = 3.1416 *(OT/2.) **2
GL = fED/AC
E?SL ~ 3.9 .. (GL*DP/li~11 ."0.313/
1 {DP.*3' 9.3066 *RfiOL**2/ (RI'I1J**2}) "*0. 333
EPSG = EPS - EPSL
IlL • ~L/(RHOL .. EPSL)
CNO = NITRO*RHOL/ll100.8
CilCG - BR:W"RHOL/15963.2
CHYO = 8HOL/l'I\lL
NAl'IELIsr/DATA/~,OELTAZ,A,!1,A3,A4,A5,AC,CLO,CPL,DH1,DH3,DHQ,DH5,
,, 1 ~?,DT,El.E3,E4,E5,E?S,EPSG,EPSL,FEED,HOIL,KC,P,PEl'IAL,PEHA2,RG,
2 3HOL,RMu,3,70,Ul,HTC,
J CIlO,C!lYO ,CRCO
I1RITE(6,150)
150 FORIIAT (1nl,46X,2911DES:::GN OF TRICKLF=-HED REACTOS)
118ITE(6,151)
151 FORIIAT(1HJ,SSX,llHINPUT DATA)
.RITE (6, DA TAl
DO 8 1=1, 111
;JEL = FLOAT (ll
Z (I) = DELTAZ .. DEL
8 ZZ(I)= Z(I) .. OP
C
WRITE(6,210)
210 FOR~lTC1HO,20X,31HI T E SAT I 0 " c Y C L E S)
C
WRITE (6, 197) (<I{I) , 1=41, 401, 110)
197 l'ORIIAT (10RO Z(I) =, lPl0E12.3)
Cll = 1./{PE~'L*DELTlZ*"2)
-
C 13 = Cl1 - (1./DELTlZ)
'FI~. 7-9 Fortran program RDMOT3 for designing a badunixed laboratory-

size trickle-bed reactor for petroleum oil hydrodesulfurization.
224
,
•
C2l = 1./{PEHA2*DELTU"21
C2) = C2l - (l./DELTAZ)
c
C •••• INITIALIZE CS ,CNS, CHrs, CHCS, AND TS .....
DO 9 1=1, 111
CS(I) = CLO
CNS (l) = CNO
curs III : Cl/YO
CHCS (I) = CHCJ
9 'IS(II = TO
C
C •••• CO"?UTE VALUES FOR EACH I-VALUE OF ALL COEFFICIENTS AND FEED
C THEl'l INTO THE ODE'S AND ALSO STORE THEI! IN DIIIEIiSICN STATEIIENTS.
C THE SUBROUTINE TRIDAG U?GRADES THESE COEFFICIENT VALUES AND THE
C O D E ' S llY ITERATIO:1 llNTIL A TEST IS !lET ••••
C
2J NCITEa : NOIT!R + 1
ITER: • F ALS E.
C •••• INTEGRATE flASS ODE FOR SULFUR ••••
DO 10 1=2, ft
C •••• CALCULATI~N OF TS(I) 3Y ~~.TCN-RAPHS~N ITEEATION ••••
21 TSI = 1S(1)
Kl(l): Al*EXi'(-El/(RG*TS(III)
K3 (I) = A 3*U P (-E3/ ('l,,*1S (I) II
K4(I)= A4*EX?(-E~/(RG*TS(III)
K5(I)= AS*EX?(-E5/(RG*TS(I)))
il 1 (I) = E:Fl" 1*0: 1 (I) * CS (11
li3 crI = cFF1*K3 (1) .CNS (I)
R4 (I) = EF!"1*K4 (1) *CH¥S (I)
RS(I)= EfFl*K3{I)*CHCS(I)
SlGMA1= (EFF1*OH1*Kl (I)*CR(I) *CLO /(1.+(EFfl.Kl(l}/(KC*A)I)) +
1 (ZYF1*DH3*K3(I)*CRN(1) .CNO /(1.+(EFF1*K3(I)/(KC*A)) +
2 (EFF1*;)HU*K4(II*CilHY(:) *CHYO/(1.+(F.!'Fl.K4(1)/(KC*A)))) +
3 (EFF 1 .DHS*KS (1) *CR HC (I) .CHCO/ (1. + (EFF 1 "K5 (1) / (KC .A) ) ) )
FTS = (TR (1) *ro) + (SIG!<A l/(HTC.A))
SIGIIA2= (EFf1*Difl*Kl (I)*ca(I)*CLO*El/(l.+
1 (EFt'1 .. ",1 (I) I (KC"A) 1"2) +
2 CErFI*DHl.K3(I) *CRN(I).CNO.E3/(1 ••
3 (EFF1.r.3(I)/(!(C*A»).*2) +
q (Ef~1*)HU*K4(I) *caHYII) *CilYO.Ea/(l.>
5 (EFF1.K4(I)/(l<:C*A»).*2) •
6 (!::Pfl.CHS*0:5 (1) .CRHC (1) *CHCO*ES/(1.+
7 (EFF 1 *K 5 (1) / (KC*A)) .*2)
orTS =SI"MA2/(HTC.A*~G*T5(I).*2)
T:5(I)= (FTS - 15(1) *vFTS)/(1.- JFTS)
1FUd3S(TSI-TS(I)).GE •• 05) GO 10 21
C •••• CALClJL ATIC, 0= OTHER PARA:lETER S ••••
C •••• i'ABAMETERS BC K1(I), .1(1), CA!'!l(!), ANOCAH{!) ••••
K 1 (I) = A l*ElCP (-;;1/ (RG*TS (1» )
.. CAM1(!) = EfF1*Kl(I)/(A*KC)
CS (I) = CE (I) *CLO/ (1. +DA~ 1 (1) )
R 1 (I) = EF?1*K 1 (1) *Cs (I)
SIGn3= (DH1*f1 (1)) + (Dil3*Fl (I) + (JH4*R4{I) + (DilS*aS (I))
DAH(I) = SIG.~~3 I(A*H7C*Te)
C •••• DEFINB COBfFICIERTS ~HICJ ARE FUNCTIONS ep cs A~O TR ••••
CCl = (CLO/(1.+DriMl (Il)l *f.XP(-El/(SG*TS(I))l
Bl = <l;:>*E?Fl*Al/('JL*CLJl
C121 = -(2.*Cl1) - (Bl*CC1)+(1./DELTA:l)
c •••• DEFINE A~, 3. C, ASD D FOR ~ASS EQUATICNS FOE SULfUB ••••
AA(I) = Cll
3(1) ""C121
C (r)= Cl]
10 D(I) = O.
C .~.SET aOUNCARY VAL7JES ••• _
v (2) = -Cl1 -
FIG. 7-9 Fortran program RDMOT3 for designing a backmixed laboratory.

size trickle-bed reactor for'petroleum oil hydrodesulfurization (continued).
225
•
B(~I = C13 + C121
C
CALL TEIDAG (2.ft.~A.~.C.D.C&)
Cll(1I1) = CR(ft)
WRITE {6. 198) (CRII). 1=41. :;01. 40)
198 FOR UT (1allO CR(I) =. Hl0E12.3)
DO 11 1= 2. I'll
IF (CR(I).LT.O.)CR(I)=O.
11 IF(CR(I).GT.1.)CP,(I) =1.
C
C •••• I~TEGRATE 3ASS ODE FOR NITROGEN ••••
to 12 1=2. 11 _
C •••• CALCULATION OF TS(I) BY NEIITCN-RAPHSCN ITERATION ••••
22 TSI = TS (I)
K 1 (I) =A ,.EIP (-El/ (RG*TS (I»))
K3(1)=&3·EIP(-E3/(EG*TS(I})J
K4(I)=14*EXP(-E4/(RG*TS{I} I}
~S(I)=lS·EIP{-ES/{RG·TS(I}})
ill (I)=El'fl*Kl (I)
.CS(I)
113 (1) =El'fl.K3 (I)
.CNS (I)
H4 (1) = EfY1"'K4 (I)
.CUIS (I)
85 (1)=£1'1'1.1(5(1)
.CHCS!I)
SIG~Al-(EFF1.0Hl.Kl (II*CB(11 *CLO /(l.+(EF',.Kl(II/(KC.'))1 +
1 (Ef'Fl*DH3*K3(1)*CBlI(I) *CIIO /(1.+ {EFF1*K3 (I)/(KC*')))) +
2 (El'Fl.0H'*K4(I) "'CBUY(I)*corO/(1.+(EFF1*K4 (I)/(KC*')))I +
:3 (El'Fl*005*115 (I) *CBRC (I) *c BCOI (1. + (EFl' 1*1\5 (I) I (KC*A) II )
FTS = (TR(I}.TO) • (SIGftAl/(8TC*'})
SIGIIA2= (El'l'l*OH1*1(1 (I) .CR (I) *CLO *Elf(l.+ •
1 (Efl' ,.11, (I)/(KC*AI)) •• 2) +
2 (EI'Fl*OH3*1I3(11 *CBN(I) .CMO *El/(1.+
3 IEl'l' 1*113 (I)/(KC.l») •• 2) •
11 (EI'F 1*OH4*K4 (I) *CR HY (I) *CHrO*E41 (1 ••
5 (E1'1'1*K4 ( I l l (r;c*lll)) **2) •
6 (EFF1*OHS*KS(II.C!lHC(II*COCO*ES/(1.~
7 (EFF1*1I5 (1)/ (KC*A»)) **2)
rFTS~ SIG:iA2/ (H:'C*A*RG*-rSO) .*2)
1S(I) ~ (FT:; - -rS(I)*OFTS)/(1.- oFTS)
IF(A2S(TSI-!S(I) .GE.O.05) GO,TO 22
C •••• CALC"LITION OF OTHER PA~A~ETERS ••••
C •••• ?AaAM3TEFS AR::: K3 (1). 1;3 (1). DAII3 (1), tAB (1), AND OS (1) ••••
K3(I) ~ O*;::X?(-E3/(RG*TS(1)1)
IJAlB(l) = Hfl*K3(Ij/(A*KC)
CNS(I) = CRN{II*CNO/(1. + 011'13(1))
:<3 (1) = EfFl*K3(1) *CNS(I)
SIG~A3= (DH1*;;1 (1) + (DU3*B3 (1)) • (DH4*R4(1)) • (DHS*oS(I)
tAHII) = SIG?U / (A.RTC*10)
,-, -
'
C •••• JEfINE CO~FflCIENTS WAICIl ARE fUNCTIONS OF CRN AND TR ••••
CC3 = (CNDf (1 •• nAII) (1))) .EX:- (-;::3/ (RG*TS (1»))
33 = iJP*Effl.A3/(UL*CNOj
C123 = - (2. *Cl1) - (B3*CC)) + {1./0ELTr7j
C ••• _ DE?INE AA. S, c, AND 0 FOR HASS ODE FOR NITROGEN ••••
AA (11 = Cl1
B ( I ) ' = Cl23
C I I) = C 13
12 D(l) = J.
C .......
SET 30JXrARY VALUES ••••
= -ell
= cn + C12)
C
CALL TilI:J ... :; (2.,1 .... A.B.C.D.CIlSI
CRN CM1) ~ CEN(~)
WRITE (6, 199) (CRN(I), 1=41. 401, 40)
199 FOR~A'! (lOHO ON (1) =,lPl0E12.J)
DO 13 I~ 2, ~1
IF (CRN (1). L:. J. 0) eRN (1) =0. -
FIG. 7-9 Fortran pro~ RDMOT3 for designing a backmixed laboratory·

size trickle-bed reactor for petroleum oil hydrodesulfurization (continued) .
.
226
13IP(CRN(I).GT.l.0)CRN(Il=1.
-
•
• • ••• INTEGRATE 'ASS ODE POR HYOROCRACKABLE CCl'IPCUHDS . , ••
DO 14 1=2. l'I
c •••• CALCULATION 01' 'IS(I) BY NEWTOH-RAPHSON I'IERlTION ••••
2] ISl = IS(I)
~l(II= Al*EXP(-El/(RG*TS(IIII
K](II= A3*EXP(-E3/(RG*'IS(!»)
1(4 (11 = A4.EXF(-E41 (RG*TS (1»))
115(1)= AS-EX;:>(-ES/(RC*TS(I) II
R 1 (1) = Efl' 1*1(1 (1 I .CS (I)
63(1)= El'l'l*II)(ll.CHS(I)
RII (1) = Ern·KIIII) .CHIS(1)
B5(I)= El'fl*K5(I)*CHCS(I)
SIG1IA1=(EI'I'1*DH1*Kl(I) "'CIi(I) -CLO 1(1.~(EI'1'1"'K1 (l)/(KC*A)))) +
- (EI'I'1*Ofl3*1I3(I)*CiN(1) *CNO /(1.+(El'l'1*1I3(1)/(KC*A»» +
2 (El'l' 1 *OH" *"" (1) *CRRY (I) *CHYOI ( 1. ~ (EI'I' 1"' ~4 (1) I (KC"'A) ))) +
] (EFl' 1 *OH 5 *1( 5 (1) *c SHe( I) *CH COl (1. + (Efl' ,.KS (1) I (KC"'A) ) ) )
PIS = (TR (I) .TO) + (SIGl'IA 11 (HIC*A)
SIG!lA2= (EFF1*OH1*K1(II.CR(II "'CLO *Elfp.+(EI'F1.1I1(I)1
1 (KC*1») **2) +
2 (EFF1*OH3*K3(II*CRN(I) -CNO *E3/(1.+(EFF1.~3(I)1
) (IIC-A))) "2) +
11 (EFl' 1-0H4*1I4 (I) .CRHT (I) .CHTO"' EIII (1. + (EPF 1"'114 (11 I
5 (KC.A) ) ) "2) +
6 (EI'1'1-DHS-K5(I) .CRHC(I)*CHCO"'E5/(1.+(Efl'1"'K5(I)1
7 (KC-A) ) ) -*2)
01'TS - SIGl'I12 /(HTC*A*RG*(TS(11 •• 21)
7S(1) = (l'TS - TS (I)*OPTS)/(1.- DPTSI
IP(lBS(TSI-TS(I».CE.O.OS) co TO 23
C •• , . CALCULllIOR OF OTHER PAR1l'lETERS ••••
C •••• P1RA~!TERS ARE Kq(I), R'(I), OAft4(ll, ~HD DAR(l) ••••
K4;I) = AlI"'EXP(-E4/(IlG*TS(II»
D11l11 (I) = El'l'l*KII (I) I(A.KC)·
CHYS (I) = CRHY (1) *CRYO/( 1. +OA!'l4 (1) I
RII (I) = EFF1*KII (I) .CHIS (11
SIGft13 = (OR1.?1(1» + (DH3*RJ(I)J + (OU4.RII(I)) + (OH5*RS(I»
OAR (1) = SIGilli) I (A*aTC*'!O)
C •••• DEFINE COEFFICIENTS WHICH ARE FUNC'IIONS 01' CRHT AND TIl ••••
CCII = C .• YO*EX?(-EII/(RG*TS(I»))/(1.+DAl'I"(I)I
84 = ~~.EFF1*AII/(ijL.CHYO)
C124 = -(2.*Cl1) - (BII*CCII) +(l./DEL'!AZ)
C •••• DEFINE A~, D, C, ASO D fOR IIASS ODE FOR HYDROCRACKABLES ••••
AA(I) = Cl1
B(I) =C12~
C(I) = C13
111 0(1) = O.
\., . C . _... SET BOUNDARY VALUES
D (2) = -Cl1
. .....
B (11) = Cl1 • C124
c
CALL TR1DAG (2,~,U,il.C,D.CR:H)
CRHY (11 1) = CRIIY (~)
liaITE (6, 200) (C"HY(I) , 1=41, 401, 40)
200 FOR!!AT (1011D C~:lY(Ij =, 1Pl0E1Z. 1 )
DO 15 1= 2, 111
1F(CRHY{I).L1.0.)CRilY(I) = 3.
lS II'(CRHY(I) .GT. 1.)CF:lY(I) = 1.
c
C •••• INTE~RAT, ~ASS ODo FOR U~SATvRAIES ••••
C
DO 16 I=2, :'I
C •••• CALCULATICS 0: "IS (1) ET NEWTON-'nPHSCN 17ERATlON ••••
24 TS1 = TS (I)
Kl (r) =A 1.F.Xi? (-;:: 1/ (P; -TS (1) ») -
fIG. 7·9 Fortran program RDMOT3 for designing a backmixed laboratory·
size trickle-bed reactor fol' petroleum oil hydrodesulfurization (contiml£.i).
.
227
•
Kl (1) =U*1!XP (- Ell (R G*rs (1) ) )
n (I) =A4.EXP (-Eltl (RG*TS (I! ) I
~S(l)=AS·7.XP(-ES/(RG*TS(II))
III (1) =£1'1'1*' 1 (I) .CS (11
B3(I) =£fFl*K3 (1) *CNS (I)
*'
Ii 11 ( I) = EFl' 1 11 (I) *;::R L S I Il
R5(r)=EFF1*K5(I) *cHCS(r)
SIG~A 1 = (tFF1*OH1*K 1 (1) *CR (1) *CLO / (1. + (EFF '.11:1 (1:) /(KC*All» +
1 (~l'I'l*OH3*K3(I)*CRN(I) *coO 1(1.+(r~1'l*K3(I)/(KC*11l1l +
2 (EFl' '.'HI4 *Kij (I) .CRffY (11 -ClIYOI (1. + (EFF 1-It4 (1) I (ltC-A 1I ) I •
3 (EFP1*OHS*KS (I) .CR HC (I) -CHC"" (1 •• (EP71.1t 5 (I) I (KC."'II)
FTS = (TR(II-TO) + (SIG~A1/(lITC.A))
SlG~A2= (EF!'1-0Hl*Kl (I)-CR(I) *CLO -E1/(l.+(£I'Fl.ltl(I)1
1 (KC*'))) "2) +
2 (EfFt.OR3*IO(I) *caNIl) .CNO *£:/(I.+(£,I'Fl*lt3(I)1
- ~ - .
3 ((I(C*');)**2) +
" (E!'F '.DB /1*1'( 4 (11 -Cl! BY (I) *CBlU~ Eltl (1.+ (EFl' 1* ~4 (Ill
5 (lC*'» I **2) +
6 (El'l' 1* DHS*K 5 (I) *CB HC (1) *CRC O*ESI (1 • + (EFl' 1 *KS (I) I
7 ~K;::*A))) ·*2)
DF'!S = SIG!lA2 / (HTC*&*RG*(TS(I) **2)1
TS(I): (YTS - TS(I1 *DFTSI/(1.-DFTSI
Il'(ABS(TSI-TS(I)).GE.O.OS) GO TO 211
C •••• CALCULATION OF OTHER PA~l"ETERS ••••
C •••• PARA~ETERS ARE KS(I). RS(I), DAMS(I). AhD tAB(I) ••••
IIS{l) = AS.EXP (-ES/ (RG*rs (1)))
D&1\5 (1) = El'Fl*KS(I) /(A*KC)
CHCS (1) = CRRC (I) *cacOI (1. +DAII5 (I) I
FS(I) = El'Pl*KS(I)*CHCS(I)
SIG!\13 = (DH1*Rl(I)) + (OH3*83(1») + (DH~*RII(I» + {OHS*R5(Xll
DAB (1) = SIG!lA3 I (A*!IIC.TO)
C •••• DEl'INE COEFFICIENTS WHICH ARE FUNCTIONS 01' CRRC AND TB ••••
CCS = (CHCOI (1.' OA1I5 (I))) *;;:XP (-ESI (RG*TS (X»))
85 ~ ~P*EFF1*AS/(OL.CHCO)
el25 ~ -(2.*Cl1) - (B5*CC5)
• (1./DEL'IlZ)
C •••• DEFINE AA, 0, C, AND 0 FOR !lASS ODE FOB IJHSA'rURATES ••••
AA(I) = Clt
BI!) =C125
C(L) = C13
10 0(1) = J.
C ....... SET 30UNDARY VALr~5 ••••
0(2) = -Cl1
B (1\) = C13 + C125
c
CALL IRIDAG (2.,.:'1, AA, 3, C, D,CBUC)
caHC (~1) = CRliC (~)
. , IIEITE(6. 201) (CEHC(I) , I=~l, '101, "Cl
2~1 POi~AI (10RO CRRC(I)=, lPl0E12.3)
DO 17 1= 2. t'11
IF(CBHC(l).LT.O.)CP.iC(I)=D.
17 IF(C2nC(I) .GI.l.ICRHC(I) =1.
c
c ...... IiiTF.;;aAI?; :tEAT OD=: f"OR ALL FEACTICNS •••
c
C •••• DElIS! AA,B,C, A~D D FCR HEAT EQUATION ••••
DC 18 1=2. !'!
C •••• CALCflLArlcN OC' TS (1) BY :iEWTCN-RA?HSON ITERA·TICN ••••
25 ':51 = IS(I)
K 1 (I) ~A l*E xt' (- E 1/ (F:; *r s (I) I )
K3(I)=Al·oAP(-E3/(RG*T5(IJJ)
K~(I)=A4*EIP(-E4/("G*TS(IIII
K5(I)~A5·ZX?(-E5/(P.G·TS(I))
El (I)=El'Fl*Kl(I) *C5(1)
R3(I)=Bffl*Kl(I)*CNS(I)
- 'A(I)=EFF1*'<4(1)*CHY5{:!:)
FIG. 7-9 Fortran program RDMOT3 for designing a backmixed laboratory·

•
size trickle-bed reactor for petroleum oil hydrodesulfurization (continued) •
•
"8
,
•
R5(ll~EH1'K5(T) 'CHCS(II
SI:;IIA1= (EFfl*Oill*Ki (II*C3(1) 'CLO ICl.+(H1'I*Kl(II/(KC*A)))) ..
1 (EFP1*OHJ*KJII)'CFNII) .CNO /(1.+(E1'Fl*K3 (II/IKC.A)))I +
2 I::ff "ilii 11 *K" (11 .CaHY (I) .Cll YO/ (1." (£1'f1*KII (I) / (KC. AliI I •
J (;:Ffl*DH~*K5 (I) *CSI!C{T)*CHCO/(1. '(EYF1'KS (I)/(KC'A» II
F7S = FR(I)*TO) .. (SIGr-A1/(iTC'AI)
SIG!!,,2= (EH1*J!ll'K1 (II'CR(I) 'CLO >E1/(I. +(E:PF1.Kl (Ill
1 (KC.~») "2) ..
(iPF1*DH)'K3(II*cil~(r) 'CNO *El/(I.+ (Effl*K3(II/
(KC*A») *.2) +
4 (::?P1*JH4*K4(T) *CRilY(I) *CHYO*E4/(1.+(EFI'I*K4 (Ill
5 (!:C*A)II"2) ..
6 (:;ff1'~'l~*KS(I) *Ca!lC(I)*CllCO*F.5/ {1.+ (EI'I'I*K5(I)1
7 (KC.A) 1)*·2)
JFT~ • 5rr.'A2 / ("TC*;"r:'~* (TS (I) **2»
'I5(!)= (F'::S - :';(I)*;JPTS)/(l.··;)F'IS)
IFIA3~('IJI'ISlr)'.GE.0.D5) GO lO 25
C •••• Ci.LCUL.7ION OF OTHER ?ARAM:':TERS ••••
C •••• i'AR'\!ETi':'l..i Alii': DAn(l), R;(O. CP. U. ASil SIGIIAD ••••
"IG~A3 ~ (DH1*Sl(I» .. (DH3*SJ(Ill • (DH4*R4(II) • (DHS·RS(I»
JA,: (ll = 5IGMA3 I (A*HrC*TO)
C _.,_ CI~CJLITION ap GAS D2SSITY UHO ••••
,; 1 = 2.03056£- CS*S*!":1:L
~) =.7.16104E-OS·~~L·NIT~0
ell = 22.414/(iiOIL*~n)
~5 = 9.3R276E-OS'3R~O.~'L
RiP= 12.02S*P/(TP.(II*TO)'(L.016*(·.-(Ql>p.-CP.(1)1) -
1 ("J*(l.-Cl1:Qlll) - (24*(I.-(IiHY(1))l - (QS*(1.-CHHC(1»») •
2 (34.032*;)1* (1.-Cli (Ill) .. (16.04J*Q3*(I.-CRN(1)1l •
) (5.6773*;>4*(I.-CRH(I»))
C •••• CALC~LATIOS OF THE S?FClf~C HEAT CP OF ~EACTING GAS ~IX ••• ,
c;'il2 - 27.698 + (0.003189 .. TO .. TR(I»)
CPH2S = 10.1243 + (3.015J6 * TO * TR(I»
(PCR" = 22.343 .. (0.04312 *
lO • TIl(II)
Ci'N33 ~ 28_0328 .. (D.02i36 * ~o *TR(!)
CP = CPH2 *(1.-(;)I*(1.-Cll(I)j) - (Ql*(1.-GIN(I»)) -
1 (Q4*(1.-CRilY(II» - (QS*(I.-CRHC(I»)) .. (CPH2S.~1.(1.-CR(IlI/2.)
2 .. (CPNi!3*;;3*(1.-CBN(I»/3.) • (CPC~4.-.14.(I.-CRHY{I»)
C ._ •• CA~CJLATIOa OF SDi'3fiI'ICIIL GAS VELOCITY 0 ••• ,
;) = (GL*T)*1.01325/(273.2*E?SC*P) )*(HOIL-( (CNO. p_-CRN (1)/3» •
1 (C'lCO* (1_-CRHC (1»» /RHCL)
C
sa =DP*EPSL/(TO*«EPSG*RHO*C?*U) .. (EPSL*RHOL*CPL*UL»I
SlG~AD= (DH"Rl(I)/DA~I(IJJ" (DH3*R3(I)/DAI'I3(I)) ..
1 (DH'+*R4(I)/DB4(I» .. (DHS.RS(I)/DA~5(I»
C22 = -(2.*C21)" (1./ilELTA2)
C211~-!lB' S IG1lAD
\,
". . AA(I) = C21
E(l) ~ C22
C (1) = C23
18 D (1) ~ C2'!
C •••• SET BOUNDARY VALUES ••••
0(2) = 0(2) - C21
B (11) ~ C23 + C22
CALL TRIDAG (2,.;."'!,AA,B,C,.D,.'IRX)
TRX(",) = TRX (M)
IiRITE (6,202) (TRqI), :-41, 'l01, 40)
202 FQR:lAT (10HO TRX(I) =.lP13E12.1)
ro 19 I = 2, M1
19 IF(TRX(I).Ll.1_)TRX(I)=1.
C
c .... '1::57.... _
:l0 30 1=2. ~
IF(AB5(!RX(I)-TR(I)}.GT. J.OJ1) ITER=.T?UF..
TR (Il =':ilX (I)
•
FIG. 7-9 Fortran program RDMOT3 for designing a backmixed laboratory-
size trickle·bed reactor for-petroleum oil hydrodesulfurization (continued).
229
,
30 CONTINUE
IF (ITER.lIID.1I0IT"R.Li:.20) GO TO 20
WUTE(6, 220)
220 FORIU.T (lilO, 13X, 11311S ~ A C 'I 0 R O E S I G N RES U L 'I S) ,
C
WRITE (6, 2(13) (ZZ(l), I~41, 401, 40)
203 FORII ...T (10HO ZZ (I) =, lPl0E12. 3)
WRITE (6, 198) (CR(I). 1=41. 401, 40)
WRITE (6. 199) (CRII(I). I=Ql, 401, qO)
WaIn: (6, 200) (CRIlT(I), I=ql, 401, 40)
WHITE (6, 201) (CRHC(I), 1=41, 401, ~C)
WRITE (6, 202) (TRX(I), 1=41, 401, 110)
'IS (l! 1) = '!'S (!\)
WHITE (6, 2(4) ('IS (I) , 1=41, 401, 40)
2011 FORIIAT(10ilO TS(l) =, 11>10E12.3)
CS (Ill) = CS (11)
WRITE (6, 2051 (CS(I), 1=41, 4Cl, 40)
205 FOR 11 AT (10HO CS(I) =, lPl0E12.3)
IIR1TE(6, 230)
230 FORIIAT(lHO,1SX,291l0AS CCIIPOSITIOII MCL-FRACTIOH/1HO,10T,
1 5HZZ (I) , 4T, 8HHYDPOGEII, SX, 3HH2S, 71, 3HNH3, 7 X, 3HCH4)
DO 231 1=111, 401, qv
HMI' = (YEEo*O.5/22.q"')*(1.-~1*(1.-CIi(:I11 - Q3*(1.-CRII(III -
1 Q4*p.-CRHI(I)) - QS*p.-CIiUC(I»)
H2S'iF= P?:Eo*S* (l.-CR(I) )/3200.6
AIIIIF = PEEo*/lITBO*p.-CRN(l») 114CO.8
CH4l!F= FEED*(l.-CRHY(II)/IIWL
SU~ = H~F + H2SKF + A~~F + Caq'F
IlYO = HIIP/Sill!
1l2S = H2SIIF/3U!!
All = All:! P/SUII
CH4 = CB4I1P/SD~
WRITZ (6, 232) ZZ(I). HTD, 82S, A~, CH4
231 CONTINUE
232 FOR/IAT (1HJ, 10X, F6.4,' 4X, F6.5, 41, F6.S, 41, F6.S. qX. FG.S)
STOP
END
C SUBROUTINE TRIOAG
C SUBROUTINE FOS SOLVING A SISTE" OF LINEAR SIIIULTANEODS EQUATIONS
C HAVIHG A TRIDIAGO!lAL COEFFICIENT !!ATRIX. THE <QUATIOl/S ARE
C IIUl'IDERED PROI! IF THROUGH L, AND THEIR SD8DIAGONAl., DIAGONAL, AND
C SUPERDIAGONAL COEFFICIEN'IS ARE STORED IH THE ABRAYS A, B, AHD C.
C THE COIIPUTED SOLUTION VECTOR V(IF) •••• V(L) IS STORED IN THE ARHAY
C V.
SUBROUTINE TRIO!;; (IF,L,l,B,C,D,V)
DIIIEIIS10li A(400),iI(400) ,C(400j ,D(400) ,V(400) ,BETA (400) ,GIIIIIA(flOO)
C
C •••• COIIPUTE IIITERIIEDIATE ARRAYS BETA AND OMIIA
BETA (IP) =B (IF)
OAlIlIl{IP1=D(IFI/BET1(IF)
,
I1'Pl=11'+1
DO 1 I=If'Pl, L
Bn! (I) =8(1) -1 (I) *c (1-1) /BET\ {I- 11
, GA/!!!A(I)=(D(I)-A(I)*GA'IlIA (I-l)I/BETA(Ij
C
C •••• COIIPU7E FINAL SOLUTION VECTOR V ••••
V (L) :GAII!!1 (L)
Lisr = L-IF
DO 2 K = 1. LAST
I :: L - K
2 VII) = 01:1I1A(I) - C(I)*V(I+l)/a::TA{I)
RETURN
END
FIG. 7-9 Fortran progra!D RDMOT3 for rl~signing a backmixed laboratory·

size trickle-bed reactor for petroleum oil hydrodesulfurization (continued) •
•
230
•
400
1.2 E+03 3.31 E+OO 2.S12E+05 6.020E-03 0.2 E+OO 8.206E+04 0.360£+00
2.12 E-02 1.296E+00 0.5 E+OO 1.5 E-04 S.S E+01 0.26 £+00 0.2 £+00
8.314E+OO 0.21 E-03 4.0 E+OO 6.4d2E+C2 0.5 E+OO 5.693E+02 2.800E+04
0.4. E+OO 7.206E+04 2.4351+05 4.686E+04 1.800E+03 2.50C£+15 1.000E+OJ
6.485E+04 4.1 E+04 1.255£+05 0.35 £+00 5.000E+00 6.7 £+02
FIG. 7·10 Input data for computer program RDMOT3.
7.3
VARIETIES OF TRICKLE·BEl) REACTORS
There are quite a variety of types of trickle-bed reactors, as shown in
Fig. 6-1. We will not treat <Ier.: all here.
We want to discuss the kinetics of a trickle-bed reactor in which the
reaction occurs both in the gas and in the liquic1 phase, as developed by
Frye and Mosby.16 The process IS the hydrodesulfurization of petroleum
oils that are partially vaporized under the rea"tion condition~. However,
the concept of reactions on catalytic surfaces used by these workers are
those of Langmuir and Hinshelwood, as developed 0y Hougen and
\\'atson,li and not the power law generally used in this book. The iso-
thermal equation developed for the desulfurization of single compounds
•
IS:
, H Po
v +
M P
where x = mole fraction of compound S in liquid

\ • Xo = mole fraction of compound S in feed liquid
k - volumetric reaction rate constant for a single sulfur
compound
PI) = \'apor pressure of sulfur compound
PH = partial pressure of hydrogen
S = amount of a single sulfur compound
v' = mole fraction of liquid vaporized
HIM = the hydrogen/oil mole ratio
- P1 = partial pressure of aromatic hydrocarbons
P = total pressure
•
= adsorption equilibrium constant for a single sulfur com-
pound = 2.8 exp(2760IRT)
K, = average adsorption equilibrium constant for aromatic
hydrocarbons = 0.38 exp(1l,700IRT)
kPo = exp( - 129,OOOIRT)
-'
,
--~-.--.'----- _ .. _- ._--_.-. . ~- ... _. -.-.- ... -

DeSIGN OF
. .._'----'- -- . --------...
TRIC~Le-B!O
-----.-----.-----~."-.---.
R!ACTOR
--,----- -- -'.- - --,,-,,~ - .. ---"- ----- - .. --. --~
'&DA:r~n-'" -'" ',- " ' u ' ' '_ _ ' _ _ ' ' ' ' ' ' ". . - ' - - ", .,
_._,,,.
1lI PU" D·
, _ _ LL,
.. •
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.,'-"---" -.
~'" 410, nr;L'~,\z" . ">'In')~Cnl)l) ,A" I~O(\.OOOOO
,AI: 28000.0000 ,~1: 1800.00000 ,AU • • 2~0000007E·,16,A~·
. H'I01.C)J()() lAC": .)1111',~,,'IP.-Ol,Cl,Oo .710~0116(,1 ,('''[,' .1.110000~2 ,nl[t • . 251200.000 ,n"~ •.. fi40~0.OOOO. ,D"~ • - "" ,.
Qln01.')OO'l ,IlW," 12o;r,~I).OOO ,or- .f>01?,)QAJ4F.-02,OT- • H'l<l'lqqAA ,~1- 82060.0000 ,ft)- 72060.0000 ,J'!4.
2tJ3>;1)'l.01)!) I ES" 46860.01)00 I EP.~= .160000014 ,J'!PSG=. 2') ]Q36146 ,EPSL' .106563b66 ,P!J'!O- .212000012!-01,BOIL*
.5001010 00 ,~C",. 15001000n-03. p= 5S.0000000 • PE"AL~ .259999990 ,PEnA2- .199999988 ,RG- 8.31'0001' ,RROL~ __,__
569.10a'),~~ ,"~1J" .',)1'JQq99A~-Ol,S" 4.00000000 ,'1'0= 648.199951 ,UL- .1112331~5E-Ol.RTC- 1.29B0003Q ,CROo
• H2241r,el ,C'IV'): .949701~24 ,CHCO" .17809.1<'>';
&ENI) ----- .. ,-"--- •
9. -----".- -"-,.,'-------- -"--'-- ----- --,. -- -~----~ _._- _. - ---", - . - - - - - - -
r T ERA 'I' ION C J C L E S

-C:-
Z C"(C:-[):---:---;>:O",OF+';1 U.O.,ri'I'.()l fi.OSOr.'~l- 0.0'>01"01 1:005£+02 1.20n'02 1.405P.'02 1.605E+02 1.805E+02 2.005£+02
cncI) ,:.. 9,.7Lli;-OJ".__ '1...•.4..2QF-Ol '1. 15r,r-(l.l_,,_B.A9L~:)J_ O,i,1_4E-01 I!.. , ,'l.'!E-O1 ~.141F,:O' 7.90'i£-~1 7.676£-0.1 7.496£-01
CRN (I) : 9.(J~OE-Ol 9.761£-0 , 9.643£-01 9.~27£-01 9.412J'!-01 9.2<)9£-01 9.197!-01 9.076£-01 8.967!-01 8.879!-01
Cl;JY (L): 1.'l0n~'0'l T. nOOE'OO ,'.010E+00 1.!l0'lE'')O 1-.-=0-=0-=0-=E"'+-=0-=0-""7'1.000£'00 '.O-OOR'OO 1.001£+00 1.00a.Oo 1.0oa+oo ,--.
cnc(r) , 6.P~r.-()1
.- --- ..-
~--~-
3.7SH-01
----.--.--~---- '--'- 2.2QH-nl
,----- _.",_. 1.409F.-Ol ---
---. ~.630E-12 .~
5.2~7F.-02
- .-- 1.2J9E-02 1. 985£-02 1.216E-02-.- 8.105E-03 - •
'l'Rt ( t ) " 1.nAE'OO 1. %7E.00 t.'ll)oe+oo 2.155£+00 2.QS2JI!+OO 2.7qaE'OO 3.0Q3E+00 3.3381"00 3.631!+00 3.851UOO
CR!I) • 7.2358-01 2.q51!~~0~1-~5~.~9~1~7~E--0~2~~1-:~J2~.6~E~.-~O~2~-2~.~9~1~J~~--~0~3~~6-.~J7671~!-~0~4~~I-.~]6~5~!~.-~074"-~3~.~0~'~2~£--~O~5-~6~.~5~476=£-~O~6r' i~62~-06
,CR~
"
III' 8.829!-01 4.9181-01 1.6<l9E-Ol fI.411E-02 1.062l'!-02 2.420l'!-OJ
- - 5.fll0l'!-01l
-- 1.
--197E-01I 2.6H!-OS
._- --" 7. 15t1l-01i --~-- - ,- .
'-"5&0-01 ) 1."'1·01 2..9121-02 6.33911-0] 1.37$11-03 2.984 !-Oll 6."U-05 1.405!-05 3.0491'!-06 1t.199s-07
.
CMC(t}-
------
3.A84R-Ol T. 025E-0 1 2.409 F.-02 5.4391':-03 1.200P.-jl" 2~-1;62p.~0-4 .. S:-039P.-0r;- 1.?7~-05 2.791P:-0'--·7·:S4QE-07'''----
TB! = 1.203E+OO 1.264HOO 1.270£+00 1.282e+00 1.2AQE'OO 1.20«;£+00 1.285£,00 1.2A5£.00 t.26'il'!+OO 1.2851!+00
(1) -,,-- --
ClI!%) • 8.13*1-01 S.2101-0t 3.1121-01 1.82U-Ol 1.062a-01 6.162£-02 3.51311-.)2
, 2.072£-02 1.202P!-02 7.6116£-03
CR~(I) = 9.2AlE-Ol, 7.880£-01 6.495E-Ol-' 5.l1SE-Ol 4.340E-Ol 1.54JE-Ol 2.892E-ill 2.361£-01 - 1~928i:-or'T~634B':ol'--"-
n.1I10R-Ol 1.?Q<)P-01 1.01)R-Ol J.147F.-02 <l.4<)OE-Jl 2.A'IIP.-0) A.r,A4Fo-04 2, «;0IlR-04 7.7'ln-05 ~. A12 £-05
'IfJ - C"HT{I)'
..... .. .
,
f\I
0tJ
••
"
case (1) & 4. 112£-01 1.37U-01 11. ),)5!- 02 1.370!-02 1I.298!-0) 1.)48!-0) 4.229 !-04 1 • 327&-04 q.165!-0'l 1.556!-05
-;;;T:::R7.x:c;(~I7)-~---;-'-.~2-;;O~)7.E7+-;'O-;'O-·--;-'-.~2o;1~7-;-f.7_"O-;;O--"-."2 "9;:-4 ;;r,"7+"O"O---I:- 2~8 E + 06 1-;?'f9 E _50'---'1' :'2QA"E'o-d--· C29"ifr.+o 0·' C';FJs£"60- - -,. 2'f'if. +00 1.2912-00
CS(I) = 3.144~::I2..L __ ~!_0?.6.~::n.L_.. f .. 8i.1E-:nl 1.5~Or.-Ol

" .. 11. ~9n-02 '1.7%E-02 2. 637 E-02 1.46~r.-02 A.150R-O) 5.009£-03
CRN (1) 2 9.2S7R-Cl 7. 7791!-0 1 6. 2621'!-/) 1 5.0041';-01 J. 9'1611-0 1 1. 1971'!-01 2.5S91'!-01 2.0~OE-Ol 1.6q~!,:-0' 1.'372£-01
-;;C:::Rc:;.'"'Y:c(;-:I:7)-=·----:R:c-.-"'16;c-:,::-r.--0;-0'1--2. q A0 E-0 , - A. li<ffE:'o":r . ~-. ,-.. --.- .. -.-~-. ---- ------- ..---- ,,",- . .. ~+ •• - . _ ••• - - - • . .
2.12AE-02 6.402£-03 1.766E-03 4.8901':-04 1.J~AF-OQ 1. 7R 1 E-Or, 1. 272E-O~
OIIC (I) = '1.1'19£-01 1.J61E-Ol 4.21JE-02 1.295E-02 - - -

J.979E-03
- -• • -.---~- - _ . _ _ ••
1. 2211R-OJ
__ •• __ •• ~-,
3.7~7r.-OQ
"-_• •- - - - - - - - - , - - , - - - , _ . , • • _--,." ---~.""---
1.HO~-OQ
---- _.- " • •, - " - - - ,
3.~?7P.-Or,
.,. +
1.315£-05
•
TU (I) = 1.217HOO 1.3271.+00 1.304£+00 1.4nl+OO 1.437E+00 1. 44ge+00 1.456r.-00 1.116IEtOO 1. ~~4 f.+OO 1.QHr.tOO
.. - .... - . .. .
~--.--
c~ (I) -- I. ~,)OE-O 1 .'I •.nc,l.-nl 1.~27~:-Ol 7.%.1F.-02 2.AOJE-02 1.00'IE,·02 1. ',2 2 F.-OJ 1. 220 F.-O 1 Q. 1 ry H:-OII 1.689E-()4
- CRN LIl"
--,-----.----------
9.710f.-01 7.3()",F-01 , . 1 fiO F.- 1'1
r,. ].300E-Ol 2. n4B-Dl 1. 791F.-Ol 7.726P.-02 4.~6H-02 2.672F-02 1.701£-02
•
CR~Y (I) = 7_717l-01 2. 22r,r.-Ol r,_ 0'73 r.-02 1.123£-02 2.Q{,5P.-OJ 'i. )Qllll-04 1.1'79P'-O~ 2. r,74P.-O~ " • ~ 1'7 F.- 0 6 1.'QBR-06
---;;-,..-;-:;c-_._.. _ . . . , .... . .....
CRIIC (t)" 4.12AE-lll 1.nU-Ol J. (0) F.-02 9. 8]7F.-OJ ... 2.f.j'fIFOJ (,. <)Y2~:\)ti 1.043F.-04ti:RJ7P.-O~ 1. 2H R-Oo; 4.02 JE-06
T9.{ (1) = 1.217E+CO 1.10'if'OO 1.145r.+OO 1.36~F.+OO 1.175

-.. E+OO
- .--.- 1.1A1E+OO 1.38~F.'OO 1.3A7E+on 1.1SQr.·OO 1.189£+0/\
_ _ , _ _ ,. _ _ " . _____ • __ • _. ___ - . _ . _ _ ._ - ,, _ _ ••• " .... _,_ • • • , "•••• __ , • • , . __ n _
',.--" --.-- .. ~ ~.----.-.
- -
CR (1) = A.OQ4E-Ol ~.64r,!-oi 2.275E-Ol 1.0Jo;E-Ol ~. 540£-02 1.<)49P.-02 8. 2~ lr.-OJ ). q 76R-OJ 1.4S"iE-()1 6.9H!-04
,
-.,...,.-=-.--.--.----~.'" ,- ... , -._._._---- ."._--_ ... - -._--,-, ,. -._- .... ,.. _.. , '" _..... __ . -- .. ,," .- ... "., .... ,-,.,.-.... , " -",-,., . .
CEl(I) " Q.?4lF-Cl 7.';(\9,-nl ~.617E-Ol 4.063£-01 2.C64P.-Cl l.QQ]R-Ol 1 • .l7~ F.-Ol q. 4o;n-02 ~. nQ F.-02 4.730E-02 •
CRH (11 " _l,tlfj9J:-() 1 2.464F-Ol

.. _--_. ~. q 10 E-O? 1.363F.-1)2 ._ ...- 1 ~ O?O F.-O 1
,
".q~7E-04 1. Sfi lR-O ij 1.4q~F-)~ 7. ~ 19F.-(\~ 2.160E-06
CRIIC (I) " 4.1Qn-Ol I.JOST-Ol J. 926 E-02 1.09Jr.-02 3.01111':-03 H.6J2R-04 2.40QE-04 &.704!-0~ 1.R6)p'-OS 5.24 JE-06
.. - ". ....... ,--, .. ,",. . . . "." .. -- .". - --
-=T::q::{CC(::r7) --,,'e~, ii:'ri (\ a-oo
-~- -'"
1.10 3E +00 1 •.119E+00 1.3~2E+OO 1.1')8£+00 1.3(,OE+OO 1.361P.·OO I. 36 1 F.-OO 1. 3~ 1.361!+00
CRlI) " R.O<;OE-01 4.66H-~1 ".Jl"F-nL __ l.0~J\.~-0..1 ._"4.9~OP.-02 ~.~7~E-02

.. _---- ----_._-,-_."---- -,.-.. -~--- •. ----.---.-,-.---.-.4.69~P'-OJ
1.034P.-02 --.- "._. ,.
2.1J3!,:-01 1.10lE-03
eRN (I) = 9.246£-01 7.S2'iE-Ol S. 6<JS 1':-0 1 4.102E-Ol 3.035E-Ol 2.1nE-Ol 1.581P:-Ol 1. UOR-01 a.219!-02 6.282E-02
- :-:::-::-:-:.-.._--------_..._--_ ...... _..... _.,.,.,-_... ",.,.-._- . __ .._".
.. , -,. ,_ _. __ .. --
- .. ... ••
C~:JY(I)" l.onnr-ol 2.4%f-Ol f.046F.-0~ 1.411F.-02 ,. 1',9 F.-O 1 7.4nr.-04 1.773F.-04 l. q ~f; F.- O~ 9. OM p.-O~ 2.572P.-06
c~~cw = 4.1<;0£-01 1.J08F.-Ol J.8%!':-02 1. llH:-02 J.l?OP.-Ol

-~---,.-.. >-
'l.11~P.-04
-----,.,'.----- - - -
2.601E-04
- - - -----
7.42QF.-OS
- - ' ----_.,.,--,.,'"
2.121£-0<; 7. 284 E-06
FIG. '·11 Computer output of program RDMOT3 for designing a tat oratory· size trickle-bed reactor.
•
"
,
•
T ox (t) • 1.212f.>OO 1. )OIlp.+OO I.J40E+OO 1. 31>6E+ 00 1.3?Q!+OO 1. nIlE+OO l.lAOE+OO 1.1A1E+00 I. lAI. e+oo 1.J92H+00
. "C"(r::":)--=---:.Q:-.-:0-:3::Q::-P'---::-O71.--;q:-.-:6C:CC:9-=r---=0""'"1---;:-2-.2"'3:-:2'""'~:-.--;OC:;'-·-:1-:
-C"""R:- . 00 BR':O 1 i/. 41 SE-a 2 -.-, • 906 E -02 --if:-f7ifi':-: OY"--·:i:·44 rp--n " 1.4A-JP.-Ol 7.2738-04
CR~LIl = 9.241£-01 1.4A~r:-Ol 5.'i90E-Ol 4.016P.-Ol

- _0'. 2.0111':-01
_ .•• ____ . _ _ _ _ _ l.q7AE-Ol
.... _. 1.376E-Ol.
_. __ . __ ,_ _ _ _ . _____ " __ , __ . _ ... _ .. _ _ _ _ ._ Q.'i52E:-0:l
.. __ ."_" __ _ _ __ • 6.625F,-O~ 4.8"9£-02
_._--- -~ .. --.-. . --_ .... -.-----. ---_._._- ~
.-- ~----
CltR! (t) = 7.8SSE-Ol 2.43 lE-Ol 5.8081:-02 1. 332E-O 2 3.0191!-03 6. A09£-04 1. 5l31!-~4 3.4461:-05 7. 7~6£-06 2.150E-06
Cltrlc(r)= 4. 14fR-Ol 1.101F-Ol 1.B0n-02 1.0A4F.:07. --~f:OSH·01 !i.~'-i'iOF.-Oq 2~40JE:04-' 6.i2)P:-65··-·Lii8IfE~n<; 6.337!-06
T!H(I) - _ 1.712£+(10
-- l.J01£+~O 1.346E+OO-----
1.164E+OO -~------~---,.
I.J72E_OO
-
J . .11 ?J:,,-,,+",,0 0 1.379£_00 1.3Aor+00
- ~-------
1.3A1E-OO. 1.3atE-OO
--
CR (I) 8.042E-Ol .4./;2~E-Ol 2.253E-Ol 1.024E-Ol 4.515£-02 1.9598,,02 R. 4.18 E-03 3.619E-03 1. "Q9P.-O 3 7.581!-OQ
-=0:-;=----- ----- ----.--..------.--- , " "- --, ,,'- -"'--- "-_._- ----. .. • __ O •• "H '._ '"
1.401P.-Ol
--~--- ... - ...
'l. 14n- 0;> 6. 71~~-n2 ~.017!-02
CR~(l) = 1. 242P.-Ol 1.4Q6f-Ol ~.615E-Ol ij. 04Ar-1) 1 2. M5P.-O 1 2.'10qP,-OI •
Ct1:IY 1U.:n ........ 7 •. R61.E-Ol .. . -

2.'146f-Ol
, ..
, '" --"
' •• n66E-02 1. 111'lF-O? ", '
1.061E-03
." _." ",""
6.q2n-O~ 1.~~or-04 1.·.11F.-O~ 7. ,.'lA E-06 2.193£-06
CRIIC (I) = 4. 14?E- 0 1 1.30.1<-01 J.Ol<;E-02 1.0QOE-02 3.07'H-01 8.659E-04 2.428 E-04 6. SOlE-OS 1.904~-05 6.423£-06
-T=11;:-;-1.""'"(I=-):--::---·C5T2".OC;-- f: 1 0-6F >DO--·-l.111~'O(i LTi,2f.+ 00-· -. CfioE+ 0·0 -Cf'lilfi-ob-·· 1.-:11, f. > 0-0" ··f.·.i7~I:.oij··· 1. 377 f: > 00 1.377!>00
Cq (.I) = ~. 04 JP.-O 1 4. 62A£-0 1 7. 260E-O 1

- 1. 01n-O 1 4.5n3E-n2
-'-
2.- 1 on-o?. 8.72'11'.-03
.---' ~--.-----.-
3.7e~E-03
--_."
1.639£-03
----- S.10~E-Oq
CSIf (r) : 9.242E-Ol 7. 499F-O 1 'i.625E-Ol 4.068E-Ol 2. S91E-0 1 2.038!-OI 1.431£-01 1.00ll!-OI 7.0211':-02 5.234 £-02 •
CRH(I)= 7. % 77-01 ._.-2: u!;Q"f::'1l ,-_.- ~,:ai11E:cj2·-·-r:. 3 <; 7f:():r-·-j;·O ARE::·OJ· - 6~9-qn-~·6ij- ·T:sa:fE ;"-6 4- -3:·572 P.- 05'· ir:063E-06 2.246£';06
CH'lC(I} : 4.147E-Ol l.l04r-lll

--- 3.D?OF.-02 1.0Q3P-02
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2.456P'-04
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1.940
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--:::-:c-:-=-:--~.- .. --~ . -~- .... ..
~ -.---.-' . . .. " " " ... , ~ ... .,'."", " ,. ...., .. '-'~
en (t) = 'I. 04n-1)1 11.6~1"-O 1 2.2~14p.-n1 1.0271:-01 4.542E-02 1. "A1P.-·O} A.~aJr-Ol··i:706F-oj I. ~98E-Ol 1. 874£-(j4
eR'I(I): <).24?E-Ol 7.496E-01 ~. 617r.-O 1
-- 4.055E-Ol 2.876E-Ol - .. _-, 2.02H-Ol
.. -_. '-"'''- _._,-- . _-_ .. 1.417E-Ol q. ~OOl!-o?
- .. - -.,-._-----.-. -- - ..- ..-
6. 91J e-o 2 5. 141 E-02
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"
eqHY(I)= 7.864E-Ol 2.446E-Ol 5.870F-02 1.351E-02 .1. 072E-0 3 6. 9501!:-04 1.0;69E-01 ·3.539E-05 7.919£-06 2.220E-06
.... _- _ ... _-- ._-- -- -----,,--,-~ ----.- --,'.---.------.---,- --,;r-;;o'''" "'" -.--. -., .- F-
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...-
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--- 1.371E>OO
-.-- --,,-
1.115E>OO --'1.._,• .177e>OO
-'""'--
1. 378P.>OO 1.37RP,+00
---._-" ._---, - .. -._-"._-----._-,,- --- ,
1.376E>00
. .
s •
"
,
.
..
R r. ACT 0 R DESIGIf RES!JLTS
zZ (I) = 1.214£-01 2.q~R~-OI 1. ~~ n- -01 q. Hq bE-O 1 -('.-O'lOFO ,-r.2'!ln::'Or-- O;Q"SBiFol- q .6"62"P'::'lff-f~-() An.:·01I 1 • 2()1 E.OO
_ CR (1) = _6.~_O'l.~!l.~Q L __ IL._62_4 L-:OJ _____ 2.2'.i_q Ec:91 ..... 1. 02 (f.~O..L ... 4.S!(2IL-:flL. __ '. 9QJ_~_::('-L"_I1L'lIlJk.Ql._. __L. 1 QH:-_~_L_.. 1 •.5.'J_~_!:-_(tL _._.7 , 61.~ E:-.O_!L _._."_
CRN (1) = 9.242E-Ol 1.Q96B-Ol 5. 617E-0 1 4.055E-Ol 2.876E-Ol 2.0232-01 1.'

, 17E-O 1 Q.900E-02 6. q BE-02 5.141£-02
7 c ----.- ------- -- ---- .. .
..-.- , .... --- - ... _._-,
~.446E-Ol
'"'
C1HT(t)= 7.864,,-01 5.870E-02 "-·1.3511:--02 -3-:'-:0:::7 2=-E--:O :J:-- 6.9SnE-04 I.S6ge-04 1.539£-05 7.91'E-06 2.220£-06
cnaClI1= 4.1Un-Ol 1.303£-01 3.816E-02 1.091E-02 3.C86E-03 ~.692E-Oq 2.443£-04 6.856£-05
-- 1.924E-05
-- 6 ,-~_O 5E-Q.~ ____
TU (tl .. 1. 212E+00 1.3061!+00 1.3461+00 1.363E+00 1.371E+00 1.3751+00 1.3771+00 1.31I1E+OO 1.378 E+OO 1.3781+00
T S (11 -- 7. 906E'02 • A'.51SE'02 8.746£'02 e.e46E'+c)2 1i-.eQ3E+02 U-:-'lS!+02 8.926E+02 8.931"+02 8.933i.02-8~93U+02-u--
Cs (X) = 't.._R3.!.-OI Z...JllL6..E::.OJ_. _'kQO.91'_-02_H __ 3Le~5J-02. __ .1.671E:02 ".244P.-03

,."._--
,_.
3.130£-03 -.... ---1.3~3E-03
",,"-_.' '. -.. ......-
,
5. A50P'-O~ 2.89l!-0'
-- ~,---.-- --- ~
alS COlPOSltlOI ROL-rR1CTtol

ZZ C: I H Y:CD:-:ll:-:O:-::G:-::E:-:~:--;-'--::H::-2::-S-----:M=-=H=)-- CH 11- ---------------------_.- .--,~ .. - ._" -- '--' .. --------------._---------------_.-
,
_______~0~.~1~2~)~q_~.L9~6~8~0~1~_~.~n~1~i~4L)_~.~0~O~luO~4~__ ,~.~0~11~5~2~_____________ _ _. ___________________________________________
0.2438 .88499 .04 H!i .00381 .06969

-------::-::-::--::::----:-::-=--=~-__::_;;_.:;_;~-_=c;;_;:_;;__------'---.----------.- - --------------
I). ](.42 .e~005 .06210 .00"06 .09059
•
0.4A46 .e'21AS .07317 .00 0 71 .0962<; _. __
0.60 '50 .81241 .07919 _ 01169 .e>m1

•
----------~_=_::_::_:c_-- ::-==---:::-:-::-::-=----=-=':--:;---- -~ "- ~".- - -. - . - ' ..
O.72~4
.a081S .08043 .01311 .09811
•
0.84'50.--.-"~-----
------~""-
.00623- ....0"142
~
.01412-
.- - .09824
-.-'----------.. -~ ,,~-... _-'-- -~ -.,,---,-~,.- . -
,
0.9662 .80503 .0818'5 .011183 .09830
1_ 0366 .00431 .ClS205 • nl<;32 .09 RJ2 --------- ---------------

1.2n70 .80392 .08211 .01562 .39834 ___ _ . . .
FIG. 7-11 Computer output of program RDMOT3 for designing a laboratory-size trickle-bed reactor (continued).
•
>
•
Frye and Mosby conclude that this equation is specific to hydrode-
sulfurization. However, their approach is also applicable to hydro-
denitrogenation.
NOMENCLATURE
Frequency factor
2
Cross-sectional area of catalyst bed, m
Bo Bodenstein number, dimensionless
Specific heat of gas, kJ/(kg . K)
Specific heat of liquid phase, kJl(kg . K)
c ~101ar concentration of key reactant, kmollkg
.\101ar concentration of hydrogen in bulk gas phase, kmoll
>\
111'
~{olar concentration of hvdrocrackable

, hydrocarbons, i.e.,
,
3
the entire unreacted feed stock, kmol/m
Inlet molar concentration of hydrocrackable compounds,
>\
1.:I110lln1'
~folarconcentration of key reactant in liquid phase or molar
concentration of hydrocarbons containing an atom of sulfur,
>\
kmollm'
Inlet \'alue of CL
, ,
C:-; '\101ar cc ,lCPntraUon of compounds each containing one atom
3
of nitrogen, kmol/m
..
Inlet \>alue of C:-;
Cox \101ar concentration of compounds each containing one atom
3
of oxygen, kmol/m
C",o Inlet value of Cox
C T
Reduced molar concentration of key reactant (sulfur),
dimensionless
C rilC Reduced molar concentration of unsaturated double bonds,
dimensionless
.>
Inlet concentration of unsaturated compounds. kmol/ms

•
Reduced molar•
concentration of hvdrocrackable
•
com-
p":JlE1ds. dimellsionless
Reduced molar concentration of nitrogen-containing com-
pounds. dimensionless
•
•
c,.ox Reduced molar concentration of oxygen-containing com- '

pounds, dimensionless
dp Catalyst particle diameter, m
d, Equivalent spherical diameter of catalyst panicle, m
D Diffusi\'ity of reacting molecules in liquid phase, nlls
2
DH Molecular diffusion coefficient for hydrogen, cm /s
2
D lleff Effective diffusion coefficient for hydrogen, cm /s
Dr Inside diameter of reactor, m
E Activation energy, kJ/kmol
HIM H ydrogen/oil mole ratio
RI Reaction rate constant for type I sulfur
k~ Reaction rate constant for type 2 sulfur
kH,S Adsorption equilibrium constant for hydrogen sulfide
Ka Axial thermal diffusiyity in packed beds, m~/s
K; fherage adsorption equilibrium [in Eg. (7-50)] constant for
aromatic h vdrocarbons
•
LHSV Liguid hourly space velocity

P Total pressure, bars
p.; Partial pressure of aromatic hydrocarbons, bars
Peclet number for mass and axial dispersion in liquid phase,
.,
\ . dimensionless
PH Partial pressure of hydrogen, b~rs
Po Vapor pressure of sulfur compound, bars

~R Global reaction rate, kmol/(s . m:l)
l
5 Sulfur concentration in the product, kmollm: or [in Eq. (7-
50)] amount of a single sulfur compound
5'! Initial content of type I (aliphatic) suI fur, kmolim:l
s~ l
Initial content of type 2 (thiophellic) sulfur. kmol/m:
T Absolute temperature, K -
Absolute inlet temperature of feed to reactor, K
•
Tr Reduced temperature, dimensionless
u Superficial velocity of the gas phase, m!s
UL Superficial velocity of the liquid phase, m!s
•
,
Vi Mole fraction of liquid vaporized, dimensionless
,
v Total volume of catalyst beds of the reactor, m

,
3
3
Gas volume in catalyst beds of the reactor, 01
3
Liquid volume in catalyst beds of the reactor, m
Volume of catalyst particles in packed beds of the reactor,
3
m
",'HSV Weight hourly space velocity
x Mole fraction of compound S in liquid, dimensionless
Mole fraction of compound S in feed liquid, dimensionless
z Axial coordinate in the reactor, m
z Dimensionless axial coordinate in the reactor
Total reactor length, m
0: Reaction order, dimensionless
Heat of reaction, kJlkmol '
TJ Effectiveness factors of various reactions
Void fraction, dimensionles'i
cc Gas-phase fraction, dimcnsior..less
CL Liquid-phase fraction or liquid holdup, dimensionless
Cp Catalyst-particle-phase fraction, dimensionless
e Time = IILHSV, h
""
< ,
iJ.L
,
Viscosity of the liquid phase, Pa' s or kg/(m . s)

Density of ga:., kg/m3 .
Density of liquid phase, kg/ms
Particle density, g/cm3
Thiele modulus for hydrogen
T Tortuosity factor, dimensionless
Subscripts
o Initial
f Final •
"
REFERENCES
1. Arthur Kohl and Fred Riesenfeld, Gas Purifuation, 2d ed., Gulf Publishing
Co., 1974.
- PROCESS DESIGN OF TRICI<LE-BED REACTORS 239
2. M. Orhan Tarhan and Louis H. Windsor, "Coke-Oven Oils Yield High

Quality Benzene," Clum. Eng. Pro?;,'. 62(2):67-72 (1966).
3. Richard A. Flinn, Hamld Beuther, and B. K. Schmid, '"!\ow You Can Im-
prove Residue Treating," Petrol. Refiner 40(4):139 44 (1961).
4. R. R. Cecil, F. X. Mayer, and E. !\. Cart,Jr., "Fuel Oil Hydrodesulfurization
Studies in Pilot Plant ReacLOrs," paper pt'esented at the Am. Inst. Chem.
Engrs. Meeting, Los Angeles, December 1968.
5. J.B. Fourier, Thione allalytique de la chalew', Oeuvres de Fourier, Gauthier-
Villars et Fils, Paris, 1822.
6. J. B. Maxwell, Data Book on Hydrocarbons, The Esso Series. D. van Nostrand,
New York, 5th Printing, 1958.
7. Roben H. Perry and Cecil H. Chilton. Chemical Engine!,Ts' Handbook, 5th ed.
McGraw-Hill, New York. 1973.
8. H. C. Henry and J. B. Gilbert, "Scale-up of Pilot Plant Data for Catalytic
Hydroprocessing," Ind. El/g. ChRlll. j'mcess D!'sign DevdltjJ. 12,328-334 (1973).
9. Charles N. Satterfield, Yi Hua Ma, and Thomas K, Sherwood, "The Effec-
tiveness Factor in Liquid-Filled Porous Catalyst." Inst. Chem. Engrs. Sym-
posium Series no. 28, Inst. Chem. Engrs., London, 1968 pp. 22-29.
10. Charles R. Wilke and P. Chang. "Correlation of Diffusion Coefficients in
Dilute Svlutions," AlChE J. 1:264-270 (1955).
I!. Charies N. Satterfield, IHass TransJer in Heterogeneous Cata(nis, MIT Press,
Cambridge, Mass., 1970.
12. David E. Mears, "The Role of Axial Dispersion in Trickle-Flow Laboratory
Reactors," Chem. Eng. Sci. 26:1361-1366 (1971).
13 . V. E. SateI' and Octave Levenspiel, "Two-Phase~~low in- Packed Beds," Ind.
•
Eng. Chem. Fundamentals 5:86-92 (1966).
14. J.M. Hochman and E. Effron, "Two-Phase Cocurrent Downflow in Packed
Beds," fnd. Eng. Chem. FundamentaL~ 8:64-7 I (1969).
15. F. DeMaria and R. R. White, "Transient Response Study of Gas Flowing
through Irrigated Packing," AIChE J. 6:473-481 (1960).
16. C. G. Frye and]. E. Mosby, "Kinetics of Hydrodesulfurization," Chem. Eng.
Progr. 63(9):66-77 (1967).
17. Olaf A. Hougen and Kenneth M. Watson, Chemical Process Principles, vo!. 3,
John Wiley, New York, 1947; 9th printing 1962 .
•
'.
•
•
C/wjJter FIXED-BED, BUBBLE REACTORS (FBBR)
If trickle-bed reactors have not been sufficiently studied, fixed-bed bubble

reactors (FBBRs) havt' been even less well studied, In 1952 Schonemann I
\\Tote that FBBRs had not yet been introduced into praCTice because the
upflO\\' would entrain the catalyst and this would limit the upflow. Of
course. today, this is no big problem, as will be discussed further belO\\'.
Fixed-bed bubble reactors are reactors in which the liquid phase is
the continuous phase and ~he gas phase is the disperse phase. The typical
FBBR is an upflow concurrent gas-liquid reactor (type II in Fig. 6-1)
with relatively low gas and liquid flow. I f the liquid flow is increased
beyond the fluidization velocity, the fixed bed of catalyst expands into
'.
, , an ebullated bed, which ,,-ill be discussed in Chap. 9. Howner, it is possible
to operate an upflo\\' fixed-bed reactor as an FBBR at or above the
fluidization velocity if the upward expansion of the fixed bed is pre-
vented by installing hold-down plates right above the fixed bed. These
plates are made of screens open enough to permit the passage of liquid
and gas but fine enough to prevent catalyst particles from going through.
If the liquid and/or gas flows are increased even higher, then the system
,,'ill enter the pulsating regime, which is discussed in Sec. S.3,
Interest in FBBRs arose during development \mrk at Oak Ridge l'\a-
tional Laboratory on a reactor to reduce uranium (VI) to uranium (1\')
nitrate in aqueous solution with hydrogen over a sup.!y)ned palladiunl
catalyst. Flooded concurrent upflo\\' operation gave higher cOl1\'ersions
2
than downf1ow trickle-beci.regime. Subsequently, Mochizuki et al.l found
-
the FBBR to be more selective than the trickle-bed reactor in the I1\'-
drogenation of phenYl acetylene (PA) to styrene over Pd/AI 2 0" catalyst,
,
the undesirable reaction being the consecutive hydrogenation of styrene

to ethyl benzene. "l.f (
•
242 CATALYnC REACTOR DESIGN
,
We really know very litd~ about FBBRs, so we will discuss both the
transport phenomena and the process design of this class of reactors in
a single chapter.
8.1
TRANSPORT PHENOMENA IN FBBRS
Transport phenomena in FBBRs have great resefi.blznce to those in
suspended-bed reactors, which will be discussed in CI-}ap. 9.
Pressure Drop across FBBRs

The pressure drop across an FBBR consists of three basic terms:
1. The pressure drop across the sparger
2. The pressure drop to overcome the liquid column of height HL and
density PL (Fig. 8-1)
3. The pressure drop due to gas flow through the submerged fixed
catalyst bed
A sparger is simply a pipe with many holes on it to distribute a gas in
a liquid. The pipe may be of various shapes and sizes. The gas pressure
in the pipe, the pressure in the liquid, the densities of the gas and the
liquid, and the temperature and the size of the sparger holes determine
the size and frequency of the bubbles.
The pressure drop across a sparger can be calculated by following
Gas
•
Gas --;>... === :::::=~ -Sparge

.
r
:--
liquid
FIG. 8-1 Schematic representation of a fixed-bed bubble reactor (FBBR).

•
FIXED-BED BUBBLE REACTORS (FBBR) 243
4
the procedure given in the Chemical Engineers Handbook and also the'
procedure suggested by Litz.3
-
The pressure drop to overcome the liquid column in the fixed bed
can be calculated jointly by using the method of T urpin and H untington
(see Sec. 6.2).
Gas Dispersion in FBBRs

While the I;quid feed is pumped in bulk to the bottom of an FBBR, the
gas must also be properly distributed in the form of bubbles at the
bOlLOffi. Of course, the fixed bed itself is a good distributor. However,
only in a small narrow reactor can one depend exclusively on the bed
for gas distribution. In a large-diameter bed it becomes necessary to
install a sufficient number of spargers all through the cross-sectional
area ul'der the bed. ASain, the fine distribution is effected by the bed.
Unlike the suspended-bed reactors, in the case of the FBBRs the size
of the bubbles is hot critical because the dimensions of the ris;ng bubbles
are determined by factors independent of the sparger, e.g., the size and
shape of the catalyst particles and the viscosities of the gas and the liquid.
Axial and Radial Disbersion

, in FBBRs
6
Halms Hofmann published correlations between the liquid-phase Peeler
number for mass and the product of the Reynolds and Schmidt numbers
(Re· Sc) for FBBRs. He found that bubble size had no effect on Pe. The
corrdation consists of families of curves depending on parameters such
as Ut; and uJuG. Hofmann investigated the celebrated air-water system •
\'..,
in an FBBR packed with 4-mm x lO-mm glass cylinders and 2-mm glass
spheres. The shape of the curves were completely different. It is there-
fore fair to conclude that the Peelet number of any other gas-liquid
system with any particular shape and size of catalyst would have to be
experimentally determined.
Heat Transfer in FBBRs

For mildlY, endothermic or exothermic reactions FBBRs can be run as
adiabatic reactors and the cooling and heating can be done by heat
exchanging the liquid with a coolant or a heating medium between beds.
For more strongly exothermic reactions it should be possible to install
cooling coils right in the.catalyst bed. The strong backmixing caused by
the turbulence of the bupbles rising between catalyst particles should
enhance the transfer of heat from the particles to the liquid and then ..
from the liquid to the coil.
•
. 244 CATALYTIC REACTOR DESIGN
Mass Transfer in FBBRs

7
S. Goto et al. studied the mass transfer in FBBRs and trickle-bed reactors
and found that the catalyst-to-liquid mass transfer coefficient k,a and the
liquid~to-gas mass transfer coefficient hl,a do not differ greatly between
concurrent upflo\\' or down flow reactors. H')\veYer. upflo\\' gives some-
what higher k,a than dow-nflow at high godS rates. 10\,' liquid rates, and
smaller particle sizes. FBBRs gi"e higher hl,a than trickle Deds at high
gas and high liquid flow rates.
Snider and Perona studied che mass tran~~er in an FBBR using the
2
hydrogenation of a-methylstyrene i'l a diffnential reactor {)\'er two dif-

ferent palladium-on-alumina catalysts. They found that gas and liguid
flow rates strongly influenced the reaction rate and that the gas How
increased the transfer rate. The effect< of temperature and composition
,
on reaction rates were much weaker The rate of Illass tran"fer of hy-
drogen in the liquid phase can be represented by the equation:
kLa
9l,. = (C* - CJ (8-1 )
p.
where Vl e = reaction rate, kmol!(s . kg of catalyst)
C'". -- equilibrium hydrogen concentration in liquid phase,
kmollm:'
Cs = hydrogen concentration in liquid phase at catalyst surface,
3
kmollm
hL = mass-transfer coefficient, m/s
,
. ,
a = external surface area of the catalyst pellets per unit bed
volume, 1060 m-I
Pc =
, ,
bulk denSIty of catalyst, kg/m' of bed \'Olume
In order to calculate kLa from this equation, ~K. and p, are obtained
from experiments, C* is obtained from the reactor pre«ure and the
Henry's law constant according to Johnson et al} and C is calculated
from:
(8-2)
where CB is the concentration of a-methylstyrene in kilomoles per cubic·

meter and A, B, and C are empirical constants in Eg. (8-2) and are
obtainable from Refs. '2 and 9 after proper adjustments for conversion
from the cgs to the SI system.
Snider and Perona obtained low mass transfer coefficients for gas
•
,
Reynolds numbers above 50. They tentatively attributed this decline to
the pulsing regime. . .
It appears that [01' any other reaction to be run in a FBBR, Cs has to
be determined experimentally from the kinetic equation ofthat reaction.
8.2
PROCESS DESIGN OF FBBRs
The first step in designin; an rBBR should be the determination of the
rate-controlling step or steps. Once this is done, the reaction rate must
be expre<;.:;ed in terms of this step.
The second step is to determine the rate of liquid upflow. This rate
must be below the fluidizatio'l rate; otherwise the FBBR would become
an ebullated-oed reactor. It is theoretically possible to use bed limiters
or hold-down plates or thp like to mainta~n the fixed bed beyond the
fluidization rates. However, indications are that the mass transfer would
suffer from pulsing under the highLr rates. Thus the hourly capacity
of the reactor would determine the cross-sectional area A.,.
The exothermicity or endothermicity of the reactions must be ex-
pressed by differential equations as a function of z and heat transfer
means must be devised to remove or supply the heat.
The combined design equation for 'nass and heat must be integrated
or resolved for the reactor height Zr corresponding to the desired con-
version x. If the desired x is highel' than the practically possible x, the
product may be distilled and unreacted feedstock recycled. Economics
would dictate how high an x should be attained in the reactor and how
\ . .
much reactant should be recycled after the product distillation.
8.3
GAS-LIQUID-PHASE FIXED-BED REACTORS WHICH
OPERATE IN THE PULSING OR SPRAY REGIMES
Reactor types that operate at hi2her flows than the trickle bed or the
FBBR are receiving increasing attention. While, in the past, chemical
engineers saw mostly their disad\"antages, such as the unsteadiness and
shaking of the pulsed reactor and the need for effective phase separation
after processing in the spray-regime reactor, they are now beginning to
see some of the advantages as well. We will attempt a brief review of
"
these fast reactor types in the following .
•
Transport Phenomena -
Most flow maps showing the transition from the gas-continuous trickle-
bed regime to the pulsing regime are based on experimental data for
•
CATAlYTIC REACTOR DESIGN
•
the air-water system and cannot be used to predict the transition to the
10
pulsing regime in other systems. T. S. Chou et a1. found that the tran-
sition from gas-continuous to pulse flow is very sharp in general and
that no hysteresis occurs. It appears to the author of this book that,
pending (he availability of extensive data on various gas-liquid systems,
the reactor designer will have to obtain detailed solid data on the par-
ticular gas-liquid system of interest.
Une known property of pulsing and spray regimes is that the coef-
ficient he for mass transfer between liquid and the caralyst particle in-
creases as one progresses from the trickle-bed to the pulsing to the spray
regime. A measure of this progress is the power dissipation by the liquid
phase per unit packed volume and per unit mass of liquid holdupll:
EL = ( - APIZ)LG UL (8-3)
€L PL
•
wrere EL = power dissipation per unit packed volume and

per unit mass of liquid hcldup, W/kg
( - MIZ)LG = pressure drop for concurrent gas-liquid flow, Pal
m
€L -- liquid holdup, dimensionless
PL
- liquid density, kg/ms
UL -- superficial liquid velocity, m/s
A double logarithmic plot of ke against EL gives a straight line with a
-•
• .
slope of + 0.22. .
.
I2
Calderbank and Moo-Young found that heat and mass transfer coef-
ficients in a \-arietv of systems and geometries depend on power dissi-
pation to the one-fourth power. The relationship between ke and E~ can
be expressed similarly:
k«Sc)2,-, = 0.20(E;' f.LdpJ", (8-4)
-
The root-means square error of this expression according to Lemay
II 5
et al. is 0.5 x 10- rnIs, which corresponds to an average relative error
for he of about 6%. This relationship is valid with certainty only for
aqueous solutions of electrolytes contacting packed spheres.
The effect of radial position on ke Wet'> studied by Lemay et al.,1! who
13 14
. man and Mevers
reviewed the models of Week , and Beimesch and Kessler
and concluded that ke is not especially sensitive to radial position.
Another known property of pulsing and spray regimes !s the relz-
tionship between the liquid-phase mass-transfer coefficient kLa and the
power dissipation EL by the liquid phase per unit packed volume:
W!m~ (8-5)
-
•
•
Lemay et al. 11 plotted KLa(Sct" against EL in double logarithmic co-

ordinates and correlated data by various workers. They found that
kLa(Sc)v2 increases with EL but the line has a slight curvature. Thus, as .
the fluid velocity and the power dissipation increase in a gas-liquid packed
bed, both kr and k1.a increase.
Choice of Fast Reactors and Process Design

Because gas-lic;uid-phase fixed-bed reactors operating in thepulsing and
spray regimes ha\'e higher gas absorption capacities than similar reactors
operating as trickle beds, these faster reactors should be used with re-
actions that have higher intrinsic reaction rates. Catalysts used in such
reactors can be made more effective by depositing the active corrponents
in a thin layer near the geometric surface.
Designers should find reactors in pulsing and spray regimes quite
attrartive because such regimes will enable them to design faster and
more ecnl10mical reactors. HO'\"Cver, this sort of design is pure pioneer-
ing in a yet unknown territory.
Lema}, et aLII compared a fixed-bed reactor in the pulsing regime
with a CSTR. \fhile the former has the advantage of increased mass
transfer, the latter can achieve the same result by using finely divided
catalyst. The CSTR was found to be the reactor of choice.
Here there are some reservations the following factors may reverse
the above choice:
. The catalyst recm'ery ~conomics of the CSTR
.
"\ , . The catalyst contamination of the product in the CSTR

. The requirement for high yield of reaction, which is impossible in the
CSTR
The design procedure for the pulsing-f1ow or spray-regime fixed-bed
reactor is basically the same as th~lt for the plug-flow type of trickle-bed
reactor.
NOMENCLATURE
•
a External surface area of the catalyst pellets per unit bed
-I
\"0 Iume, m
C* E<,!uilibrinm hydrogen concentration in liquid phase, kmoll

m .-
•
Hydrogen concentration
., in liquid phase at catalyst sur-"
fa(~. kmollnY
•
,
Power dissipation by the liquid phase per unit packed

3
volume, W/m
•
Power dissipation per unit packed volume and per UI1H
mass of liquid holdup, W/kg
Liquid column height in an FBBR, m
Catalyst surface-ta-liquid mass transfer coefficient. m/s
Liquid-ta-gas mass-transfer coefficient, OIls

Pedet number, dimension less
Global reaction rale, kmol/(s . kg) of catalyst
Re Re\"nolds
•
number. dimensionless
Sf Schmidt number, dimensionless
•
Ut Superficial liquid velocity, m/s
Liquid holdup, dimensionless

.
Bulk density of catalyst. kg/m
'\
Liquid density, kg/m'\

( - MIZ)/.(; Pressure drop for concurrent gas-liquid H()'·:. Pa'm or
bars/m
REFERENCES
1. K. Schoenemann. Der chemische Umsal: bei kontilluierlic/J dW'chgefii/l1hn Rmk-
tionen, Dechema ~lonograph 21, 1952, p. 203. .
2. J. W. Snider and J. J. Perona, "Mass Transfer in a Fixed-Bed Gas-Liquid
Catalytic Reactor with Concurrent Upflow," AlChE J . 20: 1 172-1177, 1974 i,
3. S. Mochlzuki and T. Matsui, "Selective Hydrogenation and Mass Transfer
in a Fixed-Bed Catalytic Reactor with Gas-Liquid Concurrent l' pf1()\\'."
AJChE J. 22:904-909 (1976).
4. D. F. Boucher and G. E. Alves, "Fluid and Particle Mechanics:' in Pern' and •
Chilton (eds.). Chemical Engineering Handbook, t-.lcGI-aw-HiII, Ne\\ York.. 197~).

Sec. 5, pp. 5-47-5-48.
5. W. J. Litz, "Design of Cas Distributors," Chelll. Ellg. (NO\·. 13) 162- I 6li . I 97~ ,
6. Hanns Hofmann. "Der derzeitige Stand bei der Vorausberechnung in rech-
nischen Reaktoren," Chem. Ellg. Sci. 14: 19::'-208 (196 I).
7. S. Coto, J. Levee, and J. M. Smith, "Mass Transfer in Packed Beds with
Two-Phase Flow."lnd:-Eng. Chem. P1'Ocess Design Det.elop. 14:473-176 1975,
-
8. D. L. Johnson, H. Saito, J. D. Polejes. and Olaf A. Hougen. "[fIecls ,d
Bubbling and Stirring on Mass Transfer Coefficients in Liquids:' .11CItL I
3:411-417 (1957).
•
9. B. D. Babcock, G. T. Mejdell, and Olaf A. Ho.ugen, "Catalyzed Gas-Liquid

Reactions in Trickling-Bed Reactors. Pan I. Hydrogenation of a-Methyl-
styrene Catalyzed by Paliadium," A1ChE J. 3:366-369 (1957).
10. T. S. Chou, F. L. Woriey. Jr., and Dan Luss, "Transition to Pulsed Flow in
Mixed-Phase Cocurrent DownI1O\\' through it Fixed Bed," ludo ET/g. Chem.
Process Design Develop. 16:424 427 (1977).
I!. Y. Lemay, G. Pineault. and J. A. Ruether, "Particle-Liquid Mass Transfer
in a Three-Phase Fixed-Bed ReaClOI' with COClIlTent Flow in the Pulsing
Regime," Ind. Eng. Chelll. Prou.\.\ Design Deve/op. 14:2HO-285 (1975).
• • ,
12. P. H. Calderbank and M. B. l\foo-Yollng, "The Continuous Heat and Mass
>.
Transfer Properties of Dispersions." ChI'''/' 1:· lIg . Sri. 16;39~54 (1961).

13. Vem \V. \"eekman, Jr. and John E. 1\!yers, "Fluid Flow Characteristics of
Concurrent Gas-Liquid FI()\\' in P~!cked Beds:' :\1 Ch E j. 10:95 J-958 (1964).
14. W. E. Beimesch ;lnd D. P. Kessler. "Liquid-Gas Distribution Measurements
in the Pulsing Regime of Two-Phase Concurrent Flow in Packed Beds,"
AIChEj. 17:1160-11')5 (1971).
•
,
\.
• •
•
•
Chapter REACTORS
In the previous two chapters we discussed various forms of gas-liquid-

phase fixed-bed reactors. In this chapter we will discuss catalytic gas-
liquid-phase reactors in which the catalyst does not form a fixed bed but
is suspended in the liquid by a variety of methods.
9.1
DEFINITIONS CLAS:;IFICATION
Suspended-bed reactors are a class of heterogeneous gas-liquid phase
reactors in which the catalyst particles are loosely supported in the liquid
phase. This support is provided either by vigorous mechanical agitation
as in continuous stirred-tank reactors (CSTRs), by rising gas bubbles as
in slurry-bubble reactors, or hy upflow of liquid as in ebullated-bed and
three-phase transport reactors (3<l>TR). Let us now define and describe
each reactor type before discussing the transport phenomena in each
type and then their process design.
Continuous Stirred-Tank Reactor (CSTR)

Continuous stirred-tank reactors that contain finely divided heteroge-
neous catalyst suspended in liquid are in most ways quite similar to
CSTRs in which homogeneous gas-liquid reactions ta_ke place. They b::~
ically consist of the same shape of tank with a stirrer. The main me-
chanical design differeoce is that the stirr~r must keep the fine catalyst
particles in suspension ig addition to adequately stirring the liquid. To
make this task easier the catalyst is supplied in a very fine size, preferably
less than 200 f..Lm. Figure 9-1 is a schematic representation of a typical
heterogeneous CSTR. The gas feed is injected through a sparger. The
:J!"/
,
r--, ,¥--- St irrer motor
r - - - - - - •
•
t==== -~~~Tz Gas product Tz

r--- - -.
I •I
L
- _ V Liquid 12
- -
-'-'---+---.-. ;:::-::::::-
.
o _ -
•
I
- .-
,I
•
" •
--:--:...
I .... -
.--:- •
•
• • - Catalyst Fresh
• • .4-Boffles
- '---Stirrer
propeller
,
Gos inlet
leeo
F Yo I,
Heal exchanger
FIG. 9-1 Flow diagram of a typical continuous stirred-tank reactor system.
product gas if there is any is removed overhead through a back-pres-

sure control system. T~estirrer must disperse gas bubbles sufficiently
to provide for adequate absorption time. If the absorption is slow, the
exit gas will still be rich in the gas reactant and should be recycled to
the gas inlet.
The liquid feed is first brought to the required temperature in a heat
exchanger if preheating or precooling is required. The fine catalyst is
blended into the liquid feed and introduced into the CSTR with the
feed. The liquid product has to be removed from the CSTR together
with the suspended catalyst, usually through a level-control system. The
catalyst must be separated from the liquid product by filtration, cen-
trifugation. or simple settling. Part of this catalyst might be reused while
part of it might have to be regenerated or discarded.
Like the homogeneous CSTR, the heterogeneous catalytic CSTR op- "
erates fully isothermally, its contents are thoroughly mixed, and its prorl-
uct concentration is tht: same as the liquid concentration at any point of
the reactor. Figure-g-l shows only one way of (I) keeping the fine catalyst
in suspension and (2) pl'Oviding for an efficient gas-liquid contact. These
two goals can be met in a variety of ways, some of whic~l are schematically
shown in Figs. 9-2, 9-3, and 9-4. The choice of any particular way is
,
r - --.,
I
. Gos outlet
•
PC 6 •
~Heat exchanger
Gas LC r-- --.

__ t t
-- - Liquid producl
Liquid + to catalyst
catalyst separation
Pump
FIG. 9-2 Flow diagram of a CSTR with gas spray contact.
r- - - - - - - - - - - -,
I
t
Go>
s ' I
I
I
.--{]
•
R ,I
I PC I
I I
I ,
I ,
I ,
I LC
Liquid +
cotol)5!
Cw
•
I
liquid .. Compressor
catalyst
Gos
FIG. 9-3 Flow diagram of a CSTR with gas recirculation for increasing gas
•
residence time.
••
-;::.===:::;~ .( . Recycle compressor
PC -- --,
9
)
-- --
• • •
•
•
• •
• •
•
)
Gas
..
line for ealalrs: removal
from reactor and resupply
to reactor
FIG. 9-4 Flow diagram of a CSTR for gas feed and gas product only.
253
•
254 CATALYllC REACTOR DESIGN
govel ned by the peculiarity of the gas-liquid reaction and of course by .

•
economIcs. .
Figure 9-2 shows a spray-type CSTR, which has the advantage of .
lower pressure drop for the gas flow than the bubble-type CSTR of Fig.
9-1. Also, the heat exchanger is outside of the reactor, which makes this
system easier to design and operate. The sun ing is done by pumping
around a large amount of liquid and by spraying it into the reactor
sful.Ce. Thus the reactor has no moving parts, no rotating stirrer shafts,
and no glands. The catalyst feed and removal are identical to those
indicated in Fig. 9-1. Figure 9-3 is a gas recirculation reactor. Basically
it is a reactor of the type of Fig. 9-1 with a gas recirculation system to
increase the gas residence time in the CSTR. The reactor of Fig. 9-4 has
only a gas feed and a gas product. The role of the liquid is simply to
suspend the catalyst and to transfer the heat. The liquid is of course
fully inert to the gas reactants but dissolves them easily. It is helpful if
the procuct gas is insoluble in the liquid. The advantages and disad-
vantages of CSTRs are listed in Sec. 9.4.
Slurry Reactors
A sl1l1T)' reactor is a gas-liquid reactor in which the finely divided solid
catalyst is !:eld in suspension in the liquid by rising gas bubbles. Thus
the Engli~h term "slurry reactor" is only partially descriptive: it notes
only the catalyst slurry in the liquid. The Germans call this type "Bla-
senreaktor," or bubble reactor, which is also only partially descriptive, since
\
it notes only the bubbles of gas and nothing else. Although all the
suspended-bed reactors have a catalyst slurry, the term "slurry reactor"
will be used to_denote only the particular kind of suspended-bed reactor
l
in which the slurry is supported by an upflow of gas bubbles. Fair used
the term gas-sparged reactor, which may be justified if bubbles are gen-
erated by a sparger. Besides, a gas sparger may also be used in CSTRs
and other reactors (Figs. 9-1 and 9-4)_
The slurry reactor is attracting increasing anention_ Sherwood and
Farkas~!.3 at MIT, and especially K6lbel and his pupils4-IO in Germany,
have studied it thoroughly. However, there still is much more to learn.
The various uses of the slurry reactor are illustrated in Figs. 9-5 through
9-9. Figure 9-5 shows the most genet:3 1 case, in which d gas and a li<1uid .
feed produce a gaseous and a liquid product. The catalyst addition,
separation, and regeneration steps are identical to those alr;:::ady dis-
cussed for the CSTR. -These steps have not been shown in Figs. 9-6
through 9-9 although they are included. The major difference from
CSTRs is that the slurry is kept in suspension by rising bubbles instead
of by mechanical agitation. Figure 9-6 shows a design for liquid feed
•
SUSPENDED-BED REACTORS 255
,
and liquid product. AT! inert gas is recirculated over the sparger to
maintain the slurry in suspension. Figure 9-7 shows a design for gaseous
feed and gaseous product only. An inert liquid is used to suspend the
catalyst. Figure 9-8 shows a slurry reactor for gas and liquid feed and
gas products only. The liquid is recirculated until all of it is converted
to gas. Figure 9-9 shows a slurry reactor for g"dS feed and liquid product
only. No gas leaves the reactor. The gas is catalytically condensed to a
liquid product. "
Gas oullet
Catalyst liquid
cw =--~
separation product
-- ~
Catalyst
Spent catalyst
-'-'."
."
regeneratian
L..-
•••
... , " Gas
Catalysl Fresh catalyst
addition makeup
Liquid feed
FIG. 9-5 Flow diagram of a slurry reactor system for gas and liquid reactants.
CW
· --
-- -
- liquid
product to
catalyst
separation
• •
• Gas recirculation
••
\ for stirring only
... ., .
• >
-
Liquid
feed
FIG. 9-6 Flow diagram of a slurry reactor for liquid feed and liquid product
only.
Gos product
-- -
cw -
Occasional
.• " - ~I~rry Withdrawals
~<-. and mokeups for
catalyst regeneration
•. , ,
·• •.'• Gos feed
<
inlet
FIG. 9-7 Flow diagram of a slurry reactor for gaseous feed and gaseous prod-
uct only.
•
Gas producfs
Liquid Gas recirculalion

feed compressor
Gas feed
FIG. 9-8 Flow diagram of a slurry reactor for gaseous and liquid feed and
gaseous products only.
-- - Liquid proCe::
cw (i.e.,polyme·
/.
.~
Gas recir culotion
, •• .
foextinct Ion
, "
•••
Gas feed
FIG. 9-9 Flow diagram of a slurry reactor for gaseous feed and liquid product
only.
•
\., -
,- ,
Slurry reactors as a rule have been u~e:! in the chemical industry only
• ; .I
in small-scale batch hydrogenations and are not yet common in the larger
operations of either the chemical or petrochemical industries. A notable
exception might be the Institut Fran<,:ais du Pet role's (IFP) recent de-
velopment of the slurry reactor process for catalytic hydrogenation of
benzene to cvclohexane. 11 The use of the slurry reactor extends beyond
. "
batch hydrogenations to some continuous operations such as the fischer-

Tropsch reaction·"1i and various other continuous processes of possible
commercial interest. Examples may be the hydrogenation of a-methvl-
styrene to cumel'~' n:ported by Polejes.l~ oxidation of ethylene i)) air
reported by Smidt et,al.,13.14 and hydrogenation of ethylene reported by·
Kolbel and ;\laennig.;1
.
Ebullated-Bed Reactors
The ebullated-bed reactor is a concurrent upflow gas-liquid reactor in which
•
•
SUS,DENDED-BED REACTORS 257
a strong liquid upflow expands thL bed of coarse solid catalyst up

to 100% or more of the fixed-bed volume. We can also say that the
ebullated-bed reactor is a three-phase fluidilt.'d-bed reactor in which
fluidization is accomplished by the liquid upfl()\\.
The ebullated bed may be best understoorl 1)\· watching a laboratory
glass reactor filled with a bed of coarse solid catalyst when an upf1O\\' of
liquid through it is slowly increased and when. in addition. a flow of
gas is started and increased (Fig. 9- 10). Let U" assume a \'(>I·tical glas~
reactor of 2.5 cm ID containing a O.2-m-high bed of 3-mll1 cxtl udate of
a commercial alumina-based catalyst. , Let us fill the reactor with "·.lter
and let us start a slow upflow of the water. At low liquid rates the fixed
bed of catalyst is not disturbed. \Valer f10\\~ through it. :\t a rate of
1 9 -" "
approximately 30 111' /(h . 111-), or 0.00833 Ill"" . 111-). the catalyst bed
Gas out
Liquid oul
- Clear liquid
'c,:"
.
- 100% expansion
. ..
· .
~.'t-
.:"..
- 50 % expansion
-~-:
-".",
• '''j
~;;~
: ....
- Bed top 01 rest
-< -
... ....;..
~
"
100 .~ .". .'
Packed bed at no flow

.'.::,:: 10-20 mesh Co-Mo/AlzO o
90 · . -~ .. calalysl
Bed ;;"'.
80 supporl-...,.. "'it
•
70
Liquid
c 60 flow
.- 0
~
c
0
Q.
50
~
Gas
'"
~ 40
0 flow
30
Fluidization point
20 •
10 •
0---
o 0.01 0.02 0,03
Superficial velocity uL. m3((m 2 sl
FIG. 9-10 The expansion of a catalyst bed in an ebullated-bed reactor.
•
starts to expand upwards in the same way that a gas-solid fluidized bed
"unlocks" at the fluidization point- Each catalyst particle in the expanded
bed acquires a random movement, quickly moving in all direct!ons but
still remaining in the same general location. When the liquid upflow is
further increased, the now loosened bed is further expanded according
to the plot shown in Fig. 9-10. This bed expansion is obviously a kind
of fluidization similar to the gas-solid phenomenon known by chemical
engineers for several 1 P cades. As in gas-solid fluidization, the top of the
expanded liquid-solid bed is fairly we:l defined. The liquid layer above
the bed is quite clearly distiaguish;:d.
\\'hen a concurrent gas flow is added to the liquid upflow, the bed
expansion data still fall on the same curve obtained with liquid flow only.
It is not possible to expand t!le bed by using a little liquid flow and
increased gas flow. Usually the liquid is first blown ova and 'hen pistons
of wet slugs of the catalyst bed are also blown over. This means that the
gas upflow does not affect the fluidization significantly, at least not in
the proportions of gas and liquid described above. Thus it appears that
the ebullated bed is basically a liquid-solid phenomenon. The only effect
of the gas floK is to make the upper boundary of the fluidized bed
somewhat less \\'ell defined and to intensify the random movement of
the catalyst pellets.
The catalyst size in the ebullated bed is very important. If a catalyst
of relatively large particle size is used for a first reaction and a somewhat
smaller-size catalyst is used for a second reaction, the coarser catalyst
forms a bed at the lower part of the reactor while the finer catalyst is
expanded further above the coarse bed and fmllls a second bed, both
beds being at the same temperature. This way two consecutive reactions
can be run in the same reactor.
Of course large catalyst pellets are easier to separate from the feed-
stock, but on the other hand such large pellets have a low effectiveness
factor. In order to increase the effectiveness factor Hydrocarbon Re-
search, Inc. (HRI) has suggested cataiyst sizes a::. fine as 60 mesh. An
important advantage of using relatively coarse catalyst pellets is the ability
to treat feed stocks containing particulate materials which would plug up
fixed-bed reactors. Particulate materials simply pass through the ebul-
lated catalyst bed without plugging it. In fact, in the H-Coal process the
•
feeastock consists of finely ground coal mixed with the product oil.
In spite of the vigorous turbulence in the ebullated bed, cylindrically
•
shaped cataiyst pellets are not degraded by abrasion, so that extruded
pellets can be used. #
Figure 9-11 is a schematic representation of an ebuIlated-bed reactor.

The gas and liquid inlets are both located at the bottom. The bed is
supported by a screen which permits the gas and the liquid to pass
•
•
through but not the solid catalyst. There is sufficient clear liquid on top
of the bed to allow the liquid product to be withdrawn without also
withdrawing any catalyst particles.
The solid-liquid-gas fluidized-bed reactor was first studied by E. S.
Jr,hanson of Hydrocarbon Research, Inc., who called it an ebullated bed
IS
and patented it. The H-Oil and H-Coal processes use such a reactor. 16--20
The H-Oil process is fully commercialized. Experience has been obtained
in plants at Lake Charles, Louisiana and Shuaiba, Kuwait,21-2'1 and
. . .,.{
a
nu-nber of other plants have SInce been bmlt.-·
Three-Phase Transport Reactor (3c1lTR)

In the ebu!!ated bed, the settling velocity of catalyst particles balances
the liquid upflow velocity, and the catalyst bed as a whole does not move.
When the liquid velocity IS further increased, the liquid upflow entraim
the catalyst panicles out of the reactor. If the entrained liquid-catalyst
slurry is recycled tu the bottom of the reactor and if a gas is added at
the bottom and separated at the top, we have a three-phase transport reactor
(3<1>TR) (Fig. 9-12). This reactor type was studied by B. B. Pruden and
M. E. Weber in Canada2~ and appears to have some adyantages. It can
be designed either as a concurrent or a countercurrent reactor. In either
case, the catalyst is ,-ntrained by the liquid flow, which is up or down,
respectively. The gas is, of course, always up flow. Figure 9-12 represents
., - - - - - - - -
•,
Gas •
effluent
, :-_- -='.
. ___ -r Liquid
, ---' ..• '~
•
.. - . " ' -
• product
j : J .• - 411':":0_
~. . ~ .:. "':. ;:1 Clear liquid
: .' '.
'-0'
· . · .' .
~'-"' • •
_. .•..
••
et '. . . ' , ...
..
•
• . _," IJ.
- ~ . .
·• ".
&'·,····.·0
# ... • • •
•. 0 ' 0 '0' ....

. . '
•· ••....
....
o. .,.
...+- Ebullated . . _
bed
,,~o;. .
• o· . '"
•
• o·
·. .' . ".
• •
...
· · ••
"
• 0
~.~'~.
.' .
_ •
•
_• .:. ~.'O'J .
-. .- .- ,--
•
•
.... " : . . . . .' , ' t .. •
Gas ~
.. .
• ~
--- Bed support..
-
Liouid
•
FIG. 9-11 A diaglam of an ebullated-bed reactor.

•
a concurrent 3<f>TR. Gas and liquid feeds are injected into the outlet line
of the slurry pump, which circulates the liquid-catalyst slurry at a rate
greater than the fluidization velocity. Gas bubbies go straight up and'
reach the gas space. The liquid is strongly recirculated over the down-
corner line and the slurry pump. Liquid corresponJing to the feed rate
leaves the top of the reactor through a liquid le\'e! control valve CV~.
The gas leaves the top of the reactor t!lrough a back-pressure control
valve CV}. The entire liquid prod'!ct stream must be treateri in the
catalyst separation step. in which catalyst is separatt.d from the liquid.
Depending on the properties of the cat't:yst m-:d, FIn or all of the
separated catalyst pellets can be regenerated and then recycled to the
process over the catalyst makeup step. The regenerated catalyst is screened
to eliminate fines and conglomerates. pretrea~ed. if necessary (e.g .. pre-
sulfided), and blended into a slurry along with fresh makeup catalyst
and added to the dowI1comer stream.
,-------1
I
• Gas product
~ _ liquid product
- -
:-,.: - - - to catalyst
• • • CVz separation and
. . ~. ".' . regeneration
'1 .'
•
•
•
•
••
Catalyst •
Gas feed mokeup
Liquid feed
Slurry
pump
FIG. 9-12 A diag, am of a three-phase concurrent transport reactor.
•
r-- --,
. Gos
product
,- . -"
L,q,Jld -- ·- ,
Inlet
,
•
., ,I
••
-. .--• I
,
,- '."
:0 -i.
I
,
·, •
•
•
•. ~
••
•
I
I
I~.-: I
.--.,= - -.- ,,-

Gos inlet •
Liquid
product
to catalysl
separation ,etc.
FIG. 9-13 A diagram of a three-phase countercurrent transport reactor.
The concurrent 3<bTR is suitable for reactions that require short res-
idence time for the gas_ The main ad "antage of the countercurrent 3<1>TR
is the long resirlence time it aHows the gas bubbles. Figure 9-\3 represents
such a reactor system. Gas bubbles introduced into the catalyst slurrY
, i ~
must rise against the down-flowing slurry. By varying this downfiow

velocity, it is possible to decrease the velocity of the bubbles relative to
the reactor wall and hence increase the residence time of the gas in the
reactor. Of course, the velocity• of the bubbles in relation to the slurI"\'•
•
IS constant.
. . The gas flow in the 3<!>TR is plug flow, while the liquid flow is com-
pletelv backmixed.
9.2
TRANSPORT PHENOMENA IN GAS-LIQUID-
PHASE SUSPENDED-BED REACTORS
When designing suspended-bed reactors, the main flow dynamic con- o
cerns of the designer are:

· The p,-essure drop across the reactor
· The dispersion of the 'gas bubbles into the liquid
· Maintaining the catalys( in suspension in the liquid and the means for
achining this suspension
· Achieving adequate mass transfer between the gas and the liquid and
•
•
between the liquid and the catalyst surface

•
. Heat transfer to or from the suspended bed

The major task of the designer is to design for the conditions of the
suspended bed. Once this is achieved, the calculation of the size of the
bed is usually quite simple. In many cases it does not require the use of
computers unless complex kinetic problems are involved. Thus the main
problem is represented by transport phenomena.
Pressure Drop across Suspended-Bed Reactors

The pressure drop across suspended-beri reactors consists of (1) the
pressure drop needed to overcome the column of liquid, gas, and cat-
alyst, and (2) the pressure drop in the device used to inject the gas into
the suspended bed, such as a sparger.
The pressure drop of ebullated-bed reactors can be calculated using
25
relationships developed by Ergun and Oming for expanding beds and
gas flow. When the pressure gradient becomes equal to the buoyant
wt:ight of the packing per unit volume of the bed,
dP
dZ = (1 - e)(ps - pdg (9-1)
the bed begins to expand. Equation (6-2) remains valid, the pressure
gradient being given by Eq. (9-1). The fractional void volume e increases
25
with flow rate. This relationship can be expressed by Eq. (9-2)
?
4.935 a- l.l U", •
1 - e
-- (9-2)
Ps g
where p, = density of solid catalyst particles, kg/m3
a - external-partide-surface/partide-volume ratio, m-I
Um = superficial liquid velocity at mean of entrance and exit
pressures, m/s
Umo - u~ at beginning of expansion
Z = height of bed, m
2
g - gravitational constant = 9.80597 m/5
• •
- viscosity?f the liquid, kg/Cm . s)
The Dispersion of Gas Bubbles and Liquid in Suspended Beds'

Gas bubbles are generated in suspended beds either by injecting gas
•
•
through a sparger or impeller into the liquid or by stirring the liquid'

with a propeller near the liquid surface. Designing for the desired size
and quantity of bubbles is not easy because few reliable data are available.
The bubbles play different roles in different types of suspended-bed
reactors. In the CSTR, ebullated-bed reactor, and 3<l>TR, bubbles simply
constitute the disperse gas phase and have no role in the support of the
catalyst in the liquid. In the slurry reactor, however, the finely divided
catalyst is supported in the liquid only by the effect of the rising gas
bubbles. Consequently, the size and intensity of bubbles are of para-
mount importance for slurry reactors, not only for mass transfer but for
bulk mixing as well.
Gas dispersion in the CSTR can be achieved by borrowing methods
from other gas-liquid phase reactors, such as installing spargers in the
reactors and recirculating part of the gas through the sparger. This may
be the most practical solution of the gas dispersion problem in the CSTR.
Another method of achieving gas dispersion might be to use dispersing
turbines, which suck gas into the liquid through their shaft and disperse
through the rotor. Such turbines are called cavitalors. Power require-
ments for a cavitator type of gas disperser are discussed by Michel and
26
Miller. The cavitator has certain limitations: If the reactor must be deep,
then the vacuum created by the impelJer is not sufficient to draw suf-
ficient gas and force it into the liquid. Also the mechanical design of
impellers presents certain difficulties on scale-up.
A third method of dispersing gas into the liquie! is the surface sti11'ing
method. Surface stirring by means of impellers is commonly practiced
in waste disposal plants. A halfway-immersed impeller rotating on the
•
, , surface of a liquid can dispebe considerable amounts of gas into the

liquid. However, in order to apply this method in a dispersed bed reactor
a large gas-liquid interface is necessary.
A fourth method of dispersing gas bubbles in a liquid mass is to
disperse the gas through a sparger and to stir the liquid above the sparger
by an impeller. Relationships of various parameters in this method of
dispersal have been discussed by Oldshue and Connelly.'" According to
these authors, the most effective sparger ring diameter is for overall
mass transfer considerations 0.8 to 0.9 times the impeller diameter. Dis-
persal of the gas through a center inlet pipe is about 10 to 15% less
effectiye than dispersal through a properly designed sparger, even though
in -both cases the mixture of liquid and gas bubbles is being stirred by a
mechanical stirrer. •
The dispersion of the gas in the s[11n-,1 reactor is achie\'ed by generating
a large number of buhb~es, which also support the finely divided catalyst
in the slurry. The size, shape, and frequency of the bubbles are of great
•
importance. The relationships between various bubble parameters have

been reviewed by amon~ others, Fair,l Calderbank et al.,28 Argo and
Cova,29 and K6lbel et aL ,.30 At superficial velocities (of gas leaving the
sparger) of u < 0.05 m/s the buhbles are discrete, particulate, uniform,
::nd sphericaL They are almost ordered and rise through the liquid at
almost constant velocity, the upward force of the bubbleii being balanced
by viscous drag from the liquid. The liquid has little visually observable
agitation. Bubble sizes of 0.0016 to 0.0063 m may be obtained. This
bt:bble regime is called the quiescent or lamina1" regime. At superficial gas
velor:ities higher than about 0.015 m/s, bubble size becomes independent
of gas flow rate, One result of this is that the rising velocity of individual
bubbles is also approximately independent of gas f:ow rate. Another
result is that in order to increase the gas flow rate the gas holdup lOG has
to be increased.
K6lbel et al.; measured the liquid-phase fraction El.' or liquid holdup,
of bubble columns of different viscosities as a function of superficial gas
velocity u. They found that EL decreases quite sharply and at different
linear rates for different viscosities up to u = 0.005 m/s, then goes through
an irregular transition range up to u = 0.018 m/s, and then decreases
at a constant linear rate in the practicai range up to u == 0.26 m/so
With further increase of the gas rate beyond 0.015 m!s, the reactor
tube becomes filled with bubbles. At still higl.er g<!s now rates, collision
between bubbles causes coalescence into larger bubbles. \\'hich rise faster.
At a superficial gas velocity of 0.051 m/s, the gas phase begins to slug
and the liquid phase becomes violently turbulent. The bubbles become
\ poorly defined, the contacting action is violent and erratic, and there is •
a high degree of bulk mixing. This bubble regime is called the turbulcnt
regime. While the sparger design is very critical in the quiescent regime,
it is not critical at all in the turbulent regime. However. orifices must be
well distributed over the vessel cross section and emergent velocity for
each orifice must not exceed 75 to 90 m/so However, in terms of super-
ficial velocity:!, the gas velocity should not exceed 0.15 mis, since abO\'e
1l
this limit entrainment may become excessive.: For deep \'essels and
liquids of relatively low viscosity (= 1 mPa' s). mean bubble diameter
will be in the range of about 0.003 to 0.006 m.:\I·:\~
Because the aim in reactor design is to obtain maximum capacity per
unit volume, one seldom needs to use the quiescent regime. In am'
reactor of industrial size using the quiescent regime. the bubbles \\"()uld
start to coalesce at some distance from the sparger. and the quiescent
regime would be distul'bed. Thus, one should design for the turbulent
.,
regime. However, this is easier said than done because complete reliance
must be placed on empirical correlations of experimental data and most
probably on the designer's own data. The few published data on the air·
•
water system may perhaps at least guide the designer, since they are
claimed to check reasonably well with systems other than air-water, ac-
cording to Fair, I who presents these data in the form of a plot of frac-
tional gas holdup Ec; versus superficial velocity Uti(; with reactor length/
diameter ratio as a parameter. This plot is gi\'en in Fig. 9-14.
The mean bubble rise velocit), lIn.\/ in bubble columns can be calculated
. . 'n
accordmg to Slemes" as
11 - all
lIB.\/ - I _ =--
t t.
The average bubble diameter in the air-water svs;em increases sharply

with increasing superfICial ga~ \'elocity up to about 0.005 m/s and then
increases very gradually up to 0.05 m/s according to K61bel and Lange-
mann,:lO as shown in Fig. 9-15. The rising yelocit y of gas bubbles in water
111
depends on bubble diameter. as shown in Fig. 9-16. The rising velocity
increases linearly and very sh;.rply up to abollt 0.0015 m in diameter
and then suddenly begins to decline. The minimum is reached at about
0.006 m in diameter and the ye\ocil\' increases slow I\'• from there on.
•
Bubbles rising in a bubble reactor coalesce into larger bubbles, thus

reducing the gas-liquid contact area. Bubble size and bubble coalescence
are important to kl1o\\' because if there is excessi\'e coalescence, it may
become necessary to redistribute the gas abuve a certain reactor height
in order to regain the lost contact area. Calderbank et al. studied bubble
coalescence in viscous liquids and found that rising ellipsoidal bubbles
rapidly coalesce when they come within about 1.6 mm of each other,
center to center. Even when the\". are not that close t ·)g"pther
. at the bottom
\~
••
• of the reactor, they• move toward each other and toward the center of
the reactor. When the center-to-center distance between bubbles at the
Bed length/diameter ratio

.;: OA 2
0-
'" 5
- 0.3
"0
'"
.<::: 10+
-
'"c 0.2
.-
'"
-u
'"
~
LL
01
O. I • 0.2 0.3
Superficial_gas velocity u, m/s
FIG. 9-14 Dynamic gas holdup in bubble reactors as a function of superficial
gas velocity. (FromJames R. Fair,1 excerpted by special pt rmission from Chemical
Engineering, July 3, 1967.)
•
•
•
reactor axis becomes less than 1.6 diameters, bubbles begin clustering
and coalescing to form large·spherical cap bubbles, each formed from
an average of six ellipsoidal bubbles.
The coalescence of bubbles is strongly dependent on liquid viscosity.
The fractional gas holdup EG decreases as a result of coalescence up to
0.04 Pa . s, then is constant at up to about 0.07 Pa . s, and then drops
28
sharply and levels off again at a low value of about EG = 0.007.
During simultaneous coalescence and dissolution (absorption regime),
28
the bubble .,ize remains substantiallv constant.
I
The apparent effect of gas bubbles is to expand the liquid volume in

the reactor. This exp:msion is important in:
· Vessel sizing
· LeYel control location
, Residence: time determination
· Interface area determination for mass transfer and chemical reaction
I f we call ZL the height of clear liquid at no gas flow and ZE the height
of the expanded liquid, including bubbles, the gas holdup is
(9-3)
-
The average residence time SG of the gas in the expanded liquid is:
•
(9-4)
o U
where u is the superficial gas velocity in meters per second. As already
4---------
E
E
-
-'"E
;;; 3 -
r
<:>
:0 2
-'"
, , •
1 2 3 4 5~
Superficiol gos velocity. cm/s

-
FIG. 9-15 Mean bubble diameter as a function of superficial gas velocity.
Column diameter 0.092 m; mean pore diameter 25 fJ.; temperatme 20°C; a!r-
3ll
water system. (From Kolbel and Langemann by pel'mission from Dechema.)
•
•
~ 40
E
u
>- - •
.;:; 30 I-
-
<>
4>
" "-
>
~
.0
20
J:>
::>
J:>
g' 10 t-
'-
'"
,-
a::: , 1
2 4 6 8 10
8ubble diameler, mm
FIG. 9-16 Rising velocity of gas bubbles as a function of bubble diameter.
lO
(From Kolbel and Langelltann by pe, mission from Dechema.)
mentioned, the ploL of Fig. 9-14 correlates the superficial gas velocity u
with the fractional gas holdup cc for various bed length/diameter ratios.
[n the design of elevated-pres"ur~ bubble reactors, it is important to
know the effect of pressure on bubbles. With increasing pressure, bubbles
become smaller for the flow of the same gas quantity. However, in re-
lation to the actual volume of the gas under various pressures, there is
no effect of pressure on bubble size and EL" The specific bubble surface
area is affected by pressure. Kolbel suggests that when designing pressure
columns, the superficial gas velocity, which is related to actual volume
under pressure, be set above 0.006 to 1).007 m/s, since below these values
the specific bubble area is reduced and the transport properties accord-
ingly are adversely affected.
Since the main purpose of generating bubbles in suspended-bed re-
\ , . , actors is to create a large interfacial area for mass transfer, it is also of
interest to measure this interfacial area in any given system. The chemical
method for determining the interfacial area, as discussed by Astarita,34
consists of measuring the reaction rate under conditions such that the
chemical reaction is rate-controlling and then calibrating the procedure
by running it under conditions such that the interfacial area is known,
as in a laminar jet or a wetted-wall column.
,rhen the chemical reaction is rate-controlling, the mass-transfer rate
is equal to the chemical reaction rate:
cfc
Di = d/ = ffi. = f(C) _ (9-5)
2
, where D, - diffusivity. of the ith component, m /s
3
C, - concentration of the ith component, kmol/m
-
4
- longitudinal coordinate, m
- 3
~R. chemical reaction rate function, kmol/m
•
.
and the boundary conditions at the interface are of the type:

n
c, = C, for volatile components (9-6)
dC,
= 0 for nonvolatile components (9-7)
dz
dC, = 0 for all components

C; = C..~ (9-8)
dz
where C"l is the equilibriulll concentration in kilomoles per square meter.
The solution of Eqs. (9-5) to (9-8) is clearly independent of existing
flow conditions and does not affect eithel' the ODE 01' the boundary •
conditions. At steady state we may write:

de
<I> = - DA ' = AF (9-9)
dz
• •
where A = total mterface area, m-
= transfer rate. kmolls
F = parameter which is independent of flow conditions, kmoIl
9
(m- . s)
Hence we may determine A. from the transfer rate <1>. and F can be
determined by calibration experiments, as mentioned above.
The interfacial area in gas-sparged suspended-bed reactors has been
studied by 1. H. LehreL:l~ The following equations were developed to
estimate this area within the right 0rder of magnitude:
(9-10)
2
where A = total interfacial area of bubbles leaving the sparger, m
3
V L = liquid volume at rest, m
3
Q = volumetric flow rate, m /s
Ut = terminal \'elocity• of bubbles, m/s
D B.II = diameter of geometric mean bubble, m
A( = cross-sectional flow area in reacwr vessel, m~
•
• A = 6 i'L Vo A'Sl'H
(9-11 )
utDB.\/A B
where Vo = velocity at sparger orifice, m/s
A SPH = area of oblate spheroid bubble with major-axis/minor-axis
ratio ~ 2.6 where AB < ASPH "" 1.2 A/i
AB = area of bubble
•
SUSPENDED-SED REACTORS 269

,
The reactor designer needs to know, among other things, the fractional
gas holdup 10(; in suspended beds. In bubble reactors, gas holdup lOG has
I
been cOlTelated with Froude and Bodenstein numbers.: ';
(9-12)
where Fr - Froude number

Bo = Bodenstein number
in this study. the bubble columns were small (0.02- to O.15-m-diameter

tubes), the gas was air, and the variables had the following values: u
0.0008 to 0.02 m/s, liquid surface tension 0.022 to 0.072 N/m, p 795 to
1170 kg/m:\ and viscosities 0.00 ~ to 0.022 Pa . s were used.
The gas holdup of tall industrial-size bubble columns ,'ary with height.
r
Deckwer et al.: ;* showed that this variation must be taken into account
in designing bubble reactors. Local values of Cc were described by a
regression function of the dimensionless axial coordinate Z:
(9-13)
with
(9-14)
An integrated mean value EG is defined by
~ .
,
€G = 2: EC(Z;) ~i
,
(9-15)
'. I
The mean Sauter diameter d, of bubbles was found to be approximately

3i
independent of Z. The interfacial area a is calculated from EG :
a(Z) = 6€c <p(Z)/d, (9-16)
The gas holdup lOG increases linearly with gas throughput, reaches a
maximum. and at higher gas throughput values becomes independent
30
of gas throughput. K6lbel and Langemann showed that the profile of
the EG vs. u(; graph depends very much on the kind of liquid, as illustrated
by the graphs of six liquids which they published. In these graphs Ec -
passes through a maximum and then declines. The viscosity of the liquid
has a strong effect on "lOG' With increasing liquid viscosity, the Ec maxi-
"
* Adapted Kith permission from Wolf-Dieter Deckwer, I. Adler, and A hmet Zaidi, "Detailed
Analysis of CO 2 ·Interphase Mass Transfer in a Bubble Column to Pro,'e the Validin' of a
Design Model." in Weekman and Luss (eds.) Chemical ReQ[tion Engineering Houston, 5th
[SCRE, ACS S\"mposium Series 65, 1978, pp, 359-371, Copyright 1978 American Chemical
Society,
•
•
•
mum is reached at a lower throughput value. The dependence of EC on

gas throughput can be expressed by the relationship 10;
(9-17)
where Vc is the linear velocity of fresh gas at the reactor bottom in meters
per secor:d and A, B, and C are constants. This relationship represents
most but not all of the measured data.
The dependence of Ec On the reactor diameter has also been studied
by Kolbel et al.lO With increasing reactor diameter, the Ec vs. Vc maximum
shifts to higher tc and Vc values.
The rising velocitJ of small bubbles (0.003 to 0.006 m diameter) is given
by36:
m/s (9-18)
where a = surface tension. kg/s2

2
g = gravitational acceleration = 9.80597 m/s
P = density, kg/ms
35
Lehrer orovided a reasonable estimate of fractional gas holdup in a
steady-state gas diopersion in a gas-agitated, water-filled batch vessel with
a ratio of liquid height above the sparger to vessel diameter ~ I and
with negligible wall effect:
QI(Ac . Ut) (vo/u t )
\
cc = . = (9-19)
I + QI(Ac . Ut) 1 + (vo/ut)
In this expression Q:>nd Ac are known. The terminal bubble velocity Ut
38
can be calculated by the relationship proposed by Mendelson in 1967
for the rise velocity of a single bubble in an infinite low-viscosity liquid
in the nonlaminar regime:
0.5
2a gDB
+ 2 (9-20)
PL DB
where (]' = surface tension, kg/s2
DB = bubble diameter. m •
PL = liquid den~ity. kg/ms

2
g = gravitational acceleration = 9.80597 m/s
The DB value is obtained from
DB = (D BoDBE)O.5 (9-21 )
where DBE = minimum stable bubble diameter, m

•
SUSPENDED-BED ~--ACTORS 271
A simplified equation for ERE based on balancing surface tension and

35
dynamic pressure effects was .developed by Lehrer :
80- 0.6
E- O.i (9-22)
pI
where I = friction factor and drag coefficient in the nonlaminar region.
S E6
I == 3 (4 + E6) (9-2~)
E = (W/PL Vd(O.5 "'lV~ + RT In(p 1lp2))

w = mass flow rate, kg/s
= efficiency = 0.06
Vu = velocity of gas at spargel' orifice, m/s
p = pressure, bars
E6 = Eotvos number (Weber number/Froude number),
dimension less
The backmixing of the gas and liquid phases in bubble reactors was studied
39
by Afschar et a1. If the gas phase is insoluble in the liquid phase, then
the gas bubbles travel upward in plug flow. However, if the gas phase
is soluble in the liquid phase, then the backmixing of the gas phase is
determined by the intensity of dissolution in the liquid phase. The back-
mixing in the liquid phase is intermediate between plug flow and perfect
mixing. In terms of Bodenstein numbers, bubhle columns operate at
<- ,
Bo = 1 to 16. The Bodenstein number increases with increasing gas
flow and decreases with increasing liquid flow. Of course, large Bod-
enstein numbers are desirable in certain reactions in which a high yield
is needed.
The reactor designer has a great interest in knowing the degree of
mixing in the reacting liquid-bubble system, which is especially needed
for scale-up. Information on two extreme cases can be quite easily ob-
tained. These are (1) perfectly mixed systems, and (2) systems in which
no mixing occurs. For these extreme cases, the reactor designer requires
a knowledge of the reaction kinetics and a laboratory e\'aluation of the
relevant velocity C:O'lstants. Unfortunately, it is not always known with
certainty that one of these extreme cases exist. A partially mixed system
introduces mathematical complexities. Eve:: with complex mathematics
it is necessary to know how much mixing occurs. Assuming that both
the complex mathematics and the degree of mixing are available, the
problem can be approached along the lines of either a residence time
29
distribution or a diffusion modeL The second approach is preferred
for designing gas-sparged reactors.
•
The mixing of a liquid by upflowing gas bubbles was studied by Siemes

and \Veiss,40 who measured the coefficient of mixing in the range 0.0001
2 2
to 0.0075 m /s (I to 75 cm /s), depending on the size of bubbles and gas
through put. In the laminar regime the mixing coefficient increases about
linearly with increasing gas throughput, while in the turbulent regime
the mixing coefficient increases progressively with throughput but then
reaches a peak. At low gas rates, the viscous drag of the liquid is re-
sponsible for the formation of turouIent eddies and mO\'ement of the
29
liquid, which constitutes axial liquid dispersion.
The one-dimensional axial backmixing model for the liquid phase of
bubble reactors leads to the relationship:
C
In C = - uLz1K1. (9-24)
lJ
where K/. = liquid-phase backmixing coefficient. m~/s

It/. = superficial liquid velocity, m/s
z = longitudinal coordinate (distance from sparger), III
This means that if udKL is constant, the plot of In(ClC,,) \'5. z gi\'es a
straight line with the slope - ujKL • Contrary to this model, Deckwer et
al.-11 ha\'e found that over a certain range of gas throughput for con-
current and countercurrent flow, the mixing in the liquid phase of bub-
ble columns is not uniform but splits into two different regimes:
•
-. K i . = (0.000 I 2 ± 0.0000 12) D~5 uZ 5
in the lower
region of the
.
-
column
KL - (0.00024 -+- 0.000018) DP uZ· 5
m-Is
Q
in the upper
region of the
column
K L - (0.0002 ± 0.000015) Dj" u~/
<)
and m-Is if a single
• • •
nuxmg regIme
•
eXIsts
Here. DT is column diameter in meters. _

Longitudinal mixing in gas-sparged tubular reactors has also been
discussed by Argo and Lova,29 who measured the superficiai dispersion
coefficient D, of liquids <ls a function of superficial gas ,'elocity. In open
tubes D, increased linearly above 0.025 m/s but was roughly constant
under pressure. Their data did not lend themselves to generalized
correlations.
•
Also, Peelet numbers based on tube diameter as a function of super-

ficial gas velocity have been measured for turbulent flow regime.!!'! This
Peelet number is:
(9-25 )
where VR = actual mean gas velocity ,.elati·vl' to actual mean liquid

velocity = (u/Bd - t'f., m/s
VI. = actual mean liquid velocity, m/s
Dd = dispersion coefficient, axial. m~/s
For superficial gas velocities up to 0.2 m/s, PexI \-;tried only he(\\'een O.S
and l.0.
Other relationships worth noting are as foll()\\~:
. Diffusivities increase with tube diameter.

. Gas holdup Bc; rises rapidly with superficial gas velocity, and then,
above 0.076 m/s, levels off at about c(. = 0.3 to 0.4.
A similar result was obtained bv Eissa et a!. ~~ ;Uschar et al.:\\1 observed

;
. that cc; varies proportionally with the superficial gas velocity up to 0.05
m/s a'1d then, levels off.
~he data of Argo and Cova for axial diffusiyities may be used to
29
estimate order-of-magnitude diffusivities.

-A continuous first-order reaction at steady state may be represented
by the following differential equation:
.- ,
•,
.
2
de - d e Dol. ke
..
2
• - (9-26)
dz dz VL 7.. ' I.
For a similar case of a packed tubular reactor. Dankwerts~:\ de\'eloped

the following solution:
(9-27)
where
-
- ••
l'La
A* = 2(1 + a) exp --=-- (Zr - z) - 2(1 (i) exp
2 [JaL
uLo.Zr ,>
B* = (1 + 0.)2 exp - (l - ilt exp
2 DaL
•
with
• 4k DaL
a= I -t- 9 (9-28) .
v·L
where Zr = reactor length, m

z = longitudinal distance in reactor, m
DaL = dispersion coefficient, axial, li--juid phase
VL = actual mean liquid velocity, m/s
•
k = reaction rate constant
This equation is also applicable to bubble reactors. If D af• is known,

Eg. (9-27) can be used with the help of a cc:nputer program to calculate
the reaction rate. Thus the accuracy of the reaction rate comtant k
depends on that of the axial dispersion coefficient D uL '
Radial as well as axial dispersion in concurrent bubble columm was
42
studied by S. H. Eissa et aL by means of tracer experiments. Dispersion
was found highest in the central core region with a maximum value
slightly shifted from the reactor vessel center. These authors introduced
an effective local dispersion coefficient E, which reflects the combined effect
of axial and radial dispersion. However, it was understood that the radial
contribution is very minor compared with the axial contribution. For
further simplification, Eissa et aL developed a unifOl m dispersion model
that uses mean velocities and mean dispersion coefficients instead of
point properties. The mean effective dispersion number in the bubble-flow
. .
regime was found to increase with gas velocity up to about 0.05 rnIs
(which coincides with the start of the transition regime), to decline to a
minimum value (close to the beginning of the slugging regime), and finally
• •
to Increase agam.
Axial back mixing of liquid in three-phase fluidized beds, i.e., ebullated
44
beds, was studied by Y. R. Vail et aL by a tracer technique using a
45
relationship developed by Gilliland and Mason :
(9-29)
3
where C = concentration of the tracer at axial coordinate z, kmollm
Cx = concentration of the tracer in the total flow leaving the
• 3
reactor, kmollm
v = velocity M the fluidized stream, rnIs
2
KaL = coefficient of axial dispersion, liquid phase, m /s
B = a constant
, •
•
Vail et al. concluded that:

· Tracer concentrations approximately obey a logarithmic law.
· Iucrease of the gas velocity intensifies axial backmixing.
· Increase of the liquid velocity weakens axial backmixing.
· The presence of a solid dispersed phase considerably reduces axial
backmixing.
· Radial irre-gularity in concentration increases with increased liquid
feed and decreased gas feed.
Finally, extensive pilot-plant data are being developed on ebullated-
bed fluid dynamics bv Amoco Oil Company under contract with the U .S.
Dep<>,-tment of Energy"6 in order to provide design data for the H-Coal
process. Relationships among se\~ral parameters such as u, Uv Ec. EL.
and Ep are already available.
Suspending the Catalyst in Suspended Beds

The maintenance of the catalyst in suspension as a slurry is achieved in
different types of suspended beds b)" different means:
· In CSTRs, propeller agitat;~)I1 keeps the catalyst in suspension.
· In slurry reactors, rising bubbles create the necessary turbulence to
keep the finely divided catalyst in suspension.
· In ebullated-bed reactors, the liquid upflow counterbalances the set-
tling velocity of catalyst particles in the liquid .
•
· In 3<l>TRs, the liquid upflow must be much greater than the settling
velocity of catalyst particles so that they are entrained with the liquid.
The terminal velocity of small spheres settling in a liquid is given b:-'
Stokes' law:
q
gd; Ap
11, - (9-30)
18J.L
2
where g - acceleration due to gravity, 9.81 m/s
/lp = difference of density between particles and the liquid.
kg/m3
J.L = liquid viscosity, kg/(m . s)
#
In both CSTRs and slurry reactors, it is necessary to use a very fine ..

catalyst, of particle diameter in the order of a few hundred micrometers.
•
so that it does not settle easily. The design of mixing and stirring devices
is still based on empirical knowledge. The reader is referred to the
literature on mixing. Some very good annual rniews by J. Y. Oldshue
are available,47 as well as a paper on suspension of solids and dispersal
of gases in mixing vessels. 48
In geometrically similar baffled agitated vessels. the power input frol11
the impeller is related to rotational speed by the equatipn:
-
Np - KR e -
a - P,,(u:
11V
1
D';,p ) (9-31 )
where NI' = the power number

K, a = dimensionless constants depending on the system geometry
N = impeller speed, S-l
. Di = impeller diameter, m
p = fluid density, kg/m3
P' - power, W
9
Nienow and Miles· reported values of Xp for a \'ariety of impeller-vessel
geometries as a function of the Reynolds number. These \'alues may be
quite useful in designing CSTRs.
The ebullated-bed reactors operate in a relatively narrow range of
solution upflow between the fluidization velocity and the total entrain-
ment velocity. The operators must know at all times ho\\' much the
catalyst bed is expanded and where the top of the bed is located. This
is usually achieved by measuring the bed density across the diameter at
,
several levels by means of commercially available instnllllents.
Mass Transfer in Suspended-Bed Reactors

Mass transfer in suspended-bed reactors has been fairly widely discussed
by Carberry,50 Satterfield,3! Kolbel,30 and Johnson et al..'>l The phenom-
enon is basically the same as that in fixed-bed bubble reactors except
that the quantitative relationships of the various variables change de-
pending on the choice of reactor type.
Reaction rate expressions in suspended beds affected by mass transfer
3
can be developed as follows !:
Let us call NI' the IlJ.olar flux in kilorcloles per second per cubic meter of
the key reactant in the bubble-expanded slurry. At steady state we haye:
•
N v = kL . ab(C, - Cd (gas interface ) bulk liquid) (9-32)
=
-
he . ap (CL - C.) (bulk liquid ) particle) (9-33)
= ks . apCs (surface reaction) (9-34)
•
where kL = gas-liquid mass-transfer coefficient, m/s

k, = bulk liquid-to-partide mass-lrallsfel' coefficient. m/s
k, = surface reaction rate coefficient. l1l!s
ab = bubble surface .;;·ea per unit \'olumC' of expdnded slurry .
., ~
m-tnY
al' = ext~n(\r catalyst surface per unit \'(llu1llc ot expanded slurry.
1
m"l.n:
c. = equilibrium concentration of gaseolls re;H.'tal1t in liquid.
{
kmolh,l
Cl. = reactant concentration in bulk liquid. kl1101 m"
l
C. = reactant concentration at catal\'st surface. kmollm •
In the last three equations C. can be taken from books. but Cl. and C.
are difficult to obtain. Therefore the latter qu,wtilies m<l\ be eliminated
from the expressions as follows.
Dividing both sides of Eq. (9-32) by X, and rearranging gives:
C, I + Cl .
-- (9-35)
s.•
Similarly, Eq. (9-33) gives:
CL - I C.
- .,.., (9-36)
.v
• k,ap ,",
•
And Eq. (9-34) gives:
C. 1
-=-- (9-37)
s. • k,a",
•
B\ combining Eqs. (9-35), (9-36). and (9-37) we obtain:
(9-38)
iV" •
If buobles and catalyst 'particles are spherical:
(9-39)
•
27. CATALYTIC REACTOR DESIGN
6m
ap = (9-40)
p,dp
3 3
where Ec = gas holdup in the liquid, m gas per m expanded slurry
3
m = catalyst loading, kg catalyst per m expanded slurry
p, = catalyst particle density, kg/m3
DB = bubbJe diameter, m
Su!::stituting Eq. (9-39) and Eq. (9-40) into Eq. (9-38) gives:
C, DB p, dp 1 1
= + - +- (9-41 )
N v 6kL Ec 6m ke k,
Here, we see that C.lNv is a linear function of lhn. At reasonable catalyst
loadings f7,1N" increases' with lIm. At extremely high catalyst loadings,
IIm ) 0, N" ) 6kLEcC,/dp, and the rate becomes controlled by the rate
of gas absorption AL'
32 52
The mass transfer from gas bubbles to liquids is relatively well known. •
Small bubbles «0.0025 m diameter) behave like rigid spheres and mass-
transfer coefficients from the interface to the liquid are correlated by
the same relationships that apply to small solid spheres. The mass-trans-
fer coefficient ke for "l single sphere at rest in a large volume of stagnant
fluid is given by
(9-42)
wher~ DIm is the molecular diffusion coefficient for the species diffusing
,, •
\- , in the fluid.
I 53
Mass transfer for flow past single spheres may be correlated b/ • ;
= 4.0 + 1.21 Peo/3 (9-43)
where Sh is the Sherwood number = ked/DIm and Pe is the Peclet num-

ber = dpu/Dlm' Catalysts used in slurries are not always spheres, but it is
convenient to use a diameter corresponding to a sphere having the same
ratio of external surface to volume, and hence the same settling velocity,
as the irregular particle. The termiI,lal velocity of settling for small spheres
is given by Stokes' law [Eq. (9-30)]. The corresponding Peclet number,
denoted by Pe*, is: .
•
at terminal velocity (9-44)
•
and the corresponding k; may be estimated at settling velocities Pe* < 500
by combining Eqs. (9-44) and (9-43). The results are plotted in Satter-
•
field's Fig. 2-5 (page llS of Ref. 31). The coefficient k; is the mass-
transfer coefficient between bulk liquid and a particle settling quietly .
•
•
SUSPENDED-BED REACTORS
100
•
"-
---
~
u
if)
10
5('13.7
"-"" -E
v
Cl
1
0.1 1 10
,1/! d4/3 -1
P P hP.
FIG. 9-17 Effect of power input on mass transfer to spheres suspended in an
agitated liquid. (From Brian and Hales,53,54 by pel mission froln the
Institute of Chemical Engineers.)
Under turbulent conditions in a reactor the actual value of k{ is greater

than k;. Satterfield suggests as a first approximation taking k{ as twice
the value calculated from the combination of Eqs. (9-43) and (9-44).
In mechanically stirred reactors, ke can be calculated from the power
input to the slurry according to Briand and Hales,53.51 provided the
power in pm is known. This relationship is presented in Fig. 9-17. Here,
the ordinate is Sh/Sc ' , and the abscissa is P" 'd~\ pJIJ. where pr is the
power input and is expressed as power per unit mass of slurry. Both
groups are dimensionless. In SI units P' must be expressed in wattJ per
kilogram of slurry, According to Satterfield,31 this method is the soundest
way of estimating ke> provided power input .can be calculated with rea-
32
sonable assurance, Calderbank states that when a dispersed phase is
suspended or is in free rise or in free fall and under the influence of
gravity, the heat-transfer and mass-transfer coefficients are almost com-
pletely unaffected by mechanical power dissipated in the system. In other
words, it does not pa~' to stir a catalyst suspension beyond the point at
which the particles are held in suspension. Thus it can be concluded
that the power input to keep suspended beds in suspension should not
be used to estimate k, unless (l) the power is computed properly, and
(2) no power is wasted.
Mass transfer from large bubbles is greater than that from small
spherical bubbles since the large bubbles undergo internal circulation
and their shape becomes distorted as they mO\'e through the liquid. The
correlation: •
•• <
P. g{ ~p
(9-45)
p-"
applies to these large bubbles,3I.:l2 where Sc is the Schmidt number for

the liquid, JL/pD.
Uc = average superficial gas velocity, based on inside reactor

diameter and temperature and pressure of gas, mls
N = stirring rate, rls
m = catalyst loading, kg/m:l of liquid
A,B = constants
The values of A and B depend on the mechanical construction of the

reactor vessel, agitator, baffles, and sparger and require separate eval-
uation in terms of these mechanical factors. For the two-blade flat im-
-I
peller used by Johnson et al.~ the values of these constant" were A = 29.4
and B = 6.55 X 10-1.
l7
Deckwer et al. deyeloped a modef of mass transfer in an industrial
size bubble reactor for the absorption and desorption of CO~ in H 2 0.
They started with the following assumptions:
· \'alidity of Henry's law

· .-\:~ial dispersion in liquid phase
· Plug flow in gas phase
· Radial dispersion nef;lected
· Pressure P varying line~rly with z according to P = PT [I + ex (1 - z)1
\,'here PT is the pressure at the column top
· Gas hold up Cc and interfacial area \'aning with:
· \'ariable u. • .
· Reaction of CO2 with H 20 (in the system of experiment) neglected;

gases assumed all inert
· Gas-phase resistance to mass transfer neglected
The dispersion coefficient in the liquid phase is DJ = 2.7 D~Au":l where

DJ = reactor diameter in meters. Although E(; \-aries with z, ex can be
taken to be almost constant:
ex = pg( I - El, )l//P,
where ZT is the total bubble cGlumn height in meters and u PO - x) =

11" PAl + ex)(l - xo), the subscript 0 denoting the inlet of reactor. The
• •
model equation for CO~ balance of the gas phase is:
-
dX _ -Stclfl(z)(l - X)~ (!3(:)X _ Pi (9-49)
dz Pr
•
282 CATAlYTIC REACTOR OESIGN
and that for CO2 partial pressure in the liquid phase PL is:
,pPL
9
d z-
+ a' (9-50) .
where x = mole fraction of C09-

'P(z) = a regression function of z
PL = partial pressure of CO 2 in liquid phase
6£c. ____Z...:..T_ _ _ RT d' . I
Src = kL
d, U'l(l +
• H' ImenSlOn ess
a)(l - Xo)
d, = mean Sauter diameter, m
H = Henry's constant
(3(z) = 1 + a(l - z), dimension less
= uLZr/DaL , dimensionless
= axial dispersion coefficient in liquid phase
6€c Zr .
- kL d ' dlmensionless
sUL
•
hL = liquid-side mass-transfer coefficient

UL = superficial liquid velocity
The initial condition for the gas-phase equation is

x(O) = xo
•
The boundary conditions for the liquid-phase equation are, for the case
of concurrent flow (a = -1): -
_1_-_£"""c'P!.-'(--,O)~d~PL::..;.(O~)
= Pu +
and for countercurrent flow (a = + 1):
..
where the subscript i denotes inlet condition.
"
The gas-phase and liquid-phase differential equations are nonlinear

boundary-value ODEs that have nonconstant coefficients. They can be
solved numerically by the method of Lee (see Chap. 2). For certain
parameter combinations, the method of Lee causes problems, as re-
ported by Deckwer et al.,~7 who explain at length how they circumvented
the difficulties.
30
K61bel and Langemann studied the absorption of oxygen in water
and the desorption of oxygen by nitrogen and found that the mass
transfer coefficient increased linearly with superficial gas velocity up to
about 0.05 m/s and then declined, also linearlv.•
This bend in the curve
seems to reflect the How regime change.
The mass transfer in gas-liquid fluidized beds or ebullated beds has
57
been studied by K. 0stergaard et a1. They found that 6-mm spheres
were characterized by 10 times higher mass transfer than I-mm spheres.
Surprisingly, no spheres at all gave mass-transfer intermediate between
that of 1- and 6-mm spheres. Mass transfer increased with the gas flow
rate and was approximately proportional to the gas holdup. On the other
hand, variation of the liquid nte caused little change in mass transfer.
Heat Transfer in Suspended-Bed Reactors

Suspended-bed reactors have an in;portam advantage over fixed-bed
reactors in heat transfer: exothermic heat may be removed much more
easily from the former by simply installing cooling coils in them. Another
characteristic of the suspended-bed reactors (which may also be consid-
ered an advantage) is that they are operated isothermally and are im-
.
"
""
mune to localized hot spots.
Exothermic heat can be removed fro.m suspended-bed reactors:
· By the vaporization of reactants or products
· By the vaporization of an inert solvent
· By the recirculation of the liquid through an external cooler
· By direct heat transfer to the \"essel jacket or to cooling coils installed
in the reactor (only this case will be discussed below)
Heat transfer in a suspended-bed reactor can be characterized as
fullows: -
· The liquid temperatu.re in the reactor is quite U11iform (it operates
isothermally).
~
· For reactors larger than 0.07 to 0.10 m in diameter, there is no di-

ameter effect on transfer rates.
,
. Process-side coefficients are not influenced by transfer-surface ge-

ometry (tubes vs. jackets),
. Process-side coefficients are quite high.
The heat-transfer coefficient h of various liquids in slurry reactors
have been correlated with the superficial gas velocity 11, as shown in Fig,
1
9-18. The correlation equation is (in SI units):
J1 -- <) 0 '4
o.o-t U
(I.~c
(9-51 )
where h is the heat-transfer coefficient in kilojoules per second per square
meter per Kelvin and u is the superficial gas \·elocity in meters per
secord. In uses units u is in feet per second. the coefficient of u is
1200, and h is in British thermal units per hour per square foot per
degree Fahrenheit.
Data for liquids other than water \,·ere correlated by the relationship:
t •• _~.
hot her liquid

- p ..~ otht'l (9-52)
liquid
where Pr = Cp~/AL = Prandtl number of the liql)id

AL = liquid ther'Ilal conductivity, kj/(m . S • K)
cp = specific heat at constant pressure. kJ/(kg . K)
= viscosity, Pa . s = kg/Cm . s)
Suspensions of solid catalysts tend to gi,·e higher transfer rates than

liquids only because of the scouring action of the solids on the walls.
Reliable correlations in this field hale yet to be dneloped. Consequently,
Fig. 9-18 and Eq. (9-51) can be used only for thin suspended beds of
very finely divided catalysts.
58
Seth and Stahel have discussed heat transfer from helical coils im-
mersed in agitated vessels. The reader is referred to this detailed paper.
59
Lavingia and Dickson have dewloped the following correlation for
heat transfer in an agitated vessel with coils to a n'·o-phase liquid system
4 6
for an impeller Reynolds number range of 3.7 X 10 ::s: Re ::s: 1.1 X 10 :
(9-53 )
where subscript w denotes "wall"" and :\ u is the :\ usselt number. In this
system 'both phases are liquid.
According to K6lbd et al. 10 the heat-transfer coefficient h increases
very steeply with linear -gas velocity 1.'(; and asymptotically approaches a
maximum value of 4500 kC<tI/(m~ . h . K) or 5.23 kj/(m • s . K) at a gas
2
flow rate of about 0.1 m1s. This maximum value of the heat-transfer
coefficient cannot be exceeded by further agitation by the bubbles. This
•
2000---------------------------------------
•
• + 30%
1000
800 f--
_-- - -
-- + 0 0 ++ • •--• -
L:: 600 f-- ---:- + -0 0 0 A -...!---'--30 01,
o
+ 0 a 11 -f-- 0
;
-
400 I- -
_ 0 _ _ _.+
v-
fl
---,
-v..... •
et-
_
~
-x
.x- -x- legend
0 Water
- 35
OT
• - Water _ _ _ _ 1. 5
+ - Woter
.c - o - Machine oil 0.63
200 • - Spindle oil'_ _- l
A - Woter
X - Ethylene glycol 0.33
v - Isopropanol - water 0,94
100 __ ....L..
0.005 001 0,05 0.10 0,50
Superficial gas velocity u, It Is
FIG. 9-18 Heat transfer in gas-sparged reactors for a number of different
materials. (Excerpted by special permission from James R. Fair, I Chemical Engi-
neering,July 17, 1967.)
•
value is considerabh' higher than the \'alue of heat transfer in tubing of
the same diameter in \\'hich only water is flO\"ing, The intensive heat
transfer in a bubble column is explained by the cOI1\'ecti\'e Ileat trdnsport
caused by the radial velocity component of the liquiL: around rising
bubbles. Figure 9-19 i~lustrates the radial velocity component preceding
and following a rising bubble.
• Heat transfer in bubble reactors that have diameters much larger
"
>. , than the bubble diameters can be described by Kolbel et al. 's relationshipl":
.)
St = f(Re . Fr . Pro) - (9-54)

where St = Stanton number = h/(i'C; . P . (p)
.)
Fr = Froude number = <,Z/(g . D T )
Measured data were rlotted b Kast on a double logarithmic scale with

5
St as ordinate and:' ReFrPr- as abscissa (Fig. 9-20).
The heat transfer coefficient decreases \\'ith increasing viscosity of the
. 'd PIMse. 10
\lqUl
•
9.3 •
ADVANTAGES AND DRAWBACKS OF
VAR!OUS SUSPENDED!BED REACTORS
Suspended-bed reactors have a number of interesting advantages over
fixed-bed reactors. Of course, they, also have some drawbacks. These
•
286 CATAlYTIC REACTOR
advantages "and drawbacks have been summarized on Table 9-1, where

an x in a given box means Hyes, that is true." For example, it is stated
On the first line that "diffusion of reactant through bulk liquid is min-
imized by intensive agitation." This is true for CSTR and 3<1>TR but not
true for slurry and ebullated-bed reactors. Thus in the first line an x
denotes an advantage. However, in the bottom three lines, where dis-
advantages are mentioned, an x denotes a drawback.
9.4
PROCESS DESIGN OF SUSPENDED-BED REACTORS
The strategy in designing any type of suspended-bed reactor is to first
design the method of catalyst suspension and the gas-liquid contact the
rest is then relatively simple.
Process Design of C.3TRs

In the CSTR the method of catalyst suspension is some kind of me-
chanical stirring-. Th'Is the main strategy is to design the stirrers and the
gas-liquid contact.
General Procedure
Let us develop the design equations for the CSTR. The characteristic.
property of the CSTR is that the composition at any point of the ex-
panded liquid phase is the same. Referring to Fig. 9-1, let us specify:
v 3
= volume of expanded liquid, m (net reactor volume)
Pc = mass of catalyst per u~it volume of expanded liquid, kg/m3
Reactor
wall
Gas
bubble
Va
•
V liQui
r
•
fiG. 9-19 Liquid flow around a bubble near the wall of the slurry reactor:
v. = axial component of the flow velocity; Vr = radial component of the flow
velocity. (From Kolbel, Hammer, and Langemann'o by pe/mission from Chemiker
Zeitung.)
•
SUSPENDED-SED REACTORS 287.
,
10° ~r--------
-
10-3 _.--1'_.--1'_--"-,-----'
10-1 100 101 10 2 10 3
1
2 5
(Re'Fr ·Pr · p
RG. 9-20 Heat transfer in bubble column in dimensionless t'resentation. (Fr?m
W. Kast, "Untersuchungen zur W 01 meiibergang in Blaseltsolflen," Chem. Ingr. Tech.
35(11):787 (1963), by pelllZission from Dechel1la.)
XI = fractional conversion of the critical reactant at inlet to t~e reactor

(assuming the reaction is run in more than one reactor in series),
dimensionless
-
Xq = fractional conversion of the critical reactant at outlet from the
reactor, dimensionless
TU' = reaction rate. amount of critical reactant converted per second
and per kilogram of catalyst in suspension. kmol/(s . kg)
The molar balance for a time element Lle and a volume element LlV
can be written:
(Moles of reactant fed to volume LlV)
- (moles of reactant leaving volume LlV)
- (moles of reactant converted in volume LlV)
• •
= (accumulation of reactant in LlV) (9-55)
- At steady-state operation in a CSTR, the accumulation terlll is zero_ In

a CSTR with constant concentration throughout the expanded liquid
volume, the element Ll V could be easily integrated to obtain the whole
volume of expanded liquid, which we may call the net TeactoT volume V.
Moles of reactant fed in time tle is F)'o(l - xI)Ll6
Moles of reactant in outlet stream in time Lle is Fyo(l - X2)Lle
Moles of reactant converted in volume V and time Lle is Tu,TjVpcLle
Substituting thest: expressions intc Eq. (9-55) gives:
Fyo(l - xl)tle - F)'o(l - x2)M - TjTYPc Lle = 0
•
We can divide all the terms by M, simplify, and rearrange:
(9-56)
•
TABLE 9-1
Advantages and Drawbacks of Suspended-Bed Reactors
Ebullated
CSTR Slurry bed 3q,TR
Diffusion of reactant through

bulk liquid is minimized by
• • ••
mtenslve agitation x x
Intraphase diffusion is
minimized by using finely
divided catalvsts ~
x x
Catalyst stays in reactor, no

catalyst-product separation
step necessary x
Catalyst can be constantly
withdrawn. regenerated. and
made up without shutting
down reactor x x x x
Removal of exothermic heat is
easy. high h x x x x
Isothermality favors aiming at
a given selectivity x x x x
Pelleting cost for the catalyst
can be avoided x x
Higher rates of reaction per

unit weight of catalvst x x
Catalyst
, must be added to
fresh liquid flow and removed
•
from liquid product.
Handling of slurries requires
special techniques x x •
High conversion requires

several reactors in series x x x x
Design data generalh' not
available x x x x
It is important to exactly define F. We will define it as the flO\\" of liquid

feed per unit time, kmolls, not the reactant flow!
The average residence time in the reactor can be calculated as £()lIows.
First multiply both sides of Eq. (9-56) by M/pi., where ,VI is the average
molecular weight of the liquid feedstock in kilograms per kilomole and
Pi. is the density of the liquid feed in kilograms per cubic meter.
•
VM _ FM )'11 (x~ - xd
-""- - (9-57)
Pt PI-P,T!
Here FM/pI. is the volume feed flow and has the dimensions of cubic
meters per second. while V represents the expanded liquid volume of
the reactor and can be written as
\.
V = I.
t/.
where V L is the nonexpanded actual liquid volume in the reactor in cubic

meters and EL is the liquid holdup (dimensionless). Equation (9-57) can
be , ..-ritten as:
or
rhe left-hand side of Eq. (9-58) represents the average residence time
e in the reactor and we write:
-
e= (~1-59)
Pr ,\1 TIle
The heat balance equation for the steady-state CSTR (without the
accumu~ation term) can be written as:
Heat in streams heat in streams

-
fed to volume A\' leaving volume ~V
heat transferred from

+ = 0 (9-60)
surroundings to AV
V\re must choose a base state (temperature. pressure, and composition)
from which to evaluate the energy. Let us assume that the enthalpv per
mole above the base state of the feed streams is H, and that of the product
stream is H 2 • If FT is the total molar feed rate, including both the liquid
and the gas, the first and second terms in E(j. (9-60) are FrH, A6 and
FT2H~ AS, respecti\·ely. After dividing all tem1S by as, the balance becomes:
FrH, - Fr~H~ + i(.-l},(T, T~) = 0 (9-61 )

where h = overall he:at-transfer coefficient, kJ/(s . m~ . K)
2
A.h - effective area of heat transfer, m
Tx = temperature of the exterior or surroundings or of the
cooling medium in the jacket 0\' the cooling coil, K
T2 = reactor exit temperature
•
•
In Eq. (9-61) the difference between HI - H z must be replaced by a

function of T, r w , and W. This is accomplished by considering the en-
thaIpy change when feed at T J is first heated to T2 and then changed in
composition tothat of the product:
(9-62)
where Cp is molar heat capacity in kllo~oules per kilomole per Kelvin

and W is heat of reaction per mole oflimiting- (key) reactant in kilojoules
per kilomole. The combination of Eqs. (9-::'1) dnd (9-62) gives:
FrCp(TJ - T z) - (X2 - x,)D.H Fyo + /z.;l,,(Tx - T z) = 0 (9-63)
Now we can replace (X2 - xJ from Eq. (9-56) and simplify:
FrCp(T J - T 2) - TVu. V p~H + hAh(Tx - T 2) = 0 (9-64)
In case more than one reaction takes place in the reactor, Eq. (9-64)
must be written as:
Finally, we need the rate equation in form of the Arrhenius expression:

!:Ko = 'TjYu' = "Tp4exp(-E/RT) C:C~ (9-66)
In most cases of liquid phase reactions the kinetic expression becomes
much more corn plex because of the additional involvemeni. of intra- and
interparticle transport phenomena. Thus the design procedure consists
in calculating the transport conditions to create the desired gas-liquid-
catalyst mixture, to solving Eqs. (9-66) and (9-56) for V, and from the
V value calculating the necessary heat-transfer surface A h • From V the
amount of catalyst can be easily calculated.
Example of CSTR Design

The example for CSTR design will be the same hydrodesulfurization
process used in Chap. 7 for trickle-bed reactors. Let us assume that we.
want to build the same 250,OOO-t/yr plant, but with the trickle-bed reactor
reFJa:::ed bv a CSTR of the type shown in Fig. 9-3. The following aspects
of the process will differ from the trickle-bed case:
•
· The catalyst will be smaller, Yz-mm-diameter (dp = 0.0005 m) spheres,
60
which gives an effectiveness factor of 0.99.
· A liquid/solid volume ratio of 10 : I will be assumed in the slurry.
· A gas circulation rate twice the fresh gas rate will be assumed.
· A conversion of x = 0.65 is aimed at.
•
,
Let us now calculate the total volume of expanded bed per cubic meter
of liquid feed:
1 - EG
1.1
The amount of gas recirculated is twice the amount of fresh gas dictated
by the H2/oil mole ratio. For each cubic meter of pure liquid we will
have: '
(569.3 kg/m3)(0.S m:! H 2(NTP)/kg oil)(2.)(648.2 K)(l.01325 bars)
(55 bars)(273.2 K)
= 22.88 m H2 per m~ oil
S
The dyndmic holdup EG can be calculated from Fig. 9-14 as EG = 0.26

for a maximum gas velocity. Then we will have:
EL
_
-
1 - 0.26 _
-
0 .
67"7
"- El' = 0.1 EL = 0.06727
l.1
and for the catalyst density (including pores)
= PB = 950 kg/m3 = 48 k 1m3

Pp 1 _ t 1 _ 0.36 1 4 g
The catalyst density in the slurry is

Pc = Pptp = (1484 kg/m3)(0.06727)
= 99.86 kg/m3
"
,
, The design equations are:
V = ~F)"",,'o -,-(X=-..2_-_X-'!.I) = (9.3339 kg/s)(0.8358)(0.65)
Pc 'Ww (670 kg/kmol)(0.99) PeT".
The key reaction rate is:
4
Tu' = 2.8 X 10 exp( - 82,0601RnC LOC/pc (7-28)
Other side-reaction rates are:
3
!K3 = TJ3 1.8 X 10 exp( -72,060IRT) C,,,C~O/Pe (7-30)
IS
!K4 = TJ4 2.5 X 10 exp( - 243,000IRT) CmyChy()/Pc (7 -31)
•
3
!K5 = TJ5 1.0 X 10 exp( -46,860IRT) CmcChcO/Pc (7 -32)
•
We will assume that all ~ffectiveness factors are equal to 0.99, and we
express the activity of the catalyst in the slurry reactor by the same kinetic
equation, Eq. (7-28), that expresses the activity in the trickle-bed regime,
taking in consideration that
. .. ,
•
This is a pure assumption fOl purposes of comparison of the slurry and

trickle-bed regimes and does not reflect the facts. With these assumptions
the reactor volume is calculated to be
'
\,= I~~-
.:1 I I III ~
This is, of course, the expanded liquid volume only. The total volume
of the tank must also include the gas volume and the "olume of the
cooling coils instaIIed in the reactor. Thus we can sP!ect a diallleter of
1.0 m for a reactor of the type of Fig. 9-1. Then tlIe hemispheri~al
bottom part will have a volume of:
0.5 (-rr/6) Do: = 0.2618 m'
The cylindrical part will have the volume of:

1 .:J~7~I - 0 ._
'>6100 -- 1<)1-<)
.;1 J_ nl :,
The height of that section without considering the coil "olume will be:
(1.3l52/0.5~11') = 1.675 m
'Ve will probably ha','e to design the cYlindrical part of the reactor for a
height of 2.0 m to accommodate the coils and other internals, e.g., the
sparger and the total reactor volume "'ill be:
2
(2.0)(0.5 11') + (2)(0.2618) = 2.094 m~
In comparison with this CSTR reactor size, the plug-flo\\' trickle-bed
reactor had a I.S-m diameter, and a cOI1\'ers:on of 65% was reached at
3
,
a length of 11.21 m, indicating a volume of 19.81 m .
What this example shows is simply that catalysts having the same
• activity in the trickle bed and the CSTR need a trickle-bed "olume 12.5
times as large than the CSTR volume. The catch is that the same catalyst
has a much lower activity in a submerged reaction than in a trickle-bed
regime otherwise all trickle beds would be replaced by CSTRs having
about 8% of the volume of the trickle beds. This is not being done.
Let us notice that we did not need a computer to calculate the volume
of our CSTR. However we might have needed a computer if the reaction
kinetics and transport phenomena had resulted in messy mathematics.
Once the volume of a CSTR is determined for the key reactant, the •
conversions of ot},u reartant~, e.g., nitrogen, hydrocrackables, and un-

.
saturates, can be calculated by using the already' known reactor volume
and the design equations for each reactant, i.e., Eqs. (7-30) to (7-32).
The heat of reaction can be removed through cooling jackets or cool-
ing coils in accordance with Eq. (9-65). Also part of the reaction heat
can be removed by supplying the feed at a temperature below the re-
action temperature. Jacket cooling is unattractive in high-pressure re-
,
actions such as hydrodcsulfurization of petroleum oils at 55 bars because

the reactor wall is made of thick plate, which has a poor heat transfer
coefficient.
Finally the stirrer of the CSTR mllst be designed. In the United States
we have companies specializing in the des:6"n and fabrication of all sorts
of mixing and stirring equipment. Since these companies ,\"ill supply the
actual stirrer anyway, the rea,·tor designer might just as well let them
size and specif\' the stirrer These \'elldors must be g;\'en data such as
catalyst particle size consist, concentration, Jensity, liquid composition.
density, viscosity, and temperatll:'e. and of cmrse reactor dimensions
and corrosion \·equircments. In places where the services of specialized
companies are not available, stirrer design becomes a joint task for the
mechanical designer and the reacto;· designer.
Scale-up of a Gas-Liquid CSTR

The scale-up of a catalytic gas-liquid CSTR in which the chemical re-
action is controlling from laboratory experiments to full scale has been
discussed bY ~L !\adler.';1 Nadler also modeled the CSTR and .:onc!uded
•
that the scale-up of the chemical reaction-controlled reactor "was no

problem."
The theoretical bases for dynamic similarity of CSTRs were laid dO\\'I1
41
quantitativelY by Dankwerts. : Three conditions that must be fulfilled
are: (1) the model must be geometrically similar to the prototype; (2)
the Reynolds number must be the same in both the model and the
•
prototype; and (3) gravity wa\'es, density differences, surface tension,

and other influences apart from inertia and viscosity must not strongly
affect the behayior of the fluid in both model and prototype. Ceno and
62
Parera showed experimentally that if Dankwert's three conditions are
fulfilled, the CSTR's behavior can be described as a function of Reynolds
number only. Here the Reynolds number is defined as:
~
DiNpL
Re = (9-67)
60 f-LL
where D, - diameter of agitator blades, m
• -
- .\ - agitator speed, r/min
PL = density of fluid, kg/m3
•
.
f-LL = yiscosity of fluid, kg/(m . s) or Pa . S
61
R. R. Corpstein et a1. recently discussed the problems of CSTR scale-
:
up from bench scale to pilot scale and further to industrial scale and
concluded that in many aspects of scale-up, dynamic similarity is not
•
adequate equality is necessary. For example, "when heat-transfer and

temperature control are involved in scaleup, a similar convective tem-
perature gradient (i.e., equal Nusselt number) is of little value when the
desired result is equal temperature for the process." The paper also
contains many useful references.
CSTRs in Series
The destn of several CSTRs in series has been discussed by K. Schoe-
nemann, who listed several formulas for the residence time. Here
arc some of them:
m.:..:n-l
1 e- '"
-
C", - Co 1 + 2:
m~ I m! T
exp( -eh) (9-68)
.
~
Lrl -- Co exp( - elT) (9-69)

•
Cri -- CoO - exp(-eh» (9-70)
where C, = concentration of the tracer substance of the effluent stream
or (in our case) concentration of key reactant at time e,
mole %.
C~
.. , = C r for the nth reactor
CrI = Cr for a single reactor
,
Co = reference concentration of the consumed component in

the feed, mole %
1/ = number of CSTRs in series
o. ,
Co = initial concentration of the tracer substance at time e= 0

in a CSTR, mole %
m = variable to indicate the limits for the summations in the
formulas
-I - averag-: residence time = (Vlq), s
e --
•
tIme, S
F - reaction volume, m 3
3
q - throughput, m /s
Eldridge and Piret also developed equations for CSTRs in 'series at
65 66
steady state for a variety of kinetics. Mason and Piret extended these
equations to systems of CSTRs in series during transient periods of
operation. Eldridge and Piret give the following design equations for a
series of steady-state CSTRs:
= I - (9-71 )
SUsPENDED-BED REACTORS 295
where tn = V.IF" = nominal holding time in nth reactor •
. C = molar concentration
V. = volume occupied by reaction medium in nth vessel
F. = volumetric effluent rate from nth reactor
A single CSTR is the perfect model for the ideally mixed reactor.
However by connecting a large number of CSTRs in series, it is possible
to approach the unmixed state of the plug-flow reactor. Thus a CSTR
cascade with n individual CSTRs has becoP1e a model for the degree of
backmixing in a reactor. The alternate model is the well-known disper-
sion model in the second derivative of concentrati.m and the Peelet
number.
6
L. S. Kowa!czyk ; has shown the similarity between batch reactors,
CSTRs in series, and plug-flow tubular reactors. Assuming first-order
chemical reactions, the product distribution equations are as follows:
Batch C." = CAU exp( - ke)

CSTR cascade - C.4() (I + ker"
-
C."
Plug now CA -- CAO exp( - kVIF,.)
where e- residence time in a single reactor at steady state. s

3
V - reactor volume, m
3
F,. - volumetric rate of flow, m /s
n - number of CSTRs in series
\. k - first-order reaction rate constant, S-I .
Process Design of Slurry Reactor

We will first discuss the general method of attacking the design of slurry
reactors and then review the application of an example from the litera-
ture.
General Procedure
The process design of slurry reactors consists in:
· Designing the gas and liquid transport conditions to create the gas-
liquid-catalyst mixture
•
· Setting up the reaction rate equation(s)
·
-
Setting up the design equation or mass baiam.:e equation
· Setting up the heat balance equation
· Solving these equations simultaneously
•
296 .' CATAlYTIC REACTOR DESIGN
The design of slurry reactors in which the liquid is full v backmixed

is similar to the design of CSTRs. Sherwood and Farka~:' have shown
that the liquid in bubble reactors is always backmixed with respect [0
both mass transfer and heat transfer. Thus the only I'eactions that are
plug flow or partially backmixed are gas reactions with the liquid as
catalyst carrier, as in the reactor type of Fig. 9-7.
In most cases gas and liqL.;d transport conditions lead to the de\'el-
opm~nt of "elationships that modify the design equations in unpredict-
able ways. Thus no "typical design equation" can be given except in the
most generalized terms:
•• .\/J
o
-
d -, -
JO
f (H~, x, dx, F)'(h A. n p" . , .) dx (9·72)
Such equations can be either iE;tial-va1ue or boundary-condition types.

The reactor designer must deyeJop the appropriate algorithm to inte-
grate them, using techniques presented in Chap. 2.
Slurry reactors are usuallv isothermally operated. Heat is continuously
supplied to or removed from them by me~ms of a heat-exchange coil
installed in the reactor shell.
The heat balance equation equates the heat produced or absorbed by
the reaction with the heat transferred through the coil to the heat-
exchange medium flowing in the coiL As long as the reaction teinper-
ature can be maintained constant, the reaction rate and the conversion
are not affected. For this reason the heat balance equation must be used
to calculate the required heat transfer surface area and the flow rate of
the heat-exchange medium.
The simple look of the slurry reactor hardware is quite misleading,
Actually the process design is quite involved and complex and is difficult
to model, to scale up, to obtain parameter values for, and to compute.
Deckwer has recently discussed some of these difficulties in an excellent
paper.6~
The design example select~d for this book is a relativeh simple one,
Still, it is quite involved. as will be seen below.
Example of Slurry Reactor Design

The methanation of carbon monoxide in an isobaric-isothermal slun'\ ,
reactor according to the.reaction

(9-73 )
was selected as a relatively simple calculation example. A set of data was

o
obtained from literature',i ,',9.69 and from private communications.
The reaction is known to proceed at 230 to 270°C and 1 to 10 bars

pressure, using a catalyst concentration of up to 10% and catalyst particle
sizes of 5 to 60 ILm. Paraffin hydrocarbons melting at 100 to 110°C were
used to suspend the fine catalyst. Gas flowed at J to 23 cm/so The slurry
bed was about 3 m high and had a diameter of 38 mm. The gas distributor
at the bottom of the reactor was a metallic fritte of 75- to lOO-lLm pore
• •
ulameter.
The feed gas (3H 2 + CO) moved through the slurry as buhbles. dis-
solved in the paraffin liquid, diffused to catalyst particles, and reacted
on the catalyst surface. and the product gas (CHI + H~O) diffused back
to and desorbed into othn rising bubbles. Kiilbel. Hammer. and
LangemalHl assumed that the reacti(~ll I'ate ()l1 the catahst slIl'face is
10
equal to the mass-transfer rate from the bubble to the solution. At low
tenperatllres. Iow catalyst concentrations, and high gas holdups. the
chemical reaction is the controlling resistal!ce.
The intrinsic reaction under these conditions and at stead" state is:
•
kmol CH/(m"·s) (9-74)
where x = conversion of CO. dimension less

:: - height of the reactOl' bed abo\"e the gas distributor. m
EL = liquid hold up, dimensionless
1<co - superficial CO loading. kmol CO/(I1/ . s)
•
k = reaction rate constant
c, = catalyst concentration of nonexpanded slurry, kgliil"
l
CH = concentration of dissoh'ed H" in position z, kmolfm:
= fractional exponent. approximately = 0.5
The CO loading Uco is given by:

.,
I1CO - 1.60614 v X~'o (TolT)(PIP,,) kmol CO/(m- . s) (9-75)
where v = gas flow rate, m/s

x~() = mole fraction of CO in feed gas. dimensionless
T - temperature, K •
P = pressure; bars
Subscript 0 denotes NTP conditions. -

Under experimental conditions in \\'hich the mass transfer of h::dro-
gen from the gas phase to the liquid phase is exclusivel\" rate-determin-
•
•
. ing, i.e., at higher temperatures, higher catalyst concentrations, and low

gas hold ups, the following mass transfer equation applies:
2
r = uco(dxfdz) = (kLaI3)(HPXIl - CH) kmol COfm • s (9-76)
where kI. = mass transfer coefficient for H2 from the gas bubble into
the liquid phase, m/s
a = specific phase boundary area per unit volume of ex-
. • 3
panded suspenSion, m-fm
3
H =. Henry constant, kmol/(m • bar)
X H = mole fraction of H2 in gas at position z
The variations of XH , CL> and a with z as a result of conversion x can
be handled by the following equations:
o 3 XOCOX
X Il -
XII(x) = I () (9-77)
- 2 Xcox
() . 0
- Cl. + 2 Xcox(l - €~) (9-78)
= a(J(l - 2 X~oxr' (9-79)
.
The superscript 0 means at position z = O.
At steady state, the rates of reaction and mass transfer are equal.
Equations (9-74) and (9-76) to (9-79) can be combined as follows:
o
dx
- -
kLa (1 _ 9X'J )"
- co x· HP
X~i - 3X~o X
0
dz 3uco I• - 2Xco x
dxfdz' Uco
(9-80)
kdc2 + 2X~ox(l - c2»
iO
Equation (9-80) cannot be solved analytically. K6lbel et al. solved and
optimized Eq. (9-80) by means of an analog computer. More recently,
a digital solution was obtained by Hammer and Schmal,70 who also op-
timized the reactor. This latter study is a good example of how involved
slurry reactor design can really be. The integration of Eq.· (9-80) gives
the reactor height lD for the desired conversion XD when the reactor is
assumed to have no backmixing. In order to allow for backmixing, a
residence time distribution function <p(z,N) is superimposed on the in-
tegration of Eg. (9-80)
• ~[)
XD = x(z)dz (9-81)
o
in the form x(z)<p(z,N)d: (9-82)

o
•
where N is the stirred tank equivalent number for the degret; of back-
mixing in the slurry reactor. This is quite a different way of expressing
backmixing in reactor design equations than is used in this book and is
64 il
due to studies by K. Schonemann and H. Hofmann. Thus, the nu-
merical computations of Hammer and Schmal will not be repeated here.
io
The interested reader is referred to the paper of these authors.
Other Examples
Perhaps the most impOl lant industrial application of the slurry reactor
concept is thp Fi<;che.--TrojJsch synthesis. There is now considerable lit-
erature on the so-called liquid-phase Fischer-Tropsch synthesis. Let
us mention only a few papers by Koibel, Ackermann, and Engelhardt,72
3
Kblbel and Acke.·mann,6 Zaidi et al.,69 and Hubert:
The hydrogenation of ethylene over Ram:!' nickel is of interest for
modeling studies of slurry reactors. A paper of Kolbel and MaennigY
reports on experimental data development to verify various process models.
In the past, slurry reactors have as a rule been used in the chemical
industry only in small-scale batch hydrogenations and have not been
common in the larger-scale operations of either the chemical or petro-
chemical industry. Recently the Institut Franylls du Petrole (IFP) de-
veloped a slurry reactor process for the catalytic hydrogenation of ben-
zene to cydohexane. I! Besides the IFP and the Fischer-Tropsch processes,
an increasing number of new processes are emerging through various
stages of development.
Process of EbuIlated-Bed Reactors

The first task of the designer is to determine the ebullated bed conditions
of the process:
· The ebulIating (fluidizing) liquid velocity of the particular liquid and
the catalyst material, shape, and size must be known from laboratory
•
expenments.
· The mean residence time of the liquid in the bed, which corresponds
to the desired product yield, must be known. This information may
be empiricaL
· The transport phenomena between gas and liquid and between liquid •
and catalyst must be known .
•
The actual design equ~uion depends upon the way the ebullated bed
is operated. If a high space velocity is used in a slender reactor and no
product is recirculated, then the ebullated bed can be treated like a plug-
, ,
,
flow reactor with some axial dispersion and a Peelet number can be
determined. '
dC, I d~C, ~Ji d"
- . 2 - (9-83)
dZ Pe"lI1l dZ Ul, CI.O
where C r = Ct/Cf."
Z = zldp
z = axial coordinate in the expanded bed
The gas flow can be definitely plug 110\\', and if the gas eff1uent ;.;
the main product. the design equation for it is:
- ~Jid/,
-- (9-84)
U C(;o
where CD, = CD/CGO '

If. however. the ebullated bed is operated \\'ith liquid recycle, as in
most cases, then the liquid phase is for all practical purposes a CSTR
and the design equation is:
(9-85 )
wl.~re V'= volume of expanded liquid-gas-catalyst mixture, excluding

the volume needed for internal or external recirculation,
3
m
F - feed rate, kmolls of total feedstock, liquid and gas
""'- ,
•
-- mole fraction of the critical reactant in the total feedstock,

-
)'0
•
dimensionless
"
Pr = mass of catalyst per unit volume of expanded bed, kg/m"

9l.", = reaction rate function = TJ r"
.
ru' = intrinsic reaction rate, kmol of critical reactant converted

per second and per kilogram of catalyst in suspension,
kmoll(kg . s)
x = fractional conversion of the key reactant. assuming that the
reaction starts at !h p inlet of the reactor or that x" = 0
The heat balance equations also depend upon conditions at \\'hich the
reactor is operated. Geperally, they parallel the mass balance equation,
At high liquid space velocity, in tall and narrow reactors, and \\'hen no
liquid ;s recirculated, equations developed for trickle beds can be used
,
[Eq. (7-39)]. In case of low space velocity, large diameter/height ratio,

and liquid recirculation, Eq. (9-65), developed for CSTRs, can be used.
Process Design of Three-Phase Transport Reactors (3<1>TR)

The process design of three-phase transport reactors is one of the least
knO\\'n The paper of Pruden et al. ~~ gin's only some clues. These authol's
studied a COUlttercurrenl 3<!>TR with a simple model reaction, the hy-
drogetlation of O'.-m~th)'lstyrene (A\fS) to cumene in the presence of
a palladiu'n bla-:k catalyst at ambient temperature and atmospheric
pressure,
. yrcnc
a-methvlst ,
cumene
This reaction had been used in stuc'ies of trickle beds~4 and slurry re-
l
actors.: Cumene is the only product and A\1S and cumene have 10\\'
vapor pressures.
The design equation is based on iptegrating a differential equation
that describes the reaction of indiyidual gas bubbles as they rise upward
in the reactor. The following assumpriollS were made:
· The gas upflow is plug now.

· The gas-side resistance to mass transfer can be neglected.
· The rate-controlling steps are: dissolution of H~ from the gas bubbles,
mass transfer of H2 from bulk liquid to the surface of the catalyst, and
the reaction of H2 with A!>.fS on the surface of the catalyst,
•
which is
first-order in Hq.
-
· Gas bubbles are spherical in shape.
· Catalyst particles are spherical in shape.
The differential equation is:
- I
dx F F,- Fl
--
(l -
j
-
•
+ (9-83 )
dz xl"' p, p,
-
where x - gas conversion per pass. dimensionless
z = reactor height, measured from the bottom of the reac-
tor, m
• 'I
p, = catalyst loadmg, kg/nY of reactor volume
•
CATALYllC REACTOR DESIGN
The let m F\/( 1 - x)~' describes the mass transfer from bubbles to liquid.
The (el m (1 - x)~' corrects for the decrease in bubble surface area as
the reaction proceeds.
(9-84)
wh~re Dfjo = initial bubble diameter, m

= gas-liquid mass-transfer coefficient, mfs
3
R = gas constant, m • bars/(kmol . K) = 0.08314
Vb = bubble velocity with respect to liquid, mfS
H = Henry's law constant defined by C* = HP, in which H has
3
the dimensions kmoU(m • bars)
• •
C* = saturatIon concentratIon of hydrogen in bulk liquid,
3
kmoUm
P - pressure at height z, bars
Po = pressure at bottom of reactor, bars
[he F:,/pc term accounts for m2SS transfer from the bulk liquid to the
catalyst surface:
(9-85)
, where nb(J - initial number of moles per bubble. kmol •

•
-
'- '.
fb - frequency of bubble formation, S-l

kc -- liqUId-to-catalyst mass-transfer coefficient, m/s
- 2
Sp - specific mass transfer surface. 6/p,dp. m /kg
p, -- particle density, kg/m3
2
Ac - cross-sectional area of reactor column, m
The F3/Pc term describes the chemical reaction:
(9-86)
where k = reaction rate constant· for first-order surface reaction,

m4/(kmQI . s)
2
S; - specific r.eaction surface, m /kg
.,
3
C .. :-IS = a-methylstyrene concentration in bulk liquid, kmoUm
The chemical reaction rate is very rapid, and thus the reaction term
F3 might become negligible. Equation (9-83) can be integrated by assum-
•
•
•
ing that Fl and F2 are constant:

•
ZT = 3 K/ [1 - (l - x),'J + (9-87)
where ZT is total reactor height in meters and K/ and K2 are constants.

24
The values of KI and K2 can be obtained from Pruden et al.'s paper.
Figure 5 in that paper plots conversion x vs. 0.001 Pc for two values of
ZT' By substituting two sets of values of x vs. ZT in Eq. (9-87), we can
obtain two simultaneous equations containing K, and K 2 , from which
these constants can be calculated.
Alternatively, it is possible to numerically integrate Eq. (9-83) provided
various parameters are known. These parameters and the means of
evaluating them are:
· A form of the Frcssling equations can be used instead of kr;:
50 OB
Sh = (2.)( I.04)Reo SC .: (9-88)
· Bubble diameters can be measured from ~ligh-3peed motion pictures ..
· Partide diameters can be measured by a settling velocity technique.
· The gas bubble velocity Vb can be calculated from
(9-89)
where u is superficial gas velocity in meters per second and CG ~ gas

hold up in cubic meters of gas per cubic meter of re~ctor volume, giving
9.94
, . Vb = 0.23. - 1
UL
(9-90)
cc - cc
where 11[ = superficial liquid velocity, m/so
• DB = D BO (PoIP)" (1 - X)" (9-91 )

· P = p" - z(P 0 - P.1 )/ZT (9-92)
• U - Uo (1 - x)(PoIP) (9-93)
where DB = bubble diameter, m

Pi = pressure at top of reactor, bar
Uti = initial gas superficial \'e1ocity, m/s
The 34>TR appears to be advantageous a:. compared with the slurry

••
re?ctor: at similar conditions, the conversion in thf> 34>TR is much higher
than that in the slurry reactor because:
The gas bubbles in the 34>TR have lower velocity in relation to the
reactor and thus longer contact time. However, the bubble velocity
. .• •
with respect to the liquid, which is the important velocity for mass
transfer, is the same in both types of reactor.
. The catalyst tends to agglomerate in both reactors. In the slurry reactor
this results in decreasing area and poor catalyst distribution. In the
3<pTR the agglomerates are broken down in the pump, and l'ecircu-
lation promotes good catalyst distribution.
NOMENCLATURE
a External particle-surface/particle-volume ratio, m,-I or
Interfacial area in bubbles (Eg. (9-16)], or
Specific phase boundary area per unit volume of expanding
. -I
suspensIon, m
Bubble surface area per unit volume of expanded slurry, m-I
. .)
A Total mleI'face area. w-
Effective area of heat transfer, m~
Area of bubble. m~
Cross-sectional area in reactor "esseL m~
Area of oblate spheroid bubble with major-axisrrninor-axis ra-
tio ~ 2.6, where All < A,ph ~ 1.2 All
Bo Bodenstein number. dimensionless
•
. Catalyst concentration of nonexpanded slurry, kg/m"
"
,. C Concentration. kmollm:\ or .
In Eq. (9-29), concentration of tracer at axial coordinate z,
3
kmollm
3
C* Saturation concentration of hydrogen in bulk liquid, kmol/m
c.... Molar concentration of species A, kmol/m 3
eAI) C,\ at inlet

e . . ~ls a-methylstyrene concentration in bulk liquid, kmol/m:>
CH Concentration of dissolved H2 in position :. kmol/m"
l
Cr Equilibrium concentration in bulk liquid, kmolfm:
Cco !\1o!z,.r concentration of critical reactant in gas phase at inlet,
'1
kmol/m • .
CCr Dimensionl~ss molar concentration of critical reactant in gas
phase '.
CL Critical reactant concentration in bulk liquid, krnol/m:l
CLO Cl at inlet
•
SUSPENDED-SED REACTORS 305
Initial concentration at time e= 0 in a CSTR, mole %

C;, Reference concentration of the consumed component in the
feed, mole %
Molar heat capacity, kJ/(kmol . K)
Dimensionless concentration of key reactant in liquid phase
l
C, Reactant concentration at catalyst
,
surface, kmollm:
Concentration of key reactant in the effluent of a single CSTR
at time 0, mole %
Concentration of key reactant in the effluent of the nth CSTR
J
in series at time e, mole %

,
C, Concentration of the tracer in the total flow leaving the re-

,\
actor, kmollm'
Particle diameter, n',
Mean Sauter diameter, m
2
Diffusi\'itv,
, m /s
Molecular diffusion coefficient for the species diffusing in the
• <)
flUId, nds
D" Axial dispersion coefficieI~~, m Q/s
2
DuI. Liquid-phase axial dispersion coefficient, m /s
DB Bubble diameter, m
.DBn Initial DB
\.
~0 ~
DBE Minimum stable bubble diameter, m

DB,lf Diameter of geometric mean bubble, m
D, Impeller diameter, m
DT Reactor diameter, m
2
D, Superficial dispersion coefficient of liquid, m !s
E Effecti\'e local dispersion coefficient
Eo Eotvos number, dimensionless
j Friction factor and drag coefficient in nonlaminar region
.-
j/, Frequency of bubble formation, S-I
')
F Parameter inde'pendent of now conditions, kmol/(m- . s), or
flow of liquid feed, kmoIls (in Sec. 9.3)
F, Volumetric rate of now, m:l/:"
FT Total molar feed rate, kmolls
•
Enthalpy of feed stream, kJ/kg

Enthalpy of products, kJlkg
Froude number, dimensionless
2
g Gravitational acceleration = 9.80597 mls
h Heat transfer coefficient
3
H Henry's constant, kmoV(m . bar)
Bulk liquid-to-particle mass transfer coefficient, mls
ke corresponding to terminal settling velocity, m/s
Gas-to-liquid mass-transfer coefficient, mls
Liquid-to-gas mass-transfer coefficient. m1s
Overall reaction and mass-transfer rate constant
Surface reaction rate coefficient, mls
2
Coefficient of liquid-phase axial dispersion, m /s
2
Liquid-phase backmixing coefficient, m /s
m Catalyst loading, kg/m3
M Average molecular weight of the liquid feed stock, kg/kmol
n Number of CSTRs in series
Initial number of moles per bubble, kmol
Impeller speed, S-1
Np The power number or the power input from the impeller

•
f(. Molar flux of key reactant in the bubble-expanded slurry

PL Partial pressure (of CO 2) in liquid phase, bars
P Pressure, bars
Po Pressure at the inlet (bottom) of reactor, bars
P' Power, W
PeBT Peelet number based on reactor diameter, dimensionless
Pe""" Peelet number· br mass, <txial dispersion in liquid phase,
dimensionless
•
Pe* Peelet number corresponding to terminal settling velocity,
dimensionless
3
Q Volumetric flow rate, m /s
•
SUSPENDED-BED REACTORS
ru> Reaction rate related to weight of catalyst in suspension, kmoV

(s . kg)
S
Gas constant = 0.08314 m bar/(kmol . K)
3
fR Global rate of reaction, kmol/(s . m )
fR.., Global rate of reaction related to weight of catalyst in suspen-

sion, kmoV(s . kg) .
H{"" ~jl,,. of che itl' reactant species
Se Schmidt number, dimensionless
Sh Sherwood number, dimensionless
2
Sp Specific rrass-transfer surface, m /kg
2
S; Specific reaction surface, m /kg
Stl. Liquid-phase Stanton number, dimensionless
t" Nominal holding time in the nth CSTR reactor,s
T Absolute temperature. K
Tx Temperature of th" surroundings 01' cooling medium, K
T2 Exit temperature. K
U Superficial gas velocity. m/s
2
Uco Superficial CO loading, kmol CO/(m • s)
-
Average superficial gas velocity, based on inside reactor di-
ameter and temperature and pressure, m/s
Superficial liquid velocity at mean of inlet and exit pressures,
m/s
Urn at beginning of expansion, m/s
Mean bubble rise velocity, m/s
Terminal yek::itv, of bubbles, m/s
v Velocity of the fluidized stream, m/s or
Gas flow rate in Eq, (9-75), cm/s
Bubble velocity with respect to liquid. m/s
Vc Linear velocitv of fresh gas at reactor bottom, m/s •
Actual mean li!luid velocity, m/s

Vo Velocity of gas at sparger orifice (reactor inlet), m/s
VR Actual mean gas velocity relative to actual mean liquid velocity,
m/s
•
,
V, Volume of expanded liquid + gas + catalyst mixture, m?>

Vi. Liquid volume at rest or nonexpanded liquid volume in re-
.;
actor, m'
w Mass flow rate, kgis
x Fractional conversion of CO, dimensionless
Desired x
Fractional conversion, dimensionless
X at inlet
X at outlet
Mole fraction of H~ in gas at position z [Eg. (9-76)] dimensionless
)'0 Mole fraction of key• reactant in feed stream, dimensiol1iess
z Longitudinal coordinate. 111
z Dimensionless axial (longitudinal) coordinate

Height of the expanded liquid, including bubbles, III
Height of clear liquid at no gas £10\\' or zero expansion, m

Total bubble column height. m
Time increment, s
Difference of density between particles and the liquid. kg/m~
E Void fraction, dimensionless
\, Fractional gas holdup, dimensionless
Integrated mean \'alue of E(;
Fractional liquid holdup. dimension less
El' Catalyst particle phase fraction, dimensionless
e Residence time in a single CSTR at steady state. s
e Average residence time in the reactor. s
-
eG Average residence time of the gas in the expanded liquid, s
ell Nominal holding time in nth reactor (CSTR in series). 5
Vif::csity of the liquiJ, Pa . s

P Density, kg/.m3
Pc Mass of cataLrst per unit volume of expanded liquid. kg/m3
PL Liquid density, kgf m 3
p, Density of solid catalyst particle, kg/m:l
•
SUSPENDED-BED
,
REACTORS 309
(J Surface tension, kg/s2

Transfer rate, kmolls
Subscripts
eq Equilibrium
f Final
F Frictional
G Gas phase
,
I ith component
L Liquid phase
Le Two-phase
0 I nitial or inlet
T Total
w Wall
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,
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-
8. Herben Kblbel, Hans Hammer, and U. Meisl, "Hydrierung und Oxydation
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•
•
10. Herbert Kolbel, Hans Hammer, and Horst l.angemann, "Zur Reaktionstech-
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• no. 26, 1968. .
•
20. 1. A. Vasalos et aI., Study of Ebullated Bed Fluid Dynamics fOT H-Coal, U.S.
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1763-1770.
22. Fernand Moreau, Jr., "Key l'nit in World's First All-Hydrogen Refinery.
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no. 6, pp. 52, 54.
23. Ciarence A. Johnson, Katherine C. Hellwig, Edwin S. Johanson, Roland H.
'\Tolk, and Harold H. Stoder: "H-Coal: Conversion of Western Coals," Tram.
AIME 254:235-238 (1973).
24. B. B. Pi'uden and M. E. Weber, "E\'aluation of the 3-Phase Transport Re-
actor," Can. J. Chem. Eng. 48: 162-167 (1970). (Special copyright permission
from the CanadianJouJ1lal of Chemical Engineering.)
.
25. Sabri Ergun and A. A. Ornir;g, "Fluid Flow through Randomly Packed
Columns and Fluidized Beds," Ind. €ng. Chem. 41:1179-1184 (1949).
26. B. J. Michel and S. A. Miller, "Power Requirements of Gas-Liquid Agitated
Systems," AIChE I 8:262 -266 (1962).
•
•
SUSPENDED-BED REACTORS 3fl
27. J.Y. Oldshue and F. L. Connelly, "Gas-Liquid Contacting with lmpeller

Mixers," Chem. Eng. Progr. 73(3):85-89 (1977).
28. P. H. Calderbank, M. B. Moo-Young, and R. Bibby, "Caalescence in Bubble
Reactors and Absorbers," Proceedings of the 3d European Symposium on Chemical
Reaction Engineering (ESCRE 3), Amsterdam, Sept. 15-17, 1964, Chem. Eng.
Sri., suppl. 91-113 (1964).
29. Wesley B. Argo and D. R. Cova, "Longitudinal Mixing in Gas-Sparged Tu-
bular Vessels," 1nd. Eng. Chem. Process Design Develop. 4:352-359 (1965).
30. Herbert Kolbel and Horst Langemann, "Der Stoffiibergang in Gas-Flussig-
keitsreaktoren bei verschiedenen Stromungsformen," in Dechema A1.0n0graph
49. 1964, pp. 253-275.
31. Charles N. Satterfield, Mass Transfer in Heterogeneous Catalysis, MIT Press,
Car.lbridge, 1970. (Special copyright permission from the ~HT Press.)
32. P. H. Calderbank, in Uhl and Gra\ (eds.), Mixing, vol. 2, Academic Press,
I\"ew York, 1967; Char. 6.
33. \'\'. Siemes, "Gasblasen in Fli.issigkeiten. 1. Entstehung von Gasblasen an nach
oben gerichtcten heisformigen Diisen," Chem.-1ngr. Tech. 26:479-496 (1954):
"II: Der Aufstiegvon Gasblasen in Flussigkeiten," Chem.-Inp-. Tech. 26:614-630
(1954).
34. Giovanni Astarita, - "Two-Phase and Slurrv. Reactors," in Chemical Reaction
Engineering, American Cp~mical Society, Advances in Chemistn' SeT. 109.
1972. pp. 223-236.
35. Isaac H. Lehrer, "Gas Hold-Up and Interfacial Area in Sparged Vessels,"
lnd. Eng.Chem. Prow, Design Develop. 10:37-40 (1971).
36. M. Roustan, L Gbahoue, and H. Roques, "Study of the Retention of Gases
., in Bubble Columns with Free Ascension," Chem. Eng. J. (Lausanne)
13(1):1-5(1977) (French). _
37. Wolf-Dieter Deckwer, I. Adler, and Ahmed Zaidi, "Detailed Analysis
. of COo-
-
Interphase Mass Transfer in a Bubble Column [0 Prove the Validity of a
Design Model," in Weekman and Luss (eds.), Chemical Reaction Engineer-
ing-Houston 5th ISCRE, American Chemical Society Symposium SeT. 65.
1978, pp. 359--37 L
38. H. D. Mendelson, 'The Prediction of Bubble Terminal Velocities from Wave
Theory," AIChE J. 13:250-252 (1967).
39. A. S. Afschar, M. Diboun, and K. Schiigerl, "Eine Blasensaule mit Gleich-
strom von Wasser und Lufe Ill. \\'echselwirkung z\,iscllen cl-=n Phasen,--
Chem. Eng. Sci. 23:253-265 (1968) .
•
40. W. Siemes and W. Weiss, "Fliissigkeitsdurchmischung in engen Blasensau-
len," Chem.-Ingr. Tqch. 29:727-732 (1957).
41. Wolf-Dieter Deckwer, U. Graeser, Horst Langemann, and Yal<;:in Serpemen,
"Zones of Different Mixing in the Liquid Phase of Bubble Columns," Chem.
Eng. Sci. 28:1223-1225 (1973).
•
42. Sherif H. Eissa, Mohamed M. El-Halwagi, and Mohamed A. Saleh, "Axial

and Radiall\fixing in a Cocurrent Bubble Column." Ind. Eng. Chem. Process
Design Develop. 10:31-36 (1971).
43. P. V. Dankwerts, "Continuous Fiow Systems
•
Distribution of Residence Times,"
Clum. Eng. Sci. 2:1-13 (1953).
44. Y. K. Vail, N. Kh. Manako\", and V. \'. l\tanshilin, "Turbulent Mixing in a
3-Phase Fluidized Bed," Inlml. Chem. El/g. 8(2):293-296 (1968).
45, Edwin R. Gilliland and E. A. Mason, "Gas Mixing in Beds of Fluidized
Solids," Ina. Eng. Chem. 44:218--224 (1952).
46. E. M. Vasalos. E. M. Bild, and D. E. Tatterson. Study of Ebullated-Bed Fluid
DYllamil'S for H-Coa/, Quarterly Progress Repon !'\o. 4 for Sept. 1 to No\,.
30,1978, no. FE-2588-15. U.S. Department of Energy.
47. 1- y. Oldshue. "Mixing, Annual Re\'ie\\'."llId. EllK· Chl'lII. 58(11):50-57 (1966):
59(11):58-70 (1967); 60(11):24-35 (1968); 61(11):121-127 (1969).
48. J. Y. Oldshue. "Suspending Solids and Dispersing Gases in Mixing Vessels,"
1ud. Eng. Chem. 61(9):79-89 (1969).
49. Ah'in W. Nienow and Da\'id Miles. "Impeller Power l\:umbers in Closed
Vessels," Ind. Eng. Gllem. ProCl'SS Design Dn.'e/ojJ. 10:41-43 (1971).
50. James J. Carbprry, "Heat and l\lass Diffusional Infntsions in Catalytic Re-
actor Behavior," Catal)'sis Rr,'. 3(1):61-91 (1969).
-
51. D. L Johnson. Hirotaro Saiw. J. D. Polejes. and Olar A. Hougen, "Effects
of Bubbling and Stirring on Mass Transfer Coefficients in Liquids," .1lChE
J. 3:401-417 (1957).
52. Thomas K. Sher'wood and Robert L Pigford.-4.bsOIjJlioll a lid Exlmclum, McGraw-
'\ ... .,
-
Hill. Kew York, 1952. '
53. P. L T. Brian and H. B. Hales. "Effects of T ranspirating and Changing
Diameters on Heat and Mass Transfer to Spheres:' A.ICltE J. 15:419 125
1969.
54. P. LT. Brian, H. B. Hates, and Thomas K. Sherwood. "Transport of Heat
and Mass between Liquid and Spherical Panicles in an Agitated Tank,"
.4./ChE J. 15:727-733 (1969).
55. Daizo Kunii and Octa\'e Le\·enspiel. Fluidi:.o.tioll Engineering, John Wiley,
:'\ew York, 1969, p. 197.
56. Liang-Tseng Fan, Y. C. Yang. and Ching-Yung \fen. "Mass Transfer in
Semi-fluidized Beds for a Solid-Liquid S\'stem," AlChE J. 6:482-487 (1960) .
•
57. Knut 0stergaard and \'\'. Suchozebrski. "Gas-Liquid i\fass Transfer in Gas-
Liquid Fluidized Beds:" Proc. -Ith Europran S,nnp. Chi'lllical Reaction Engi-
nen-ing Brussels, 1968, p'p. 2 J-29.
-
58. K. K. Seth and E. P. StaheL "Heat Transfer from Helical Coils Immersed
in Agitated Vessels," Illd. Eng. Chem. 61(6):39-49 (1969).
•
59, Pramod Lavingia and P. F. Dickson, "Heat Transfer to a Two-Phase Liquid

System in an Agitated Vessel with Coils," [nd. Eng. Chem. P1"Ocess Design
Develop. 10:206-209 (1971).
60. J. J. Van Deemter, "Trickle Hydrodesulfurization A Case History," Pro-
ceedings 3d European Symposium Chemical Reaction Engineering Amsterdam, Sept.
15-17,1964, pp. 215-223.
61. Murray Nadler, "Scaleup of a Liquid-Gas Stirred Tank (LGST) Reactor:'
Paper 44b pl'esented at the 57th Am. Insl. Chem. Engrs. Annual ~leeting.
Boston, Dec. 6-10, 1964.
62. Ramon L. Cerro and Jose M. Parera, "Dynamic Similarity in Continuous
Stirred Tank Reactors," llld. Eng. Chelll. Fundamentals 9:181-18:\ (1970).
63. R. R. Corpstein, R. A. Dove, and D. S. Dickey, "Stirred Tank Reactor De-
sign," Chem. Ellg. Prog/". 75(2):66-74 (1979).
64. K. Schoenemann, "Der chemische Cmsatz bei kontinuiedich dmchgeftihr-
ten Reakthnen," in Dechema Monograph 21, 1952 pp. 203-236.
65. John W. Eldridge and Edgar L. Piret, "Continuous Flow Stirred Tank Re-
"ctor <;ystems. l. Design Equations for Homogeneous Liquid Phase Re-
actions. Experimental Data," Chem. Eng. Pnlgr. 46(6):290-299 (1950).
66. Donald R. ~IasoI1 and Edgar L. Piret, "Continuous Flow Stirred Tank Re-
actor Systems Development of Transient Equations." 11Id. El/I[. Chem.
42:817-825 (1950).
67. Leon S. KO\\'alczyk, "Application of Difference Equations in Design of CSTR's
in Series:' paper 55d at the Am. lnst. Chem. Engrs. 62d Annual ~Ieeting,
Washingtun, :\0\'. 16-20, 1969.
\ . ,
68. Wolf-Dieter DecKwer, "Blasensaulen-Reaktoren: ihre modelmassige Erfas-
sung und Berechnung," Chelll.-I71gr. Tech. 49:213-223 (1977).
69. Ahmed Zaidi, YClssef Louisi, !vlilos Ralek, and Wolf-Dieter Deckh'er, "Er-
mittlung \"on StoffUbergangszahlen fUr die Fischer-Tropsch-Fliissigphase-
Synthese:' Chelll.-Ingr. Tech. 50:628-629 (1978). .
70. Hans Hammer and Martin Schmal. "Zur Optimierung von Gas-Fli.issig-
phase-Reaktoren mit suspendiertem Karalvsator," Bl-eJlIIsto(f-Chem. 49:225-228
(1968).
7l. Hanns Hofmann. Dissertation, Technische Hochschule Darmstadt. 1955.
Herbert Kolbel, P. Ackermann, and F. Engelhardt. ":'\eue Ent\\icklungen
zur Kohlenwasser·stoffsvnthese."
, Erdiil Kohle 9(3):153-156; Q(4):225-228;
9(5 ):303-307 (1956).
73. Hans-Jlirgen Huben, "'Bau unJ Betrieb einer Fischer-Tropsch-LaboraI'lage
mit Fli.issigphase ReaktGr," 0:TIS Report BMFT-FB-T 80-033, 1~SO.
74. Charles :\. Satterfield, A. A. Pelosof, and Thomas K. Sherwood, "~lass
Transfer Limitations in a Trickle-Bed Reactor," AIChE J. 15:226-2~H (1969).
•
Chapter
DESIGN OF TORY
PILOT-PLANT REACTORS
This chapter covers laboratory and pilot reactors, including their me-
chanical design. The sizing of laboratory reactors is almost always made
approximately and does not require the tedious process design necessary
for full-scale reactors .
•
10.1
DEFINITIONS AND GENERALITIES
Laboratory reactors are small-size exploratory or experimental reactors that
can be set up on a laboratory bench. There is really no definite size limit
, which would distinguish laboratory reactors from pilot reactors. Labo-
• •
. .
ratory reactors are normally used to determine whether a given reaction
does or does not occur or whether a catalyst shows sufficient ?ftivity,
sufficient life, the desired selectivity, or the like. Most im'estigators use
laboratory reactors for exploratory work and once they have a promising
reaction, they immediately build a small-scale pilot reactor, 'on which
they begin to measure the specific properties of that reaction.
We can distinguish between general-purpose and special-purpose lab-
oratory reactors. Exploratory bench-scale reactors are examples of the
former. There also are special-purpose laboratory reactors that are de-
signed only to determine certain kinetic properties of reactions. Both
categories will be discussed below.
Most often a laboratory reactor is designed with very little knowledge
of the reaction on which 'one wants to experiment. Therefore, it makes
sense to he cautious and t<'1 carry out the preliminary experiments safely
-in strong reactors, if necessary behind safe barricades.
On the other hand, if one is absolutely certain that no pressurt is
needed and will not be developed during the reaction, it is practical to
"r
•
316 CATALYTIC REACTOR DESlGN
design a simple glass reactor in order to see what is happening inside.

It is still advisable to place a strong Plexiglas shield between the appal'atus
and the experimenter. A laboratory reactor must either be so easy to
change or so cheap that it can be tl1I"own away and another one built,
or be uniYersally useful and versatile. like an autoclave. With the advent
of gas chromatography, it has become possible to work with very small
amounts of reactants, and consequently one can design and build very
small continuous reactors which are easy to modify or replace if they
plug up.
The laboratory reactor should not take too long to put together. A
chemist or chemical enginePr who has an idea should oe able to try it
irI)mediately. Some questions just cannot wait too long to be answered.
If a good batch autoclave is available, it may be extremely convenient to
try pressure reactions in batch operation. Also, if a simple bench-scale
continuous microreactor system is available, 'nany fixed-bed catalytic
• • •
reactions may be tried without nn,ch preliminary preparation. Some

people try to foresee reaction results by elaborate calculation5, but since
their input never contains unforseen factors, these people will always be
open to surprises until they actually run an experiment, which, by the
way, can be much faster than most elaborate cG:nputations.
Pilot reactors are intermediate reactor stages between the experimental
or explorative bench-scale size and the full-scale commercial size. The
function of the pilot reactor is to obtain:
· Process information such as effects of various parameters on yields or
selectiyitv• .
· Transport information for scale-up
· Data to fit process models
The commercial function of the pilot plant resides in the fact that we
try to make all our mistakes with it so that we can make all our profits
with the commercial plant.
Pilot-plant reactors are designed on the basis of fairly good knowledge
of the nature of the reaction or reactions to be studied in them. A
thorough experimental design scheme is worked out and a pressure-
temperature tolerance of the reactor is specified accordingly. Conse-
quently, a pilot plant is always.designed for considerably greater severity
than a plant reactor.
•
Sizewise, pilot reactors can span the range from large bench reactors
to small commercial reactors. The nature of the process an0 the extent
-
of prevailing ignorance and caution determine how closely pilot reactor
design approaches full scale. Of course, there are compelling economic
reasons to keep the number of pilot stages and the reactor sizes smalL
•
DESIGN OF LABORATORY AND PlLOT-PLANT REACTORS 317
However, the minimum size of the last pilot stage is dictated by the
suitability of the reactor to clearly and reliably show the full effect of
transport phenomena on various process parameters.
10.2
LABORATORY REACTORS
Most heterogeneous catalytic reactions that involve gases also require
elevated pressures to enhance catalyst surface concentrations and ele-
vated temperatures to improve reaction rates. Thus, in the majority of
cases laboratory reactors are designed to withstand both pressure and
heat.
General-Purpose Laboratory Reactors

The chemical reaction engineer must have uni\'ersal tools to explore
ideas \\'ithout too much fuss and red tape. For heterogeneous catalytic
reactions that can be studied in the batch mode, one generally uses either
a shaking autoclave or an upright stirre~ reactor when dealing with
liquids, Basicalh', both n'pes are designed quite similarly except that the
stirred reacror has a built-in stirrer, frequently of the magnetic type,
Both do about the same thing except that th., shaking autocla\'e is simpler
and has no mO\'ing parts inside the reactor. Thu:;, ",hat one may say of
the construction of the shaking autoclave is also true of that of the stirred
reactor,
, The Shaking Autoclave

". \
The shaking autocla\'e is a pressure vessel that is attached to a shaking
mechanism. It is standard equipment in any petroleum or hydrocarbon
research laboratory and is a practical tool for testing gas-liquid-phase
reactions, Results obtained in a shaking autocla\'e may be used to build
a pilot unit to measure specific parameters,
1
Shaking autoclaves are built for volumes of 100 to 1000 cm: and can
be pressurized to 1700 bars at 200°C or heated up to 650°C at somewhat
lower pressure, They are quite useful to have at one's disposaL If one
does not knO\\' what is going to happen, one can always place the reactants
into such an autoclave and run the reaction behind a sturd\, barricade,
•
The mechanical design of the autoclave reactor is tricky, Of course,

\\'hat we will sa:' about t~e shaking autoclave also applies to any other
autocla\'e, f'.Iany types of autoclave closures develop leaks when heated
above 300 to 350°C. In some cases a new reactor does not leak, but as
one goes through several heating and cooling cycles, the leakage becomes
intolerable and nothing helps. There is one type of autocIa\'e closure
•
318 _ CATALYTIC REACTOR DESIGN
Cover Set screw
_lock nut
~T rust ring
Resiloent rlOg ---f=
'--Main nut
Cupper goop
applied 10
these Ihreads
Seal ring --¥7'-1 '-h MaSl spray

applied
Reaction
React or bod y ---' l.J--'-4 ------..::!::.:::::::._---L.
I
Resilient ring
- -
B-_,+
A
. - - -.~
I, :,
j
,
_._._-_._"
,. i,
Seal
- MoS 1 is
nng sprayed on
Ihis surface
FIG. 10-1 Gasche closure with resilient ring.' (Courtesy Autoclave Engineers,
Inc.)
design that does not have this drawback. This design is shown in Fig.
l
10-1. It was invented by Gasche by modifying the old Bridgeman clo-
2
sure. An earlier design by Gasche,3 shown in Fig. 10-2, can also be used
satisfactorily. The properties for both closure designs are given in detail
in the respective U .S. patents. The common characteristic of both designs
is a seal ring as shown in detail in Fig. 10-1. Increased pressure in the
reactor makes the reactor closure tighter. The resilient ring in Fig. 10-1
takes up some of the slack during the differential expansion of the
closure on heating and keeps the closure tight. Also, the opening of the
set screws is considerably simpler and easier with the closure of Fig.
10-1 than with that of Fig. 10-2.
The Gasche closures are the best oTles known, but st:1l they can be
very troublesome if not used properly. The main problem with these
closures is that they gait Galling is the sticking together of metal st'rfaces
at high temperatures aud pressures. Sometimes even at room temper-
ature, closures gall when subjected to high pressures. Galling is the fusion
of the surface molecules of two identical or similar metal surfaces that
are pressed together. In the Gasche closure the lower side surfaces of
,
DESIGN OF LABORATORY AND PILOT-PlANT REACTORS 3t9
the seal ring tend to gall either with the surface A of the so-called dead
man (Fig. 10-1), or with the inside reactor wall at B. It is known that
galling does not occur between dissimilar surfaces. Therefore, when the
reaction chemistry permits it, one of the surfaces, for example the seal
ring, is made from a different material. In high-pressure reactors used
for hydrocarbon reactions such as those involving coal tar, coal, or pe-
troleum products, one must use highly alloyed stainless steels to with-
stand hydrogel, and tydrogen sulfide at hign pressures and tempera-
tures. A sligh: modification I)f this composition is not enough to prevent
galling. The only working solution in hydrogenation reactions is to spray
4
a thin film of :.1OS 2 on the surface edges that are prone to gall. On
heating, this sulfide film sufficiently changes the metal surfaces to pre-
vent them from galling. Such spray!> are commercially available.
An absolute necessity for successful 0F~ration of autoclaves is that
closures and closure surfaces must be handled with great care. Labo-
ratory personnel handling autoclaves must be properly trained, weli
supervised, and kept on the job.
Cover Set screw
- Lock nut
-Main nut
-Seal
.
-, - , ring
Reaction
space '- Reactor
body
-
f---Sea, ring
•
FIG. 10·2 Earlier Gasche closure.' (Courtesy Autoclave Engineers, Inc.)

•
When similar materials are used on the seal ring and on the touching
reactor surfaces, keeping the reactor closure under 1700 bars nitrogen
pressure at room temperature for several hours can cause severe galling .. •
Figure 10-3 shows the general arrangement of a shaking autoclave,

both from the front (a) and from the back (b).
The Swagelok Reactor

Home-made reactors can be put together quite easily by using 'itainless
steel tubing iengths and swagelok fittings. * If the ends of the tubing
pieces are well prepared by filing them properly and annealing thel1l,
the swagelok reactor is a very safe pressure reactor and does not need
any state inspection or any code stamps. A \'ery elaborate micro reactor
system using such a swagelok reactor has been described by Harrison et
5
aI. A considerably simpler, and of course less costly, microreactor system
is shown in Fig. 10-4. Such a system can be assembled in a relatively
short time for use. for example, in hydrocarbon hydrogenation reactions.
Product samples are collected and analyzed elsewhere by specialized gas
chromatographers. The micro reactor itself has a reaction volume of 8
3
cm . It is assembled from IJ2-in (0.0127-m)-OD tubing as the reactor wall
and I/H-in- (O.0031-m)-OD tubing as the inlet and outlet pipes. Reactor
and tubing are immersed in a fluidized-bed sand bath. Tiny rounds of
wire screen are installed on both ends of the microreactor to prevent
the catalyst charge from plugging the inlet or the outlet pipe. The fluid-
ized sand bath is a very satisfactory method of uniformly heating the
reactor. The feed can be preheated in the same sand oath by passing it
'\ ,
.- '. through a coil before it enters the microreactor.
It should be emphasized that this simplified version of the micro-
reador system is only suitable for quick exploratory work. Anyone who
expects to do frequent exploratory investigations would do well to set
up an elaborate micro reactor system with automatic sampling, on-line
analysis, and automatic computer processing of the results. The devel-
opment of analytical techniques useful in automatic microreactor systems
•
is presently expanding at an explosive rate.
Larger versions of the swagelok reactor, up to I-in (O.0254-m) OD by
over 1 m long, can be assembled by using special-order swagelok re-
ducing fittings to connect the l-in-OD reactor tubing to 1/4-in- (0.00635- .
m)-OD inlet and outlet tuGings. Such reactors can be heated by placing
them in special electJ;ic furnaces or by wrapping them with electrical
heat-tracing wire units;
*Swagelok fittings are pressure finings manufactured b\ Crawford fitting Company. 29500
Solon Road, Solon. Ohio -H 1:i~1_
•
DESIGN OF LABORATORY AND PILOT-PLANT REACTORS 321
-
•
FIG. 10-3 A rocker-shaker.autoclave assembly: (a) front view, (b) rear view.
(CourteS)' Autoclave Engineers, Inc.)
•
,
,
Ruplure disk 12.7 mm - 316 stainless tubing

Reactor
8.5 mm ID x 15.2 mm long
Feed •
resevotr
•
Condenser
,/' Back'pressure
regulator
Steam jacke: --,
,
ReceIver
Gas
90 cc sample
Reactor ~
Swagelok '- --+-

reactor
heads '-+-- -Ftuidized sand both
Pump
Electric furnace
4.8 kW
Wet gas
3,17 mm OD 6.35 mm OD meter
316 SS tubing 316 SS tubing
FIG. 10-4 A microreactor sYstem. J

•
The temperatures can be sensed at the outside of the reactor skin by

means of thermocouples '\Tapped together with the reactor with asbestos
tape. While this is not an accurate temperature measurement, it may be
close enough for exploratory purposes. Surprisingly enough, these
homemade reactors can be operated leak-free above 300 to 3S0°C. How-
ever, they do gall and are difficult to open after use. Depending on the
wall thickness and the material of the tubing, a 2S-mm-OD swagelok
reactor can be used at se\'erities as high as SOO°C at 100 bars.
Again, it should be emphasized that these larger versions of the swa-
gelok reactor are no substitutes fOl: properly designed flow reactors that
are used in well-plann<;d bench-scale or pilot programs. They do how-
ever fulfill a definite purpose: that of quickly improvising a catalytic
reactor for a brief exploratory study that requires suhst.;mtial qua;ltities
of samples.
Reactions that do not require high pressures and elevated tempera-
tures can be explored in simpler microreactor systems built of plastic
swageloks and tubing, which are much easier to assemble and operate.
•
DESIGN OF LABORATORY AND PILOT-PLANT REACTORS 323
, '
,
Special-Purpose Laboratory Reactors

There are quite a number of special-purpose laboratory reactors that
serve to determine the kinetics of catalytic reactions. The advantages
6
and disadvantages of these reactors have been discussed by Weekman
-
and by Carberry. I
Differential Flow Reactor

The differential flow reactor (see Sec. 3~3,Fig.3-7) is a long, thin tubing
containing a small amount of catalyst that causes a differential conversion
in a How reaction. Depending on the temperature and pressure of the
reaction, the tubing is of either glass or metal. In any case it must be
run absolutely isothermally. tor this purpose, the reactor tubing is con-
tained in a cooling jacket or a heating jacket as the case may be. The
accuracy of the analysis of the converted reaction products determine
how small a differential catalyst
•
bed is used .
Integral Flow Reactor

The integral flow reactor (see Sec. 3.3) is a :ong, thin tubing that is filled
with catalyst. The major problem is again isothermality, which is obtained
in much the same way as in the differential flow reactor. Because a
sizable fraction of the feed is converted, analvtical problems are easier.
The Continuous Stirred-Tank Reactor (CSTR)

A continuous autoclave can be used for liquid reactions. Actually, any
continuous-flow stirred pot can be used for gas-liquid reactions if pres-
sure-temperature conditions are met (see Fig. 3-12 and Sec. 3.3). For
solid-catalyzed gas reactions Carberry introduced the continuous-stirred-
tank catalJlic reactor (CSTCR), which consists of a rotating basket of cat-
alyst particles (Fig. 10-5).8 This CSTCR reactor operates isothermally
and delivers integral reactor conversions. It accommodates commercial-
size pellets and extruded catalysts. It is now available commercially. Ross
9
and Calderbank used the eSTeR in the study of naphthalene oxidation
over V20 S'
Numerous \ariatioQs of the eSTeR idea have been proposed. One
that claims to enhance '~uniformity of composition of both.gas and liquid
phases with independent control of individual film resistances and in-
terfacial area" has been published by Levenspiel and Godfreylo who call
the apparatus a "double mixed contactor." It extends the concept of
gradientless reactors for heterogf'neous catalysis to two-fluid systems.
•
sheave
Glycerol s€ol--------. •
·~-Beor ing coolonl

Teflon bearing
~+--Oring
Thermocouple well-----l ~Producl gas
Bronze Feed gas
bearir.g --~,,--:
Catolysl I
baskels --i----
----1- Heat ing tape
Baffles --t--
Propellor ---+-
Agito1nr shafl
-Catalyst
--- Pellets
FIG. 10-5 Continuous stirred-tank catalytic reactor of J. J. Carberry (From D.

G. Tajbl,j. B. Simons, andJamesJ. Carbeny, «Heterogeneous Catlysis in a Con-
tinuous Stil1'ed Tank Reactor," Ind. Eng. Chem. Fundamentals, 5:/72 (1966), by
•
\.
'>0, I
pennission from the American Chemical Society.)
The Recycle Reactor

The recycle reactor (see Fig. 3-13), like the eSTeR, combines the ad-
vantage of isothermal operation with delivery of integral reactor con-
versions. The original recycle reactor, which consists of a small packed-
bed reactor with an external loop and pump, is quite tricky to operate.
The external loop is plagued by mechanical pump problems, which
require cooling and subsequent reheating of the recycle stream. I I A .
number of \'ariaiions of the recycle reactor have been developed which
use a packed bed with an internal recycle. Bennett et aI.,12 Livbjerg et
aI., 13 and J. J\,L Bertyl'U~ describe such reactors. The Berty reactor is now
being commercially produced and appears to be widely used. Although
it was originally designed for gas reaction:;, it is now being adapted to
11
gas-liquid reactions as well. Figure 10-6 shows a Berty reactor.
•
DESIGN OF LABORATORY AND PllOT-PLANT REACTORS 325
•
The design of any of the above-mentioned laboratory reactors re-

quires hardly any computation for process sizing. Most of the design
problems are of a mechanical nature.
10.3
PILOT REACTORS
Pilot reactors can be as varied as plant reactors. They can be built from
standard Pyrex glass pipes and fittings, from ordinary pipes and fittings,
or if intended for high-pressure use, they can be built from high-strength
steels or stainless steels. For quick and inexpensive experiments one can
use large swagelok reactors similar to tpose discussed above for labo-
ratory reactors.
The recommended closure for an elevated-temperature, elevated-
pressure pilot reactor is the Gasche closure with the resilient ring. This
is true both for fixed-bed service or suspended-bed service. These clo-
sures are costly and usually have a long delivery time. However, once
•
"." .
"
FIG. 10-6 The Berty reactor. (Courtesy Autoclave Engineers, Inc.)

•
one good reactor has been purchased, it can be used for many process
development studies. .
The mechanical design of pilot reactors is based on the same principles
as the design of commercial-size reactors, as discussed in Chap. 12. How-
ever, it is much easier t:) design a small-diameter pilot reactor than a
full-scale reactor because for a given temperature-pressure severity the
wall thicknes~ is proportional to the inside radius of the reactor. Thus,
a high-se\'erity reaction that can easily be contained in a 5-cm-diameter
pilot reactor with a thick \nIl may become a really difficult design prob-
lem for a 2-m-dicmeter comPlercial reactor. Such problems are discussed
in Chap. 12.
Because of the high cost and long delivery time of properly designed
pilot reactors, fron time to time many researchers have to resort to
homemade reacto,s that can be quickly a"semblpd when an urgent and
unforseen need arises. Figure 10-7 shows a cold-sealing closure. The
principle of this design is to keep the sealing pan of the closure far from
the high-temperature zone of the reactor furnace. Then the closure can
be designed for temperatures below 300°C. A metal block called the dead
mall is used to fill the reactor space outside the heating zone. Such a
reactor should have no leakage problem since it av.oids the critical dif-
ferential expansion problem.
Finally, Fig. 10-8 shows an old type of reactor closure that is relatively
inexpensive to fabricate and to maintain. However, it is recommended
, (' • Bolt s or set screws
•
• •
--Seal ring
,..- Cap
--Dead man
- Reactor body
.,..- - Furnace
-
•
•
.l+-t- ...._ - - Reaction space
FIG. 10-7 A cold-sealing reactor closure with "dead man."

•
DESIGN OF LABORATORY AND PILOT-PlANT REACTORS 321
y Boils or set screws

•
I
•
•
_Cop
• Thrust ring
Head
• +-Seol ring
I I
~
•
Reaction space of reactor

!"IG. 10-8 A reactor closure that is tight up to about 300°C.
only for reactions below 300°C, where it can be operated without serious
leakage problems.
The following criteria must be met in designing pilot reactors:
· The reactor must be easily removed from its location. Unlike a: plant
reactor, c pilot reactor is frequentlv opened.
· The closure must be easy to open, clean, and reuse.
· It should be possible to remove the catalyst from the reactor easily
and completely.
•
· The reactor must be easily cleanable.
The de!Oign of reactor internals must also follow the same concern for
ease of removal and cleaning. The inlets and outlets of many fixed-bed
reactors are filled with inert alumina balls because the ends are not
heated to preserve the closures. Alumina balls filled unused reactor
voluITlP in very much the same way a dead man does. Stainless steel
screens are used to prevent these balls from blocking reactor inlet or
outlet pipes.
REFERENCES •
1. Fred Gasche, "Seal," C.S. Patent 3.144,163, Aug. I I, 1964 .

•
2. Fred Gasche, "Design of Reactors and Closures. ··/nd. Eng. Chem. 48:838-840
(1956). # •
3. Fred Gasche, "Closure for High-Pressure Vessel." V.S. Patent 2,424,449,

July 22, 1947.
•
•
4, E. S. Hodge, C. B. Boyer, and F. D. Orcutt, "Gas Pressure Bonding," fnd.

Eng. Chem. 54(1):31-35 (1962).
5, D. P. Harrison,j. W. Hall, and H. f, Rase, HAn Automatic Precision Micro-
reactor," fnd, Eng. Chern. 57(1):18-25 (l965).
6. Vern W. Weekman,Jr., "LaboratOl'Y Reactors and Their Limitations," AfChE
I 20:833-840 (1974),
7. James J. Carberry, Chemiwl & Catal),lic Reactioll Ellgi71eenll:;, McGraw-Hill,
:\'ew York, 1976.
B. D, G, Tajbl,J. B, Simons, and JamesJ. CarbelTL "Heterogeneous Catalysis
ill a Continuous Stirred Tank Reactor," hul. Ell!!, Cliem. FUruWmentals 5!171-1 75
~
11 966).
g, G, L Ross and P. H. Calderbank, "Kinetics of the Catalytic
, Oxidation of
:\aphthalene over V203 Using a Spinning Catahst Basket Reactor," Chem.
E Ilg. Sci. 26:2003-2008 (1971),
10, Octave Levenspiel and J. H. Godfre\', "A Gradientless Contacto;· for Ex-
perimental Study of Interphase Mass Transfer with/without Reaction," pa-
per presented at the 66th Am. lnst. Chem. Engrs. AnnllaI Meeting, Phila-
delphia, l'\ov. 11-15, 1973.
11, J. A. Mahoney, "The Use of a Gradientless Reactor in Petroleum Reaction
. Engineering Studies," paper presented at the 741h l'iational Am. lnst. Chem.
Engrs. Meeting, New Orleans, March 13, 1973.
12. C. 0. Bennett, M. B. Cutlip, and C. C. Yang. "Gradientless ReaGvrs and
Transient Methods of Heterog""neous Catalysis:' Chem. Eng. Sci. 27:2255-2263
(1972).
, 13, Haw, Liybjerg and John VilIadsen, "Internal Recirculation Reactor for the
Oxidation of Sulfur Dioxide on Vanadium Catalyst," Chem. Eng. Sci,
26: 1495-1503 (1971).
14. J.t..L Beny, "Reactor for Vapor-Phase Catalnic Studies," Clum. Eng. Progr.
70(5 ):78-84 (1974).
15. J M, Beny, J. 0, Hambrick, T. R. Malone. and D. S. Ullock, "Reactor for
Vapor-Phase Catalytic Studies:' paper presented at the 64th National Meet-
ing of the AIChE at New Orleans, Mar. 16-20. 1969.
-
•
Chapter REACTOR SAFETY AND ST
E\'ery reactor designer, and of course every chemical plant operator, is

highh' concerned about the safety of reactors. l\lost catalytic I-eactors
keep operating smoothly in the way they are designed to operate and
ne\'er cause any insurmountable problems_ Only a few reactors mal-
function seriously, in which case they may cause man\" deaths. While
J ' "
safely operating reactors are hardly e\'er remembered. the bitter memory
of exploding ones lingers even long after their scrap has been reproc-
essed into a new generation of reactors_ Thus it is the duty of the reactor
designer to check and make sure that the reactor will operate smoothly
and safely .
•
+ , A thorough and complete discussion of this subject would require far

more space than is available in this book. Because of this space limitation,
this chapter is presented as an O\-en-iew of the field to briefly acquaint
the reader with the subject and to point out major problems and pitfalls
in reactor safety, and stability_
,
11.1
VARIOUS CAUSES OF REACTOR MISHAPS
Catalytic reactor mishaps may have a nrietv of causes_ The most com-
mon of them ,,-ill be briefly discussed here.
Defects in Mechanical.Fabrication
There ha\'e been cases .of reactor failure due to weak welding seams
because some careless welder used the wrong electrode and the error
remained undetected because of poor supervision and inspection. Such
reactors usually fail without warning_ This kind of mistake can be avoided
•
if the company that is going to operate the reactor sends in its own
inspector to continuously observe and check everything during the fab-
rication of the pressure vessel.
Excessive Thellllal Excursion during Catalyst Regeneration

Catalysts that al e regenerated in situ require that the reactor vessel be
designed for two sets of conditions: (1) the temperature and pressure
of <he steady-state process and (2) the temperature and pressure of the
catal:'st regeneration step (see Sec. 1.5). Usually the catalyst is regen-
erated by burning off carbon deposits with oxygen diluted in nitrogen
or steam. Oxygen is used at a concentration of about 0.5%. The com-
bustion reaction progrEsses as a hot front from the inlet of the reactor
to the outlet. This reaction must be carefully controlled so that the front
does not become too hot. If the catalyst is in direct contact with the
reactor vessel, the reactor wall must be designed to withstand the ex-
pected temperature of the traveling hot front. Once in a while, because
of poor control and surveillance the combustion temperature may rise
far above the permissible limits and this might not be noticed by the
operators. The temperatu:-e excursion might weaken the welds, and
shortly after the reactor is put back in normal operation, the pressure
vessel might burst open. This kind of catastrophe can be prevented by
designing the reactor vessel to withstand higher temperatures during
regeneration and by controlling the regeneration extremely closely. Re-
cordillg the regeneration temperature will ensure that excessive tem-
peratures will be noticed in time to avoid putting the reactor back on •
stream with a weakened shell. Of course, the problem can be entirely

circumvented by a'.'Oiding in situ regeneration altogether. In this case
the catalyst is simply stripped and dropped from the reactor, to be
immediately replaced by a second batch of catalyst. Operation can be
resumed with little loss of time while the dropped catalyst can be con-
veniently regenerated somewhere else and recharged when the second
batch requires regeneration. When in situ regeneration is not practiced,
the reactor can be designed only for one set of conditions, those of the
steady-state process. However, a second vessel must be designed to re-
generate the fouled or coked catalyst. That vessel is designed to withstand
only high temperatures but not high pressures. Even in case of severe
temperature excursions, the regeneration vessel will in all probability
not fail at its seams betause there will be no pressure to cause such a
failure. ~
-
Catalyst Failure during Regeneration

Certain regeneration procedures are known to affect the mechanical
strength of some catalysts and result in the formation of dust in the
•
REACTOR SAFETY AND STABtUTY 331
catalyst bed. During the following on-stream period, the dust might
catalyze some unsuspected exothermic side reaction and lead to strong
exotherms and sometimes to reactor failure. Such catastrophes can be
avoided by carefully checking for dust formation during regeneration
as early as the bench-scale studies. Usually modifications in regeneration
procedures can prevent dust formation. If this is not possible, the catalyst
can be sieved after each regeneration and the reactive dust kept away
from the reactor.
Dangerous Reactions
Some catalytic reactions are inherently anJ notoriously dangerous. Some
are sensitive to temperatures, others are prone to develop dangerous
side reactions, and some cause occasional explosions without apparent
cause. If the products of such reactions are industrially important, some-
one will have the unpleasant job of designing reactors to contain these
dangerous reactions. The best thing this person can do is to make sure
that no problems occur that are related to pp:ssure vessel design, fab-
rications, or catalyst regeneration. Then the reactor is safely placed be-
hind barricades or reinforced concrete walls. Everything in the reactor
is designed to be remotely operat~d and controlled. Thus if the reactor
still explodes, at least people are protected. The probability of explosion
simply increases the cost of the chemical product because of high in-
surance rates.
Process Control Problems

•
<. , Sometimes even a perfectly "'ell-designed and fabricated reactor can fail
because of inadequate process control systems. In most exothermic proc-
esses certain parameters such as reactant ratio, heat-exchange conditions,
and the like have to be very tightly controlled (see below on parametric
sensitivity). If this control is insufficient or simply not well conceived,
then serious temperature excursions, which can lead to reactor failure,
can occur.
For example, in hydrogen generation from natural gas, the feed is
treated with steam over a first catalyst to partially convert it to CO + H 2 •
Then the CO is further treated with steam over a CO shift catalyst to
form CO 2 and more H 2 • The CO 2 is absorbed by monoethanolamine
washing and finally the last traces of CO + CO2 are removed in a meth-
anator by conversion to CH 4 + H 20. Methanation is a highly exothermic
reaction. If for any reaso.n at all, such as a power failure that would shut
down the monoethanolamine pumps~ the CO 2 content of the methanator
stream should appreciably increase, the control system should imme-
diately act to by-pass the methanator. Any failure of the control system
to do so would, if nothing else, cause the loss of the methanation catalyst
•
by overheating. If the hydrogen process is designed for elevated pres-

sures, it is quite likely that the reactor vessel would fail as well. Thus, in
certain reaction systems safety depends primarily on process control.
In general it is highly desirable to analyze and model the reaction
system at ~and before the design task begins. Any good simulation is
likely to pinpoint potential thermal excursions and weaknesses in dy-
namic process control and prevent the occurrence of control problems.
l\fodeli'lg can also bring to light problems in parametric sensitivity.
11.2
PARAMETRIC SENSITIVITY
When a small change in one parameter of a reactor system causes a big
change in another parameter of that reactor, the phenomenon is called
parametric sensitil'itJ • For example, if we make a small increase in the
coolant temperature of a NINAF reactor and observe a large increase
in the temperature maximum, or hot spot, of the catalyst bed, we say that
the hot spot temperature is very sensitive to the coolant temperature.
This subject has recently been discussed by Lopez et aLl The i\INAF
reactor has a number of othel parametric sensitivities such as inlet tem-
2
perature and concentration. V/elsenaere and Froment c:tlculated the
sensitivities of an ideal one-Gimensional NINAF reactor with constant
700 p=0.019 0.0182
><: 675
-
650
•
0.5 1.0
•
Reoclor lenglh. m
FIG. 11-1 Temperature profiles in a NINAF reactor showing the sensitivity
with respect to patlial pressure of reactant. (From R. J. van Welsenaere and
C. F. Froment, "Parametric Sensitivity and Runaway in Fixed-Bed Catalytic Re-
actors," Chem. Eng. Sci. 25:1505 (1970), reprinted withpennissionfrom Pergamon
Press, Ltd.)
•
REACTOR SAFETY AND STABILITY 333
BOO - - - - - - - - - - -
•
p = 0.017
I
700
.....- 627 K
6 5
600 - - - - - - - - - - - -
0.5 10
Reactor length. m
FIG. 11-2 Temperature profiles in a NINAF reactor showing the sensitivity

with respect to the inlet temperature To; Tu = ~vall temperature. (From R. J.
van Welsenaere and G. F. Froment, "Parametric Sensitivity and Runaway in Fixed-
Bed Catalytic Reactors," Chem. Eng. Sc~. 25:1505 (1970), reprinted with pelmis-
sion from Pergamon Press, Ltd.)
wall temperature for :l single reaction, constar,t fluid density, and no

difference in temp<>rature and partial pressure between fluid and solid.
The sensitivity of the reaction temperature T to partial pressure p is
shown in Fig. 11-1. We can see that there is hardly any hot spot at low
p values. As p increases above 0.016, the temperature begins to exceed
650 K. At P = 0.018 a hot spot of about 680 K develops at 0.7 reactor
,~, length. Here the sensitivity is sharpened. For an additlo.:,al increase of
the p value of only 0.0002, the hot spot increases by about 37 K, and
finally wtlen preaches 0.019, the temperature gets out of control and
runs away. The sensiti\'ity of the reaction temperature T to inlet tem-
perature To (which is set equal to the wall temperature Tu.) is shown in
Fig. 11-2. Here again we can see that from 625 to 627 K we cannot
discern any large increases in the hot spot temperature. However, a
sudden additional increase of only I K causes the formation of a sharp
hot spot peak of about 766 K. When designing this or any other type
of reactor, the designer must first study all such sensitivities, preferably
3
by thorough simulation and modeling. The process designer must try
to minimize these sensitivitie-s by judiciously manipulating various pa-
rameters and in additiolJ must use proper process controls to preven't
runaway temperature. It follows from the foregoing that parametric
sensitivity and reactor sa(ety are very closely relatsd.
Of course KINAF reactors are not the only types of reactors that
display the kind of problems discussed above. Other types of reactors
display similar sensitivities and there is a fairly large literature on the
. •
334'CATAlYTIC REACTOR DESIGN
4
subject. Perhaps one paper by Hlavacek should be mentioned in par-
ticular in this connection. That paper discusses, among other things, a
. method for rapid testing of parametric sensitivity in a NINAF reactor
system. A calculation procedure can determine whether any such sen-
sitivity exists. This book will not go any further into this subject. Instead,
. I~
interested readers are referred to a number of good papers.
11.3
REA~TOR STABILITY
The tellll stability in general usage denotes stableness, lack of change,
and durability. However, in chemical reaction engineering reactor stability
is concerned with the existence of more than one steady state for a
reactor.
Definition and Description of Multiple Steady States

Let us assume a re:lction run in a NINAF reactor which produces a
certain quantity of heat. Let us plot in Fig. 11-3 the total heat content
Q of the reacting system against the reaction temperature T. We have
an S-sh:1ped curve P showing a very slight reaction rate, and hence very
low heat production at Iow temperatures. Then as the temperatu-:-e in-
creases, Q increases exponentially, converting most of the reactants. At
still higher temperatures the rate of increase of Q slows down because
the reactants are substantially depleted. Finally, when everything has
been converted, Q reaches its maximum value, i.e., it remains constant
from there or..: Thus curve P becomes parallel to the temperature axis
OT at very high temperatures. The heat consumption curve C is a straight
line because heat transfer across the sidewalls of the NINAF reactor .,
is linear with temperature, everything else being constant. Curves P and

C intersect at SI, M, and S2, at which points the production and removal
of heat are equaL These three points are steady-state positions.
Let us first assume that the system is at point SI' Any perturbation
that would heat the system slightly above the temperature of S I would
increase the heat removal much above the heat production. Thus the
system would soon cool down and return to SI' On the other hand, any
perturbation that would cool the system slightly below SI would decrease
• the heat removal much below heat production. Thus the system would
soon heat up and return to S I' The same situation exists at S2'
•
Let us assume that the system is at point M and its temperature is M',
Any pertl!rbation t!1at neats the system slightly above M' will increase
heat production much more than heat consumption. Thus, the system
will tend to heat up further and move toward S2' If on the other hand,
the perturbation is such as to cool the system slightly below M', heat
•
REACTOR SAI"EIV AND STABIUTV
•
p
•
I
1 •
-,
-'" I
•
0 I
E 1
-'"
~
>-
1
1
....-
'"
c:: I
I
I
-u I •
-- I
0
I
'" I I
I I
-0
c::
I I
1
1
-'"
c:
0
I
I
I
I
I
I
u I I
-'"
0
I
I
I
I
I
I
::r: I I
I
s; Sz
Reaction temperature T. K
FIG. 11-3 Schematic of total heat content Q of a NINAF reactor as a

function of reaction temperature T. Curve P is the heat generation curve, while
Curve C is the heat consumption curve.
production will be reduced much more than heat removal. Thus the
system will tend to cool down further and move toward SI'
While the system seems always to retu.n to points S I and S2 after any
perturbation, it is displaced from point M by the slightest perturbation.
Points S I and S2 are called stable stead.) ·states, while point M is called a
• metastable steady state. Studies have shown that when a system has three
steady states, the outer ones are generally stable and the middle one
metastable.
What has just been described above is the classical example of steady-
state multiplicity that was first brought to the attention of the scientific
7
community by van Heerden in 1953. For some obscure reason, a 1918
8
publication by F. G. Liljenroth on very much the same subject failed to
9
attract attention.
Obviously, it becomes extremely important to know whether a reacting
system has one or three steady states. Suppose someone designs a NINAF
reactor for this system without being aware of its stability problems.
Suppose this reactor is designed to be operated at temperature TI a.no.
the pressure vessel is designed to withstand 100 bars pressure at tem-
perature T 2 , which is .below S;. As soon as the new reactor is put on
stream with the reactaIlt preheated to T I , the temperature will keep on
increasing by itself and swiftly go toward S;. Of course the reaction will
not proceed at S2 for very long because soon after the reactor vessel
exceeds the temperature T 2 , it will explode. Let us assume now that the
•
•
NINAF reactor was designed to be operated at a temperature T s, which

is slightly below M', again without the designer being aware of the sta-
bility problems. As soon as the new reactor is put on stream with the
reactant preheated to T 3 , the temperature will decrease steadily by itself
and swiftly drop to S;, at which point hardly any product will be obtained.
Once the multiplicity of steady states is known and established, there
are a number of things that can be done to locate the design at a stable
point in Fig. 11-3. One option is to change the intensity of heat removal,
e.g., by installing a larger surface area per unit volume of catalyst and
thereby bringing S2 to a lower temperature T J• In practice, this would
mean a smaller-diameter reactor tube and more tubes. A good solution
of this problem would be to intensify the heat removal to such an extent
that the line C is moved into position C'. In that case, curves P and Cl
have only one intersection, which is a stable steady state, and the in-
stability has been removed. Th;s result might also be achieved by a
somewhat different manipulation of parameters. We are not going to
discuss this problem further.
In cases in which it is not possible, practical, or economically desirable
to get rid of multiple steady states, the line C may be moved just enough
to bring M' and Tl together and the process then is operated at the
metastable steady state M by providing it with powerful process controls.
In case~ whe!"e the process can be designed to operate either around SI
or S2 by slight manipulation of line C, the existence of multiple steady
states might not be any reason for concern at all because the r:::actor
would run at a stable steady state.
For further enlightenment, the reader .is referred to two hooksIQ,J!
- 12 13 .
and three selected papers" , on reactor stabdin·.
Varieties of Steady-State Multiplicity

We have described multiple steady states by taking a NINAF reactor as
an example. It must be said immediately that this phenomenon is not
limited to NINAF reactors. Any type of reactor must be suspected of
potential steady-state multiplicity. To a\'oid a steady-state multiplicity
caused by heat transfer problems, the heat production curve must be
obtained and a heat removal curve must be dewloped that places the
operating conditions of the reactor on a stable-steady-state basis.
Among gas-phase reactor types discussed in previous chapters, only
the NINAF reactor can have heat transfer of the multiple-steady-state
type. Among gas-liquid-phase fixed-bed reactors. trickle beds are always
designed adiabatically and consequently should not be afflicted with this
type of multiplicity. However, FBBRs might conceivably have heat-ex-
change coils installed in the flooded catalyst beds to handle highly ex-
• •
REACTOR SAFElY AND STABIUTY 337
other mic reactions and then should be classified as nonadiabatic. Thus

non adiabatic FBBRs and all ~ypes of suspended-bed reactors should be
suspected of having multiple steady states caused by heat-transfer problems.
Unfortunately, it cannot be stated that any reactor that does not ex-
change heat with its surroundings is immune to stability problems. It is
9 14
not. Adiabatic CSTRs can have multiple stead v states. . .1:'. Actuallv, adi-
;
abatic CSTRs, like gas-phase adiabatic reactors, can absorb the generated
exothermic heat by simply heating the reacting mi"wre to a temperature
above the feed temperature. The conditions under which adiabatic CSTRs
display a steady-state multiplicity haw been analyzed and discussed by
Y
Aris and others.
If the generated heat cannot be fully absorbed by the reactants, the
CSTR must be cooled. Then we have a nonadiabatic CSTR at hand. The
stability problems of these reactors have been analyzed quite intensively
by many investigators. Under certain conditions nonadiabatic CSTRs
can display more than three steady states and can oscil!ate.6.15.16
Actually the stability problem goes even deeper than that. Irrespective
of reactor types or adiabaticity, some types of heterogeneous catalytic
17 IH
reactions can have stability problems at the catalyst pellet level. . Beusch,
18
Fieguth, and Wicke report on a reaction in which H2 was oxidized over
a O.4o/c Pt-on-silica-alumina catalyst at 139°C. When the H2 content of
the gas stream was gradually increased, the temperature rlifference III
between the catalyst surface and the bulk flow slowly inc-eased to 20°C
(Fig. 11-4). However, <'.t 5.5% H2 content of the gas At suddenly jumped
to 185°C. When H~ content was decreased again, At did not drop to
~.5% but fell somewhat gradually, forming a hysteresis loop. This loop
represents the range of multiple steady states. When gas flow was in-
creased, temperature "ignition" occurred at lower H2 content and the
area of the hysteresis loop was d e c r e a s e d . -
When the same reaction was run at fixed flow rates and at 30 to 80°C,
it was observed that the particle temperature and effluent composition
(reaction rate) were oscillating (Fig. 11-5). These oscillations had a period
of 1 h.
Why these oscillations occur and what their mechanism is is not quite
understood. One could suspect, howeycr, that they might have some
relation to the adsorption of the catalyst surface of certain species, which
then react and vacate the active sites. Then the cycle
, would start all over
again. Recently Takoudis, Schmidt, and Arisl9 studied a case in which
"the kinetics of the surface is controlling, i.e., where heat and mass
transfer and reactor flo,": effects are absent so that the temperature and
- pressure at the surface are constant." The study is ora purely theoretical
aature and applies to a chemical reaction of the type A ) B + C, where
only reactant A is strongly adsorbed. Calculations show the existence of
,
CATAlYTIC REACTOR DESIGN .
•
•I
150 ••
I•
I
I
I
100 A
I
<J
0
--
<l
I
t
I
t
I
50 •
1
I
o ~~ _____~L-- _ __
j 2 3 4 5 6
Volume, % Ht
FIG. 11-4 Stepwise t13ositions between lower and upper stable states of Ht
oxidation on a singl ~ catalyst pal tide in a packed bed of inactive pellets. Linear
gas flow rate (slandald conditions, empty tube): v = 1.7 cm/s; Ht percentage
increasing: 0, decreasing: •• Temperature of fUl'Dace and gas flow is 139°C.
(From Beusch, Fieguth, and Wicke,·8 with pe,.mission from the American Chemical
Society.)
multiple steady states under certain conditions. Although these results

have not yet been confinned by experiments, the experimental work by
•
Wicke and coworkers I.' suggests that eventual confirmation should not
•
surpnse us.
11.4
DISCUSSION AND CON·~LUSION
In the foregoing the reader was strongly warned of the existence of a
number of reactor safety and stability problems, so that all potential
sources of danger may be checked before beginning the design 'wrk.
It is of course impossible to list here all potential sources of reactor
failure. The designer must thoroughly study the literature, use some
established techniques along with intuition to list as many of such sources
as possible, and then check them all and make sure that they will not
plague the design. .
Reactor stability is a relatively new branch of chemicai reaction en-
gineering. Many predictions of steady-state multiplicity are based on
certain reactor models t!}at simulate reality with various degrees of suc-
cess. The degree of success determines to a great extent whether the
steady-state multiplicity indicated is real or not. It also determines whether
reactors that are indicated to be stable are really so. This dilemma is best
,
illustrated with the help of Fig. 11-6, published by Froment,20 where

each curve represents the temperature profile in a N INAF reactor ac-
cording to a different model of the reactor. Let us assume that the de-
signer's model gave Curve 6, but that in actual plant operation one would
obtain CUl'\'e 7. which is a runaway. The designer and the Flant operators
would be in serious trouble. On the other hand, the reverse may happen:
the designer may use a model from which C'lrve 7 is calculated, while
actual plant opel'ation produces Curve 6 0r 1. [he d..::signer would Cf'r-
tainly be overcautious and the resulting redctor design , .. ould be un-
necessarily consenatiye and costly.
Consequently, it is difficult not to conclude that a wise catalytic reactor
designer should insist on receiving adequate experimental data before
beginning- the design work. Properly performed ber:::h-scale tests should
certainly detect whether any steady-state multiplicity exists on the catalyst
particle level. l\Il\'AF reactors can easily be checked by piloting a single
reactor tube under various conditions. Similarly, any reactor type sus-
pected of instability should be investigated experimentally to back up
stabilitv• calculations derived from mathematical models. Granted, models
are indispensable and wonderful tools for reactor design. However, when
confronted with the possibilities of parametric sensitivity and instability,
nothing is as reassuring to a concerned designer as good experimental
data.
The most ambitious goal of chemical reaction engineering is to enable
a designer to make an a priori design of any type of reactor for any set
225
200
175
'-'
o E
a.
>-
- 150 a.
125
1000
900
50 ---- --- -
_--= 800
o 20 40 60 80 100
Time, min
FIG. 11-5 Oscillations of tl'mperatures of a single catalyst particle (Tc center,
T, surface) and of reaction rate (C HzO in the eilluent). Gas temperature Tg = 70°C;
18
3.14 vol% H%; v = 36 cm/so (From Beusch, Fieguth, and Wicke with permission
from the American Chemical Society.)
•
I
420~ 7 5
4
3
400 2
u
o
r-
- 1
380 6
OE 0.50 0.75
Z,m
FIG. 11-6 Two-dimensional heterogen<.ous model. Radial mean temperature
as a function of bed length. Comparison with other models. Curve 1: Basic
one-dimensional pseudohomogeneous model; Curve 2: One-oimensional het-
erogeneous model with interfacial gradients; Curve 3: Two-dimensional pseu-
dohomogeneous model; Curve 4: Two-dimensional heterogeneous model; Curve
5: Two-dimensional heterogeneous model. Boundary condition at the wall:
o'T,Ior' = 0; Curve 6: Two-dimensi,mal heterogeneous model. Boundary con-
dition at the wall T, = Tu.; Curve 7: Two-aimensional heterogeneous model.
20
Radial heat transfer only through the fluid. (From C. F. Froment with the
pern.ission of the American Chemical Society.)
,. of reactions of any imaginable complexity. Such a dream could only be

• • realized if we could know evernhing about nature. Since this does not
seem likely to happen, at least in the foreseeable future, the \,'ise designer
\,·ill always try first to mentally model nature and attempt £0 predict hO\,'
nature is going to behave. HOKever, the designer will not trust these
predictions until nature is actually observed to behave in the predicted
\,'a y .
•
REFERENCES
1. A. S. Lopez, H. 1. DeLasa, and J.
A. Porras, "Parametric Sensitivity of a
Fixed-Bed Catalytic Reactor Cooling Fluid Flow Influence:' Chel!l. Fng.
Sci. 36:285-291 (1981).
2. R. J. Welsenaere and Gilbert F. Froment, "Parametric Se,lsiti\it\ and Run-
away in Fixed-Bed Catal~tic Reactors," Chem. Eng. Sci. 25: 1503-1516 (1970).
3. E. D. Gilles and H. Schuler, "Zur fruhzeitigen Erkennung gefahrlicher Reak-
tionszustande in chemischen Reaktoren," Chem.-Ingr. Tech. 53:673-kl82 (1981).
4. V. Hla\"acek, "Aspects in Design of Packed Catalytic Reactors." Ind. Eng.
Ghem. 62(7):8-26 (197C).
,
5. Gilbert F. FromelH, "Some Aspects or the Design of Fixed-Bed Reactors f()r

H vdrocarbon
, Oxidation." Period. Polyfl'(h. 15(:-\ ):21 ~1-24·1 (1971).
. '
(i. K. R. \\'estenerf>, "~laxi!1lllm All()\\'ahk Temperatures in Chemical Reac-

tors. " ('/
. 1/'111. j': IIg . .l,n.
"' l~
/:. !')')-4"'~
_" :>, ( I()(")
, )_ J.
7. C. "<illHeerdell, '":\lItotherrnic l'roce,se, Prllperties and Reaclor Design,"

Jilt!. Ft/!!. ehrlll. 45:1242-12·17 (I(I:-,~l!
"
S. F. C. Liljenrot/J, "Starrillg and Stabilil\ l'ilenOIllt"lla of" ;\IIIIllIHli;, C"i<iatioll
· '1 ,11' R t',KlIollS,
an< I .S1nl! . '" C",111'111 ...\[ d. f':111:.
.
19 :_<';-_
,),,- 'h)"
..) (. I'!I'
. 1"i),
'I. Rwherf()rd :\ris, '"SOllle Problems ill tilt' Allah'ls of Tr;llIsient Beh;Jlior
and Stability of" CJlt'lllical Reactors.'" in (,'fit/lino! /(1'11(111111 f:lIgl/II'l'ri,'~. ,\d-
1;IIKes ill Chemist n Serin 1(J'I, AlIleriG!Il (:hellJi, al SOl i"l \. 1'172, I'll. :, 7S~i()·1.
10. DanielD. l'erlllluuer. Sllihilily of Lhi'lll/fI;! Rmclll'<. 1'1'(,1111((,-11:.11. Fngk\\'()()d
( 'I'f'"
. ItS. '"
i"., , " I()-')
. I _ .
11. JdIllt'S \1. I)ouglas. j>,-o('l'" /)Yll(lNIIC\ (jUI;' (.'(!!{{rll!. \o!. 1: ·-\!{({(Yli, of 1J.lll(n!lic
S,."If'llIs. \'01. 2: COlllrul \\'/('711 .'lvllflil'lll. I'rcIllic<,-l-Iall. Eflgle\I'()()d Cliffs. :\..1 ..
1972.
I:.:'. C. \all Heen;en, "The Character of t!le SUliollan Stale of EX()lhermic
Processes." Chl'ln. Fng. SIl. 8:1,):-1-14:) II'F,K) .
..
I cl. E. Wicke, "l.'ber die Slati()naren 7ust;inde e"orhenller (;,lsreakti()J1en an
pori)sen Katalvsatoren." Chl'm.-fllg;. Ire), 29::iIl.')-:l I1 (I ~l:)7:.
H. Rwhedilrd Aris, EI"1I101!illl Chcmiw! 11,(;''(01 .\uflf.... ,i,. l'renlice-I-Iall. Engle-
. d ('I·f'f··
\\00 n .J. . 1,Hd.
~ 1 S. 11.' ('(
p. '_.')_.
)-')
l'i. J. c:.Chaq)entiel', "C"'-Liquid ReactOJ'." in Clil'llli(li/ F\moio/l EIlr;illl'erillg

Rn '1nl'S Howioll. S,'mpmium Series 7'2 ..-\mencan Chemical Society, 1971),
pp 223-261.
\
16. Peter Hugo and H.-I'. \\,irges, "Theorelical and Experimental Stud\' of Self-
Sustained Oscillatiom in a Stirred Tank Reactor." in Clil'lnim/ Rf(Jctio/l EII-
gillPerillg Re"ieIL's HO/i.llo1!. Symposium Series 6.'), American Chemical So-
ciet\', 1978. pp. 49S-S11.
17. c:. \lcGrean and J. \1. Thormon, "Stabilit\' Studies of Single eau!:'st Par-
ticles." in Climliw/ R('(v/ii;1/ EIl!!:illrrnnz . .-\d\'ances ill Chemistr\' Series 109,
~ J , •
American Chemical Society. 1972. pp. 6()7--D(J~1.

I R. 1-1. Beusch, P. fieguth. and L 'ficke. "l'llstable Beil,lIior of Chemical Re-
actions at Single CalailSI Particles." in ('lion/col R{'act/on FlIgW{'crillg, Ad-
lances in Chemistn Series 109. ,-\merican Chemical Societl. l(l72. pp. 615-
621 .
1'I. C. C. Takolldis, 1.. D. Scilmidt, and Rutherford :\ris. "\!ultiple Stead\ States
•
in Reaction Controlled Surface Calailzed Reactions," ehclII. t;/Ig. Se/.
36:317-386 (l9H I)
LO. Gilben F. F romen L ....\ Ilahsis
. and Design
'---
of Fixed Bed Catalnic Reactors," ,
in Chemical Reaction f:lIg/l/eering, Ad\'ances in Chemistry Series 109, Amer-

ican Chemical Society. I CJ72, p. 30.
•
THE MECHANICAL DESIGN

ClwjJter
OF COMMERCIAL REACTORS
The mechanical design of commercial-size reactors is considerably more

difficult than that of laboratorv or pilot-scale reactors. rvlanv sets of
temperature· pressure conditions, \\'hich would be easy to meet on the
pilot-scale reactors, prese!1t formidable problems in commercial scale.
The purpose of this chapter is not to teach tLe mechanical design of
catalytic reactors but simph' to give the reader an ~)\'en'iew and under-
standing of the major problems and their solutions in this discipline.
The catalytic reactor designer must acquire a thorough understanding
of these problems because the\' are intimately connected with the process
desIgn. Even the most elegant process design of a reactor is worthless •
unless a corresponding workable mechanical design can be developed.

Sometimes high pressures set the limit, at other times corrosion problems
cause the difficulties. While the catalytic reactor designer must be quite
knowledgeable in mechanical design, a sound and safe mechanical design
bv an up-to-date and experienced mechanical engineer is still essentiaL
As a mattu of fact, designing reactors is not a routine job that any
mechanical engineer can tackle. It is a very special field that has to be
learned and mastered.
Since most catalytic reactions are run at elevated pressures and tem-
peratures, the first problem of the mechanical engineer is designing
vessels that can safely contain the particular combination of temperature
and pressure. -
•
12.1 ..
DESIGNING FOR PRESSURE
Designing pressure vessels is not a pure engineering task. It also has a
legal aspect.
,
Design Cedes
The pressure design of reactors is carried out in conformity with the
pressure vessel code of the country where the reactor will be erected
and operated. In the United States, we have the Pressure Vessel Code
of the American Society of Mechanical Engineus (AS1\1E),1 which has
been adopted into law by all stales in the United States. all provinces of
Canada, and a number of municipzlities in both these countries. The
AStv1E code, and with it the statp~' codes. are amend"d fr()n1 time to
time to conform with progress in pressure vessel kchno\()gy.~ The state
codes sometimes differ slightly from eac1 othc:-. Otl~er ind 113trial coun-
tries ha\'e, of course, their own codes.~-~ Some de\eloping countries
would probably accept a pressure vessel design if it conforms to the code
of one of the foremost industrial nations, :;uch as the enited States or
the Federal Republic of Germany. Altho'lgh an international cude of
pressure vessel design is reported to be in the works,' American designers
are still using the ASME Code. While code data may some\\·hat r1iffer
from country to country, the codes all follow the same principles, which
the catalytic reactor designer must understand.
The Strength of the Reactor Wall

Mechanicallv. all catalvtic reactors are metallic vessels with walls lhat
" ' /
can resist the pressure of the reacting mixture at the temperature of the
reaction. Figure 12-1 schematically shoKs a section of a reactor wall on
which the internal pressure is exerted. As a result of this force, the
material of the wall is pulled apart. AD\' point A inside the \\'all is sub-
jected to tension in two directions: the first is circumferential or per-
pendicular to P and in the plane of the:. figure; the second is longitudinal
or perpendicular to the plane of the figure at A. The longitudinal tension
is caused by the heads of the cylindrical reactor. The property of a metal
to resist these tensile forces is called tensile strength and the test that
measures this strength is called the tensile test. At no time should the
pressure-induced tensions in a reactor wall exceed the tensile strength
of the wall metal at that temperature or the wall may fail, i.e .. crack or
burst open.
·A
p
p ~ Reactor
p
woll
•
FIG. 12-1 Forces on the inside wall of a reactor.

THE MECHANICAL DESIGN OF COMMERCLA.L REACTORS 345
! ~-----~/ I n
1
Li ~~~/~~~~~~~~~~ ___ ~I
U
FIG. 12-2 General shape of tensile specimen of metal.
Basically, in the tensile test a specimen of ~tandarc! size and shape

(Fig. 12-2) is stretched in a special testing m;lChine utltil it breaks. The
applieo I(Jdd is ~'xpressed as the stress u. \\'hilh is ddinec! as the load
per unit or original cr<'ss-secrional area of tile specimen ;tnd is expressed
in pascals or nc\\'tons per square Illeter. The elongation of the specimen
PCT unit ut OrIginal length (a dimensioniess (ju<lIl!i!\) is called straill E,
Figure 12-3 shows a curye recorded \)\ a SlreSs-le,,! IllachillC. The tested
material was ASTM A588 Graoe B steel. a high-qrcngth. low-alloy struc-
tural steel. The' ordinate represents load ill pounds and the abscissa
indicates the elongation. The shape uf the Ull\ e uf Fig. 12<~ is typical
of low-allm', carbon steels. l'\ormali\, . the data obtained from the test
machine are plotted in a graph \,'ith stress er in pascais as ordinate and
strain E as abscissa. Figure 12-4 represellts such a t,ypical graph (it is not
a plot of Fig. 12-3 data).
The section OA in Figs. 12-3 aane! I ~-4 rerre~el1!S the proportional
region. The elongation resulting from allY IOdd in this region disappedrs
as soon as the load is removed and the specimen returns to its original
size. This is expressed b~' Hooke's lazl'." \\'hich states that the strain in
proportional to the stress applied:
(12-1 )
"
and the proportionality factor E is called the 1II0dulus of elastici(v. 10.1 I In
other words, the steel behaves as an elastic material in this region. For
carbon steels E is in the order of 2.07 x 10" TI.!Pa.
If the stress is increased beyond the point A. the proportional limit, the
steel no longer follows Hooke's la\\' and one obtains an appreciable amount
of elongation without increasing i he load. This is called yielding. The
stress cOITesponding to the point B is called the yield poillt. Upon further
stretching of the specimen the steel rec()Yers its re,iSl:IllCe and the tensile
force increase results in additional elongation up to point C, \\·here the
force reaches a maximum. The stress that corresponds to this maximum
force is called the ultimate strength of the materiaL Beyond C, the bar is
•
stretched even if the load is decreased, and it finally• fractures at D .
Unlike the proportional region OA. any elongation be\(md A is irreversible.
When the specimen st.retches under the influence of a load, it also
shrinks in cross section. This lateral contraction in the 0.4 region is elastic
and reversible. The ratio of this lateral contraction to the axial e1onga-
tioIl, expressed by the same unit. is constant inside the elastic limit for
,
I . U:1imole strength' 80,140 Ib/inl (55524 MPa)

4000 >-
3840 - - - - - - - - - - - --- ~-~_ _~C:;..c,
3000 IF A
2840 ---- B
o
L '\..Y,eld strength' 59,270 Ibflo (408.65 MPo)
- I
g 2000 ~
-'
I
1000 I
~
v
Elongation
FIG. 12-3 Load-elongation diagram of a normalized ASTM A588 Grade B

steel. (Courtes)' Fazil Erdogall, Lehigh Ullh'ersity.)
any given material. This la\\' is calL,d POI.IIOII·., Iou', the ratio is known as
POi.IS(lIl'S miio, and its constant '·alue \,·ili be designated 1)\· fl.. In case of
ordinan, structural steel f.l can be taken as O.:W.

Poisson's law can be expressed as
( 12-2)
where E, is the strain (unit elongation) obtained in the direction J of tne

load and Ex is the strain (unit contraction) obtained in the direction x
perpendicular to the direction y of the load.
Beyond the proportionality limit, the lateral contraction of the spec-
imen is also irreversible.
There are big differences among the stress-strain diagrams of various
materials. Figure 12-5 is the load \'s. elongation diagram recorded by a
test machine for a tempered bainitic steel that contains Cl', \fo. and V.
While this material has a yery di5tinct proportional region, its \ield point
is not visible. In this diagram it \,'<lS determined lw cOIH'emion as the
intersection at 0.02% elongation, of a line parallel to the proportional
line with the nonelastic part of the cune. The cune of Fig. 12-5 is of
interest mostly because of its different shape,
Figure 12-6 shows a l);pical stress-strain diagram for cast iron. Cast
iron has a very low proportionality limit, which is \'e1'Y difficult to de-
termine. It has no definite yield point. The stress-strain diagrams for
brass and aluminum also look quite similar to that of cast iron.
•
THE MECHANICAL DESIGN OF COMMERCIAL REACTORS 347
The tensile test gives very important information on the mechanical

properties of a construction materiaL All construction materials such as
beams, rods, sheets. CIC.. are used \\-ell below their proportionality limit.
It is usually trickv to measure the exact point at ,,'hich proportionality
ends, In order to circlIm\'ent this difficult\'. it is customary in mechanical , ,
design to calculate a ;l'())'/iillg strl'ss CT bv cb'iding the yield stress eT, by a

sail't.. factor 11,
(12-3 )
or by di\'icling the ultimate strength IT" b\ a different safetY factor 111

,
eT d , = CT)]I] (12-4)
When designing \\'ith structurai steeL Eq, (12<1) is used and a safety
factor of 11 = 2 gi\'cS a cOllsenatin: \~duc for the working stress. pn)\'icied
that onl\' constant or static load, ha\'c to he handled. For machine parts
exposed to variable LJads. larger factors of safet\' are necessary.
In pressure \'esse! design the AS\[[ code gi\~s lIlaximum aUowablr stress
data for each material at various temperatures. These data include the
necessan safet" factors and can be used as is. Such data can be found
, '
l
in the .-\S)'[E Boiler and PressUlc \'essel Code and also in the Chemical
E ngi 1/ 1'1'1.1' Ha /ill boo/i, ! C'
The maximum allo\\'able stress of steels is almost constant up to 350
to 45(rc. abO\'e which it declines quite rapidly. Figure 12-7 shows the
plots of tbe maximum allO\\'able stress data for three types of steel as a
function of temperature, It can be seen that the simple carbon steel
, begins to weaken at 3400C. The lo,,-allo\ s~:.?el containing 2.5'7c Cl' and
1'7c I\10 is unchanged up to 440°C, while the weakening of type 316
austenitic steel \\'ith 18Sc Cr, lO'7c :\i. and 2'7c Mo does not occur until
475°C. It is possible 10 increase the strength of the steels by properly
adding allo\'ing components such as Cr, l\i, 1\'10, and some other ele-
ments. AlIo\'ing also affects the corrosion resistance of steels.
c
~
, "
•
A
0
CL
b
• --.., -
~
~
~
•
-
~
(/)
•
",
S'roin E. dlmensionless
FIG. 12-4 Typical shape of a stress-strain diagraIll of ordinary carbon steel.
,
,
30,000 Cy-28,200!b (12,791 ~,gj
!---
A ,/~\
"-Yield po:nt /Breok Ir,ad '
27,500 tb(12,471 kg} 0 , 21,0001b
20,000 r \
=
~
I
/ \
\
\
\
\9,525 kg)
\
~
~ I, \
0
0
, I \
,
\
,
10,000 i \
,
/ I
!
\
•I
i
,
I
/ •
I
! •
I • i
0 ">
,,
..~
01 0.2 ,,~
u. v 04
% elongation
FIG. 12-5 Load-elongation diagram of a tempered bainitic steel containing
Cr. Mo, and V. (Courtesy Fazil Erc!.Jgan, Lehigh University.)
In addition to losing e
their strengths.
_
some steels also creep at tem-
peratures above 370°C. Creej) is vC'y slow £10\\' under SI ress. I t is or course
yen important that creep be kept to a minimum in reactor dC'iign, The
crajJ test measures the rate of eL:ngation of a specimen under constant
tension and gives the temperature at which I ex creep occurs ill 10.000
h or in 100,000 h. Thus high-temperature properties of metals are just
as important as their ambient-temperature pl'Operties \\,hen selecting a
reactor plate steel.
• l\lost reactor vessels are cylindrical. If a relati\'ely low to moderate
pressure is to be handled, the reactor wall does not have to be \er;' thick
and the tensile stress does not vary appreciably uet ween the inside and
outside surfaces of the wall. However, if high pressures ha\'e to be con-
tained in the reactor, the wall thickness has to be increased, the distri-
bution of the stress inside the thick wall becomes nonuniform, and design
calculations become quite complicated. Thus we \\-ill discuss the design
of thin-walled reactors separately from that of thick-\\-alled reactors.
Design of Thin-Walled Reactors

If uniformly distributed radial forces are applied to the inside of a tbin
circular ring in the form of fluid pressure, as seen in Fig. 12-80. the ring
will be enlarged uniformly. In order to be able to size the wall thickness
to contain the radial fortes, we must calculate the tensile force FT in the
ring. Let us assume that the ring has a radial thickness t and a longit udinal
thickness l. Let us cut it into two halves at the horizontal diameter section
so that the upper half-circle behaves as a free body (Fig. 12-8b).
Let us consider a section of the circular ring of central angle et \\'ith the
,
horizontal, and a differential section of angle da. Let us calculate the

f()rces that act UpOIl this differential portion of the ring. The main
intern,!l force is the pressure /' (l(>rct~ per uIlit area). The intern:!l surface
area of the differential ring section is rh/ex, "hen' r is the inside radius
of the ring. Thus the force Ih;H acts UpOIl Ihis differential surface is
Pr/do.. 'file \'el,tical component of this (JI'el' acting upon the horizomal
cenleriine is Pr/do. . sin 0: and is directed ujl\\ard ... , \\'e can take lilt' sum
of the \'enieal cOlllponcllts of all Ihe force, :tni!lg (JJ] !he hall-ring ane!
babnce them \\'ith a downward directed force F{ ;ll each end of ,he half-
ring. These balancing fonTS arc lht' lensiil' f()rces:
--"
-() J: / .-- PI! . sill (, . d ( t = f)rI! - «)Set - «(Jllsll~
_ iI
Pr! [1.0 + COllst] - 1- 1.0 + (Oml] = '2Prf
t,
;
I,
,,
c
Cl.
b
c"
~
~
-~
C'O
I
,
I
FIG. 12-6 Typical shape of a stress-strain diagram of cast iron.
Low alloy steel SA - 387 D 25 Cr 10 Mo

,
~
ci" 10'- - - - - - - . . . ,
____ Austendic stainless steel
8 V< SA-240 type 316
18CrlONi2Mo
6~
-- L
"
E 4
co
E
Carbon steel
SA-201 A----
o' - - _ - ' - - - - _ . L . - _ - ' - _ - ' - _ - - - - - ' , - - - - - ' - -
•
---~
o 200 400 ~ 600 800

-.
Temperature, 'C
FIG. 12-7 Maximum allowable stress curves of three types of steel as a func-
tion of temperature, plotted from data in the ASME Boiler and Pressure Vessel
Code. I By permission.
•
The tensile stress in the ring may now be obtained by dividing the force
F-r by the cross-sectional area tl of the ring:
(J = Frlt! = Pr/I (12-5 )

l
When cksigning according to the AS:'l E code. one uses the following
formula for thin-\\'alled pressure vessels:
! = h!(SE - (l.GP) ( 12-6)
\I'here I - minimum required thickness of shell or head after forming,

excl usi \'e 1)1' corrosion allo\\d nce. m
P design pressure. 1'<1
) - inside radius of shell course under considerati(,n, m
S' - maximum all()\\'able stress. 1'a
E i()\\'esl efficienn of any joint in the head, dimensionless
In uses units. I and rare gi\en in inches and P and S are give.} in
pounds per square inch.
The parameter E expresses the confidence in the qualit\' of a seam.
Its maximum \'alue is 1.0. \\'hich is its \alue for a seamless head. The
efficiency of \\'e1ded or ri\eted joints can be obtained from the ASME
code. I
If the wall thickness of a reactor is all'ead:: gi\'en, the maximum pres-
sure it can withstand can be calculated from the formula I:
P = SEtl(T + 0.6 t) (12-7)
Other formulas are anilable for designing thin-wall reactor heads.1.I2
Design of Thick-Walled Reactors

For a constant internal radius and construction material, we can increase
the internal pressure P if the wall thickness t is also increased propor-
tionally, as per Eg. (12-6). Bnond a certain point, a further increase in
t causes the distribution of the tensile stress throughout the wall to be-
•
come nonuniform. Thus the wall thickness must be increased more than
in proportion to the pPessure. :\5 long as the deformation of the thick-
wall reactor remains bel",,\' the elastic limit of the steel, we can calculate
its thickness as a function of the internal pressure.
ComingslO used a de\'elopment somewhat similar to that we used for
•
, \
\ \
\,
, \
,
•
;' )
/
/
/'
/
( a)
I b)
FIG. 12-8 Tensions in thin-walled reactor under internal pressure.
thin-walled reactors to calculate stresses and strains in a thick-walled

reactor and obtained the following formulas (see Fig, 12-9):
• <)
(I~. /'!t + 1
" (12-8)
(r~hl)- 1
(12 -9)
where (o-Jr - tangential stress at inside radius

(o-r)r - radial stress at inside radius
PI - inside pressure
1'1 -- inside radius
1'2
-- outside radius
Equation (12-9) represents the maximum radial tensile stress at the inner
surface of the pressure \'essel and that stress is equal to the rCJ.c~ion
pressure,
The longitudinal stress 0-, is gi\en by:
0- , -- (12-10)
•
(Jr+dO-r
(Tr
'2
- C' ,,
FIG. 12-9 Force balance on section of thick-\\'alIed cylinder. (From Com-

mings,'O bJ' permissivn.)
COlllin~sl" has dClllOI1SITated t:l;\1 a thid;,-\\'alled cylindrical reactor

subjected to internal pressure alone is consiclerabh' more stressed near
its inner surface than near its oLlter surface, Thus it is pel-fectly possible
to ha\'e the iIlner la\ TS stressed to near or abO\'e the elastic limit while
,
the outer layers still are under relati\Th' 10\\' stresses, It call be concluded
, ,
that limiting the reactor desi~ll onl\ to elastic strains \\'()uld not use the
strength of the steel effectively,
Several ways ha\'e been devised to use the strength of the steel more
effecti\'eh', These methods will be discussed further belm\'. The general
idea is to build up the wall in ia: :::1's. \\hich are prestressed bv the proper
amount. \Vhen internal pressure is applied, the initial stress is o\'ercome
and re\'ersed. Such reactors can be designed and fabricated for operation
under stresses that are uniform I\" distributed throughout the thick wall
at a specified operating pressure. l;nder these conditions and at this one
operating pressu re. the thin-walled formula of Eg. (12-5) applies.
Design procedures for multila\'er thick-,,"alled pressure \essels ha\"e
( ' .
I)een presentee1 I)\ ,ol11mgs. III
The AS~IE code recommends desi<>nin(Y i) 0

unla\ered
'
thick-\\'alled re-
actors accordingc, to the formulas:
I = I'(~"' ~ I) (12-11)
-
where ~ (SE -;- P)!(SE ~ P)
•
and P_= SE(Z' ~ 1)([ -,- I) (12-12)

",here Z' = «I' +
These formulas are \'alid when the thickness exceeds 0.5 1'1 or \\'hen P
THE MECHANICAL DESIGN OF COMMERCIAL REA(;TORS 353
exceeds 0.385 SE. The ASME code provides for other formulas tOl" thick
spheI-ical shells and thick hemispherical heads.l.J~
When designing thick-walled reactors that are built of se\'eral layers.
the stresses and strains have to be calculated as accurately as possible.
Designers usuallv check \\'hether several safety criteria are met. These
criteria are formulated as theories, e.g., the shear-with-friClion theory
or the distortion-energy theory. l'\ot only the present properties of the
shell are considered, but also changes of these properties \\'ith time, such
as possible creep of the steel. Some reactor shapes can be assumed to
be composed of sC\"eral sim plc geometric rings and shells and the stresses
and strains for each of these simple forms can be anahzed and calculated
separately. When all the calculations arc combined. a detailed anah'sis
for the entire presSllre \'essel is obtained ....... technique \\hich does just
that is called illteractio/l (lllo/)sis. U A computer rrogram emitled CALSOR
has iJeen dew·loped to do routineh' all the complex calculatiolls for even'
reactor vessel designed.
The abO\'e informatioll OIl pressure design of reactors is being pre-
sented with the purpose of giving sufficient ul1cL:rst<lnding to permit
the catalnic reactor designer to talk intelligentiy to the expert mechanical
designer. Actual I\' the subject is considerably more cOl11ple:o-: and 50-
phiqicated. Besides the design of the cylindrical re;'ctor \\alls. it includes
the design of the heads. the closures. and other detail,; ;hat \'Quld be
\,'ClI outside the competency of the catalytic reactor de~lgner. who nor-
malh' is a chemical engineer. For sllch detailed mechanical design, the
reader is referred to the AS:v1E Code. J the Chemi((J/ Engilll'l'rs' Handbook. l~
J4
, and a recent book by Henry H. Becinar.
• •
In this section we discussed hO\\' \\'e can calculate the \\'all thickness
of a reactor required to contain a reaction at a given tempfTature and
pressure. :\0\" \,'e \,'ill discuss hO\\· reactors are built mechanically.
12.2
VARIOUS METHODS OF REACTOR CONSTRUCTION
The methods of construction of catalnic reactors depend mainh on •
meeting three conditions:

1. Temperature
2. Pressure
•
3. Corrosion resistance
•
Some reactors ha\'e to meet t\\'O sets of conditions. one for stead\'- ,
state operation and the other for in situ catalyst regeneration. :\ormally,
catahst regeneration conditions are low press lire and high temperature.
•
Inlet
/"' Gos ond liquid

distributors
___ Stainless steel Or

olloy steel shell or
clad shell
•
-l--Fixed bed of calalyst
•
-~~_Alumino balls
:"--Cotalyst drain
conr~ction
Out let
FIG. 12-10 Typical mechanical constructio:1 of fixed-bed reactor for low-se-

• •
verity reactIon.
Low-Severity ReJctors
For low-se\'erity• catal,·tic reacrions. such as the G!rbon monoxide shift
•
reaction or carbon monoxide methanation. one Llses IO\\'-alloy• steels and

manages to contain the pressure directly in the steel shell, as shown in
fig. 12-10. If corrosion resistance is an important requirement, one uses
steels that resist the particular corrosion, or if this is too costly, one uses
clad steel plates. A clad steel is a high-strength. low-alloy steel \\'hich has
been rolled together with a thin sheet of stainless steel or other cOITosion-
resistant metal. Titanium-clad steel plate can also be manufactured by
the so-called explosion cladding process.I,>.lti The lining is just thick enough
to meet the corrosion allowance. The \\'elding of clad plates must be
done by highly skilled welders, and even then it must be done extremely
carefully. It is advisable to closely and totally inspect these ,,·elds.
An alternative to cladding is the use of corrosion-resistant shrouds. A
shroud is a lining that is installed in the field 1)\ introducing pieces of
it in long slices through the inlet or outlet opening of the reactor :l.I1d
welding it together inside the pressure \'esse!' Of course, the shroud
transmits the inside press u re to the wall w!thout itselfresisting the pressure.
High-Severity Reactors
As the temperature-pressure severity increases. any available and rea-
sonably costly steel can no longer contain the reaction in a thin-walled
•
TI-lE MECHANiCAL DESIGN OF COMMERCIAL REACTORS 355
reactor. In case of high-temperature, moderate-pressure reactions such

7
as the Litol process" for the hydro-refining of coke-oven aromatics, one
can still use Cl thin-walled desi<Tn
n bv
, installing a thick la\'er of imj)crvi- t.. I
ous refractorv, imulation inside the steel shell." The shell is maintailled
at a low temperature, where it can keep its high tensile strength. Such
a reactor is shO\n1 in Fig. 12-11. I n order to prevent the penetration of
the reaction mixture into the insulation and further lO the steel shell, it
is customary to install a shroud im:de the insulation. The catalyst charge
is then fIlled into the pdcket formed bv the shroud. The shell skin
temperature of sllch reactors must he cOl'linuous!y monitored in order
to detect anv hot 'pot due to crack formation in the inner insulation.
This method of reactor construction can handle reactions that typically
operate at GOO to 650°C and 50 to 70 bal's.
For reactions that are run clf temperatures below 4:JUoC but at high
pressuresofseverai hundred bars. thick-walled reactors must be designed.
The first thick-hailed reactors "'ere fabricated by casting huge low-
allo\' steel ingots and forging these O\'ersize ingots in special large forges.
The machining required huge lathes. The smallest i1<II\' in the steel
casting or arising during forging could cause the \'essel to fail during
the final hydraulic Drooftest. Th us this type of reactor fabricatiOll turned
out to be extremeh costh'. Costs could be some\\'hat reduced by designing
,
='
___ -O"'e' ,'nsu'ol'OO
... " 'I,j iV"
I I
~- Cold shell
I ,
\,
,
,
,~
____ Corrosion - proof
I .k'" inner liner
\1 ,, . ,-
\
,, !
I Fi 'ed bed 01
eOlalrs1
,' 4I--1nner ,nsulollOn

/
i\
,,,
,
,!,
I
'--- Alumino balls

!,
,
•
I
Calalysl/
drain conneclion i , '.
, v _ ' ,t,
-
FIG. 12-11 Typical mechanical construction of fixed-bed reactor for high-

• •
seventy reactIon_
•
356 CATALYTIC REI'.CTOR DESIGN
the reactor wall in two layers. Both were separately cast, forged, and
machined. Then the outer layer was expanded by heating and was fitted
over the inner layer. Upon cooling the outer laver exerted a compression
on the inner layer. However, when put into operation at the operating
temperature and pressure, both layers were under about the same tension.
The cost of thick-walled reactol'S could be further reduced bv, de-
signing and fabricating them as multilayer vessels. One method is to use
se\'eral steel plates that are welded at a longitudinal seam. Welds ap-
parently weaken this type of "essel construction, as was later found. This
idea was improved upon by wrapping a steel plate around a relatively
thicker reactor core. The best results were obtained by wrapping profiled
steel strips with grooves and tongues around a core without welding
them together. This is the old German Wirkf/ pror('ss. Figure 12-12 shows
a ;)referred steel profile and its use in the Wickel process. j'j The subject
is extremeh' interesting but too broad to be discussed here. For further
information the reader is referred to four good papersJ"-2~ and two
books. J(J.J~
Meeting of Corrosion Resistance Requirements

When designing a reactor for a well-known catalytic process. the designer
will know the corrosion requirements and have no trouble specifying
the compo~;tion and thickness of the corrosion allowanc(' of the reactor
wall, lining, or shroud that will be used. The corrosion resistance of the
particular wall material is usually expressed in inches per year in the
United States and meters per year elsewhere. This figure is multiplied
by the life expectancy of the process to obtain the thickness of the cor-
rosion allowance.
J
8
t
~~-79---l
FIG. ~2-12 Cross section of strip winding in the German Wickel process. (From
E. Karl,19 by pe1 mission from the American Institute of Chemical Engineers.)
THE MECHAI'J!CAL DESIGN OF COMMERCIAL REACTORS 357
In new processes, the seal"Ch {pr the proper corrosion-resisting ma-

terial starts immediately after the com pletion of bench-scale proce"s de-
\'elopmeni studies, Very eXiensi\'(~ corrosioll studies are periodicallv pub-
lished for a large , num!wr o! chemicals ,tl1(1 construction materials b\',
Ihe ~ational Associaticl'l of Corrosion Engineers (~ACE),~:\ It is quite
like" that a solution [0 any particular corrosion problem at hand can be
found in (111:se publications, If llO S;ttisbctory solution can be found,
samples of v<JI'iolls .natel'i,ds ;!re tested O\lT periods of several months
in sIllall alll,)lllatic bench-"Gde re;!ClOrS, One \\'a) of exposing a particular
metal or alloy tn reaCl;O!l cOIlditions is to construct a dead man hee Fig,
I O-i) of it ann use it ill the ;!lll()Il1;!licalh' operated corrosion test reactor.
Finding adequate materials to resist corrosion in h\'drodesulfurizatiol1
rl'<lctors for petn,lelll1l-derin'd or coal-deri\'cd hnirocarbons j, partic-
ularl\' challenging. HOI h\'(lrogell unci,'!' pre~sure makes some allO\'s
brittle; thus austenitic sLlin1<:ss steels of particular composition are called
for. When the effect of H~S partial pressure is added to the h\(irogen
embrittlement problem, the challenge becomes even more difficult to
meet. The XC/WIl CUIl'I'S":; ,!IT quite helpful in this resp':ct. For a discussion
of new reactor steels, the reader i" referred to articles by Estefan,c'
,,'):" ')( - ') 'lS
Clarke,-' Lancaster.-' Gul\'<I ,
,iild :'farshall,-· and a:1 anonymous
. author.-·
Corrosion data for a peuoleum hvdrodesulfurization reactor have
been discussed bv :'fcCo\ and Hamef'L;' and the development of ~he
engineering design of petroleum oil hydrodesulfurizers at a British Pe-
troleum CompanY plant has been reviewed in detail by Lister."
NOMENCLATURE
E Lowest efficiel1C~' of <lnyjoint in reactor wall, dimt:llsionless [Eqs,
(12 -6 ), (12 -7), (12 - I I ), and (12 - 12) 1
E Modulus of elasticity,
•
Fa
FT Tensile force, 1\
! Longitudinal thickness, m
11 Safet \., factor
1'.11 I nside radius of reactor. m
r? Outside radius of reactor, m
p Pressure, bars •
PI Inside pressure iwreactor, bars

5 Maximum allowable stress, Pa
t Reactor wall thickness, III
•
Central angle c~
.
E Strain, dimensionless
Po;:,son's ratio
Stress, Pa
(Tu Cltimate stress
(Ju. \rorking stress
(J, Yield stress
(J, Longitudinal stress
(J,), Tangential stress at insicL radius
(J,l, Radial stress at inside radius
REFERENCES
I. AS:\lE Boiier rllld Pressure \les.l"i Cllde,
Fl!!: Cuflrl'd Pressure '·('sse!., and
Sl'e.
<lmend'llellls. The American Society of Mechanical Ellgineel's. 1~l(i2.

2. F. L E\;ms, "Recent Development in ASME Pressure Yessel Code." Nwim-
cmLou j'rc;rcs.,- 54(12):5:'1-55 (1975).
3. I. Berglund. "Guide to Swedish Pressure Vessel Code:' flyr/lo((lIhlJl/ Prllc!'.I.\.
-4(1 9_):{J"t
:J ' ., ('Cj--'
J . IJ).
4. F. DalrOra. "European Pt'essure Vessel Codes," Hydrocarboll Process. 50(<1):93-96

(1971).
5. \1. l\.oike, "Guide to Japanese Pressure Vessel Code." Hydro((friJol/ Proccss.
• 54(12):65 (1975): "Guide to Japanese Standard Pressure Vessel C"nslruc-
lion," Ibid. 54(12):66 (1975); "Guide toJapanese High-Pressure Gas Control
L a\\', "lb"le.. ~~·19)fi-(19--)
~.( _ : 11 _ t:l .
6. R. ~fazzoncini. "Guide to Italian Pressure Vessel Code." HvdrorarbOll Proccss.

54(12):63 (! 975).
7. H. StefTen, "Guide to German Pressure Vessel Code." Hydrocar/)(1Il Pro("-'5.
-
54(12):62 (1975).
8. P. \'an Rossen. "Guide to Dutch Pressure Vessel Code." Hydrocor/;oll
- Proass.
54(12):61 (l~l75).
9. R. Hooke, De Potelltia Rcstitutiva. London, 1678.
10. E. \\'. COl11ings. High Pressure Tcch'l"log:r, i',1cGra,,'-HilL Kew York. 1956.
11. S. Timoshellko, Strength of AloteriIlL" part I: Elenu'lItar)' Them), alld Problems,
3d ed. Van 0:ostrand, , New York, 1958.
12. J H. PelTY, Chemical Engineering Handbook, 4th ed .. 1963, pp. 24-7(0 24-33;
5th ed., 1973, pp. 6-91 to 6--105.
13. D. E. Wirkin, Use of Interaction Analysis to the Design of High Pressure Vessels,
Monograph b;' National Forge Company.
•
14. t1enn' H. Becin;u', j'rnsurr VI'-'sc/ Design Handbook, Van Nostrand Reinhold,
:\el\ York, 1% J.
I :J. C. 1'. \\,illi;!!11S, --E"plosion Clad Titanium/Steel Plate,-- Chl'lII. F:/l~. I'IO!!;L
66i lO):4K-:-,:! (I <')7()i.
i(i. C R. COI\';!n et ai.. ["plosive Bonding, US Patent :~,137,937, 1'l(i4 (to

E. l. dll POlll (le :\el1lours & Co.)
17. \1. Orhall Tarhan and Louis H. \Vindsor, "Coke Ovens Yield High Qualitv
l'H~n!{:ne. -- L"fII'J!/. I":ng-. E' rog,.. 62('))
...: ('-
)/-/-')_ (1"('('-
, '::J) )).
IS. D. \\'. \!cJ)()\\"(:11. Jr.. J D. MilligaJl, and A. D. Korin, "Cold \,. Hot Wall
Pressure \'e,sels:' HwlrocarbvlI Profl'SI. 45(3):157-160 (19Iiti).
1'1. L Kar!. --St rip- \found Pressure Vessels," Chl'lIl. En,!;. I'ro!!;r. 68( II )::i(i-()(l
1I'!7:!)
:!(J. T \ !cLean.! aspcr. .. \1 ult ila\'el' \'esse!s for High Pressure and Temperall! ,'e."
., "11' /'.,l,i.....'
\I . f,.
t' I 'r I )/. 1"/' -')
'. ~
I,~. <J_
-'lI -'»-<l(' (I'J-('
\' I") --,
_., _ ,....) J)
,,-.
~ I. J Scltierellbeck, --K,'ilische BetrachlUngen zur Herslellullg von Hochdrllck-

!](Jhlkijrpcrn ill \lehneil-Ballan flir Hochdrllcksvnthesen," HU'III1.(/lIjf-C/iI'II/.
_.-)_''1 -_'1'1
3 b._,), ')11 ( Ill""
• ,J.)).
:!:!. S. StrelwfTand L C. Pall, "Designing Pressure Vessels," Chl'll!. Fng. 39, :\0\'.
!. 1l)(iK, PP l'JI-Il!~.
::>3. Ceorge :\. :\eisoll, CorrosiO/l Data Surv!'J, Shell Pevelojlment Company, San
Francisco, I ~l:,(I. These data have been updated and sur __ ",vecl by the :\aliollal
:\'s()c!atioll of Corrosion Engineers (NACE): l'\. E. hal11ner, Corrosion Data
-'-;/II"f'I ,\le/rd,';r'ctioll :,lh ed., 2d printing. 1979.
24. S. L. ESlefan, --Design Guide to Metallurgy and COITosion ill l'hdl'Ogen

Processes," Hw/rocar/JrJII Process. 49(12):85-92 (1970).
25. J "\rh~' l'\otJust
S. Clarkc, Build Reactors to the Code?" lh-drowruUII Process.
. i'{"
49 -Cl "} ( Il)-O)
J):/,-h,I , I.
-
<:l('
.). J F. Lancaster, "l'.S. vs. European Reactor Steels," Hydrocarboll Process.
491 G):84-l)O (l'l70)
J :\. Gulva and E. G. Marshall, "New Property Data for Hydrocracker

Steels," Hydrocarbon Process. 49(6):91-96 (I970).
28. "\\'hich Steel for Hydrodealkylation Units?" H)v1rocarbonProcess. 48(6): 131-132
( 19(9).
29. J D. McCov and F. B. Hamel, "New Corrosion Rate Data for Hydrodesul-
furization Units," Hydrocarbon Process. 49(6): 116-120 (1970).
30. J. D. McCoy and F. B. Hamel, "Effect of Hydrodesulfurization Process
\'ariables on Corrosion Rates," Mater. Protec. Peifomwnce 1 O( 4): 17-22 (19'/ 1).
::: 1. A. Lister, "Engineering IJesign and Development of Desulfurizer Reactors,"
Proceedings of the Third European Symposium on Chemical Rl'action Engineering,
Amsterdam, Sept. 15-17 1964; Chem. Eng. Sci, (suppl.) 225-235 (1964).
•
A jljJl'l IIfix ITERATION TECHNIQUES
Iteration aims at cOlllputillg .\ b\, repeated calculations or

x = Icy) (A-I)
It is desired to fillCj x f()r which .\ fCy) b\ assiglling yalues to x such

=
a~ .x", .X ,. 'Y c' .....Y". The fil'SI \ <tItle is x". Then:
X, fix" )
.\" ' )
- J(.\ i )
x" -fix"~- )
, . - . . . . . . . .
until
where E is a yery slllall numbeL For the purpose of reactor design

E = 0.001. This method is called FiulIr!·.1 iteratioll.
There is another technique. called the .\'r,dulI-Raphson iteration. \\'hich

is more pO\\'erful than Picard's iteration. Here x" is an initial guess; then
an improved solution is:
•
(A-2)
,
Simibrlv,
,
Cl still hetter solution is:
[(XI) - xl.f'(x,)
X'J
I - r (x,)
,1I){1 so OIL
In ol"(ln to ha\e an efficient iteration, nothing but x must varv in

Eqs, (A-I) or C-\-:!)· ~Jd"~I'wlse there will be pulsations. Strong pulsations
usualh lead (() the breakdm\"l1 of the computations.
•
,
NAME INDEX
Ackcrmann, P .. 254, 299. 30'1 Carhern, .Iamesl., ti:!, 63.70.71,7-1,75.

..\fschar. A. S .. 271. 273 82-84,89,92.'11.1%,1:'16. FiO, 176.
AI\ 'c'~. G _
.E '>4S
AI-:.htar. Saveed, ISS. 186 '
're.
_, u, "<)" "<)0
.:J_~),
Carnahan, B., 25, 46

~)_o
• "_ t
\ I .,
: go. \\. cs Ie). B .. 264 , <)_ -I ....<) , '_) i- "~/,":)q I !. Cassiere, C;., 67, 75
Aris. Rutherford. J 1, 337. :-141 C·,cC!'1 . .I'.. I" 1"-
;) R " 1-- .:1:), I. ')f)CJ
'!(j-
_ ~ _
Astarita. Gio\'alllli, 267 c,· .. ru. Ramon L.. 293

Chang. P.. 208
Babcock. B. D .. 24') Charpemier, J. c., I S4, 341
Barnett. V. D., 185 Chilton, Cccil H, 239
Bednar. Henry H., 353 Chou. T 5., 246
Beecl-:.. Otto, 54 Chung. S. F., 185
Beirnesch. W. E., 246 Clarke. J. S., 357
Bcnenati, R. F .. 80 Coleman. D . .I., 139
Bennen. C. 0., 324 Comings. E. W., 350. 352, 358
Berglund, I., 358 Connellv, F. L., 263
Berty. J. :-'1., 324
•
Cooper. A. R., 11. 74
Beusch. H .. 337 Corpslein, R. R., 293
Bibbv. R., 3 i 1 Coughlin, Rober< W., 49
Bild. E. \1., 312 Co\'a. D. R .. 264, 272, 273, 311
Bondi. Arnold A" 187 Co\\'an. G. R., 359
Borchers, E., 254
Boucher. D. F., 248
Boudart. Michel, 11, 51, 63 Dall'Ora, F., 358
Hover. C. B., 328
,
Dan'\';erts,
k ' <)-<> <)"3
P. \ '.,_/~'),_"':1.
Brellon, R. H., 97 Davidson, J.
f.. 170
Brian. P. L. T, 279, 312 · HT
Dcc k\\er, nO If- D'lcter,...
>
):1, <)-<)
')64 ,_<)(-n .... 1 .... , 2"
I..) 1 •
Brosilow, C. B., 80 • 283,296,299,313

Brunauer, S., 52, 54 DeLasa, H. I.. 340
Butt. John B., 54 DeMaria, F., 136, 167, 184,220
Dickson, P. F., 284, 313
Calderbank. P. H., 246, 264. 279. :., J 1. Douglas, James l\L, 341
323 Dufal!, Andre F., 310
,
364 INDEX
Dutkai, E., 184 Hellwig, Catherine C., 310

Henry, H. Clarke, 171, 186, 207, 209
Hinshelwood, C. "., 55, 231
Effron, E., 165, 167, 169, 171, 185,219, Hla\'acek, V., 334, 340
220 Hochman,.J. M. 16:-" 167, 169, 171, 185,
Eissa, Sherif H., 273, 274 219,220
Eldridge,john W., 294 Hodge, E. S., 32H
Elkin, L M., 139 Hofmann, HallIls, 2·B. 299
-')
E mmet!, P . H .,:L Hoohendoorn. C J.. I H4
Engelhardt, F., 299 Hookc. R. 345
Ergun, Sabri, 79, H4, 102, 162,259.310 Hougen, Olaf 1\., 55, 6 I, 231. 249
Esehard. F.. 310 Huben. Hans-jiirgcll. 2lj'J
Estefan, S. L., 357 H ugo. Peter, :H I
Euler, 16 Hurningwn. R. L. itiO. Iti::. 1!i5
Evans, F. L., 3SS
Ewing. Roben C, 310
jameson. G. S .. 17'2. 18"
Jasper. T. "!CLean. :F,(;
· Jarnes R ". "-4
F aIr, _J . 'r _ )J. 2"0
_b4, ')('- 0 '3~ ()'j~
y
jeffrns. C V, I I. 74
Fan, Liang-Tseng, 312 johanson, Edwin S .. 2 c,LJ, :1 I (J
Farkas, Ed"·ard.l .. 254, 296, 309 johllSon. Clarence A .. :1l ()
Ficguth. P., 337 Johnson. D. L.. 244. '276. '21-'(1
Flinn, Richard A., I ~b
Fourier, J. B., 198
h.arl, E.. 359
Franks, Roger G. E .. ·~
I\.eenan. R. G., 'i4
Friedman, Lee. 153
h.essler. D. P., 246
Friedman, Sam, 185. j 86
h.irk, R. S.. 184
Froment, Gilben F., 135, 332, 339-341
h.lassen. J.. 184
Fr\'e, C. G., 231, 236
•
h.oh1, Arthur, 23il
h.oike, ,,1.. 35il
I ' "lbeI . H er be rl. 'r
n.O 4 <) - " ')c, ')6- 269"
..... :)'._Jb._u't._)/,
\ Gasche, Fred, 318
270.276, 283-2il5. 297-299, 309, 310
Gbahoue, L., 311
"onn. A. D .. 3-<)
F'
".
Gilbert, John B .. 171. 186,207,209
h.owalczyk,. Leon 5 .. 2CJ'i
Gilles. E. D., 340 (l\..Ufill,
. . . DalZO.. ... 1()0 -I . ,_',1 9_
Xlll.
Gilliland, Edwin R., 274
Glaser, M. B., 165, 185
Gnielinski. Volker, 87 Lace;-. lames j., 186
Godfrey,.J. H., 323 Laddha. G. 5., 171
Coto, 5., 244 Lancaster. J. F.. 3'i 7
Guha, J. A., 357 Landis. P. S .. 184
(..
Ldngernann, l-f ors!. q~4')'~')"q?"3
~.) . _[1.). _u_, _0 .
297.310
Haddad, A. c., 310 Langmuir. Irving. 'i5. 2:, I
Hales, H. B., 279, 312 Lapidus. Leon, 46, 10'i. 16fi. lil'i
Hall, J. W., 328 Lavingia. Pramod, 284. 313
Halsey,
•
G., 54 •
. , 29. 32. 283
Lee, E. Stanlev,
Hamel, F. B., 357 • LeGvff,P., 184, 185
Hammer, Hans, 254, 297, 298, 309, 310 Lehrer. lsaac H .. 268,270,271
Hanika, J., 176, 180, 187 Lema\', Y., 246, 247, 24'1
Harrison, D. P., 328
•
Le\'enspiel. Octave, xiii. 11. 61. --

I J, 165,
Hayward, D., 54 167,219,220,312.323
,
INDEX 365
Lichtenslein, 1., 165, lil5 Orcutt, F. D., 328

Liljenroth, F. G., ~~35 Orning, A. A., 162,259,262.310
Lips,].,184 Qstergaard, Knut, 283
Lister. :L 357 Otake. T .. 170-171
r'
LIt?, \,.
\. J" ')4'~
_ •
Livbjerg. Hans, 324
Lopcz, :\ S., 332, :·\40 Pan. L C, 359
Louisi. Youssd, 2~(1, :-1 1:-1 I'arera, Jose ~!., 293
Lovc. h. S., 54 Parks, Ceorge S., I :l'-l
Lu,bel1.
, \\'. L., 7 Pelossof. A . .-\., 313
I'erimllller, Daniel D., :-I.!l
Perona, J- J-, 244, 248
Ma, Yi Il ua, 20H
Pern, J- H., 358
\!cCm. J D, 357
Pern, RuDert H., 2:-\~1
\1cCracken, Daniel D .. ·Hi •
Pigford. Roherr L, :-112

\!cDowe, IID\ . \'" ' J'r ....
',eq
L
Pilcher, G .. 139
~!cGrea\\, C, 341
. I-1.- 1-1 ., ,)c, "-h _ "<;0
l'iret. Edgar L. 294
\!aennrg. _.h, _.')\J. .",
Polejes. J. D .. 255
~!aerker. J. B., 153
Porras, J. A., 3·10
\fahollev, j. A., 328
Porter. K. E., 185
\!arshall, E. G., 357
Prata, C. D., 89, 91
Martin. Holger, 86
Prosl, c., 184
Mason. Donald R., 294
Pruden, E. B., 259, :,01, 3(B
\1ason, E. A., 274
\!axted. Edward B., 54
MaxwelL J. 13 .. 203-20:')
Ralek. \filos, 299, 31:~
\1azzoncini, R., 358
Rase, H. F., 328
"{ears, David E., 168, 217
Reiss, L Philip, 184
Meisl. C, 254, 309
Reznik, Alan A., 186
Mejdell. G. T., 249
Rideal, E., 54
Mende!son, H. D., 270. 271
Riesenfeld, Fred, 238
Michel, B. j., 263
Rollison, Leonard, J 86
Miles, Da\id, 276
,
Roques. H., 311
Miller, S. A., 263
Ross, G. j., 323
Milligan, J- D., 359
Ross, Leon D., 170. 171 •
Mochizuki, S., 241

Rossini, F. D., 153
l\lohunda, D. M., 171
Roustan, \1., 311
\oloo-Young, M. B., 245, 311
Ruckenslein, £., 184
Moreau, Femand, J r., 3 I 0
RukO\'ena, Frank, 186
Mosh\, J E., 231, 236
Ruzicka, V,, 187
MusiL L. 185
Myers.John E., 159, 161. 172. 17:-\,185.
246
Sater. V. E., 165, 167,219,2::'"
Satlerfield, Charles 7'i., 89, 91. 110, 170,
Nadler. ~lurray, 293 lil, li6, 180, 181, 187. :2'18, 209,
Nelson, George A .• 357 276.278,279,311,313
Newinh. Ray, 153 SchiLrenocck, J., 359
NienO\,·. Alvin W., 276 Schiesser, William E., 46. 97. :S:!. 165,
•
.. 166, 185
SchlUnder, E. U., 80, 89. 94
Okada, K .• 170-171 Schmal, Martin, 298
Oldshue, J- Y., 263, 2iG Schmidt, L D., 33i
•
366 INDEX
Schoenemann, K., 241, 294, 299 van Rossen, P., 358

Schuier, H., 340 van Swaaij, W. P. M., 184, 185
Schwartz, C. E., 80 Vasalos, E. M., 312
Seth, K. K., 284 Vasalos, I. A., 310
Shaffer, '.1. R., 80 Venuto, Paul B., 184
Sherwood, Thomas K., 165,208,254, Villermeaux, J., 185
296,309,312,313 Vortmever,
•
D., 87
Shulman, H. L., 186
Siemes, W., 265. 272
Simons, J. B., 328 Watson, Kenneth M .. 55,61,231
Smidt, Jurgen, 256 War, •
Peter F., 110, 177
Smith, J. ?\!., 11,61, 74, 80, 89, 130 WeOer, M. E., 259, 301
Snider, J. W., 244, 248 Weekman, Vern W .. Jr., 4,10,15, 161.
Sporka, K., 187 172, 173, 185,246,323
Stahel, E. P., 284 \'\'eintraub, M., 186
Steffen, H .. 358 Weiss, Alvin H., 153
StellOfT. S .. 359 ".
\ '\'eJSs. \",,'., ....<)-2
1
SlOt/er. Hamld H .. 310 \\'eisz. Paul Burg, 89
Stri);le. Ralph. Jr., ISo Wells, :-.i., 186
f · , I (i?
,5 weene\', D ...
•
._ Welsenaere, R. J., 332, 340
Wen, Ching-Yung, 185.312
Wendel, Martin '.1.,83
Tajbl. D. G. :128 Westerterp, K. R., 153, 341
Takoudis. C G .. 337
Wheeier, Ahlborn, 55, 74,89
Tarhan. '.L Orhan. 97. 152. 153. 158, White, R. R., 167, 184.220
239. 359 Wicke. L, 337, 338, :34 1
Tatter'on. D. L, 312 \Yllhelm, Richard H., 74, 97, 102
Ta,lor,
• • H. S .. 54
•
Wilke, Charles R., 116, 208
TellcT, Ed\\'ard, 52 \\,illiams, C. P., 359
Templeman, J. J., 185 Windsor, Louis H., 153,239, 359
Thiek, L \\,., 68, 89, 208 \\,inkoop, R., 74, 102
Thonon. CB .. 310 \\'irges, H.-P., 341
Thornton. J. \1.. 341 Witkin, D. E., 358
Timoshenko. 5., 358 Wolk. I{oland H., 310
Trapnell. B. \1. W., 54
Turpin. Jirn l., 160. 162, 164. 185
Vagi, Sakae, 187
Ulrich. C. F., 186 Yang, Y. C., 312
Yamrskv,, Paul M., 185,186
"an DeeOller. J. J., 313 Zaidi, Ahmed, 299, 313

"an Heerdeo, c., 335. 341 Zellner, Matthew G .. 38, 46
•
•
SUBJECT INDEX
A priori design. S. :i:-l') Bodenstein number, 169. 21,. 26,1

Adiabat ic fixed·bed reactors. 78 Bo!tznlann constant, BB
Adiabatic gas.liquid reactors. interbecl Boundarv·value ODEs. prugram for ",1\.
cooling in. 17:) ing, 28~37
.-\diabatic gas reactors. I06~129 Bridgeman closure, 318
.~\diahat~c reactor. 3 Bromine number, 203
definition of. 106 B U bbl e reactor, ~_. 9. 9
9"
_.l.J~_:J.7. ?4' ""
_ ..)-_ ..
design examples for. 111-129 (See a/.lo Slurr\' reactor)
Adsorption. 1'11\ sica!. 52 Bubble regime:
Air oxidation of naphthalene to phthalic quiescent or laminar. 263
anln·dride. 136-151 turbulent, 264
Algorithm: Bubble rise veloci!v, mean. :'(,'i
definitioll of. 15 Bubble surface area, specific. 26,
• Euler·s. J 6 Bubbles, effect of pressure on. 267
RUllgc-Kutta, 20
stabilit\ of. J 9
•
American Society of :'--Iechanical Enf,>ineers Carberry• reactor, 63

(AS:'--l El. 344 Catah-sis,
, 47-55
Arrhenius equation. :Jfi heterogeneous. 2
Autocatalnic reactions. 57 homogeneous, I
Axial dispersion: Cata!yst(s):
of mass. H2 classification of, 48
in trickle·bed reactors. 165-169 definition of, 47
limit set b\ '.!cars to. 168. 217 failure during regenerati01l. 330
Axial Ho\\" rale. 1"'rlial distribution of. SO heterogeneous, propenies of. 49
Axia; Peclel number for maSS. KI poisoning, 54
porosity of, 54
su pports, 51
Ben\• reactor. :324 • Catalytic agents, 51
Biot number: Catalytic promoters, 51
for heat. ')2. 93 Cavitators, 263
for mass. 90. 92 Chemisorption, 49-53
for \\'all. CJ3 rate, 52
,
368 INDEX
Classification of reactors. l, 78, 155-158, Development of design equations (Coni.):

'r
_:l 1-2-u30 for fixed-bed g;" reaclOrs, 131-136
Claus reaction, 1 for "\I,,\AF gas reactors. 131-13Ii
Complex rpaction systems, 70 for slulTY, reactors. :!'I'i-:!96
Computer program: for three-ph;"c transport reactors, 3(J1-
RDMOTI for adiabatic reaclOr' design, 304
117-121> fOl trickle-bed reactors: for h<tckIllixed
RDMOT2 for :\I:\:\F reaClOr design, pilot-size rcan',!s, l'Ji-200
137-15! for plug-II()" C<Jllllllcrcial 1C'''ctorS.
RD\10T3 I(lr backmixed trickle-bed re, I ,.1 ')-1'1-
~ _ I
actor design. 220-2:)(J Dillerential allah'sis,

•
li()
RD1\10T4 {')r plug-Ho\\' trickle-bed re· Differenti,,1 e'l"ations:
actor design. 209--21 (j ordinal \' (ODD. I:',
Consecuti",: reactions. 70 bOllrtd;Jr\' conditioll. \·1
Continuous stirred-tank catalnic reactor
•
initial-value. 1-1
(CS~ Tf'R
1 '-~ ''')''
). ~")_'-"} 11th order, ~~
Continu 'US stirred-tank reactor (CSTRl. sinlullaIl{'olls. ~:)
')
.... r<) "(",
,u_,_). partial (PIlE). 1-1
desc:iplioIl of. 2SJ-2S4 algorithllls for sohillg. T7 .. ~ I
process ,Iesign of. 2H6-295 DilfereIllial Ilo\\' ,CdctO'. :>S. :123
scale-up of gas-liquid, 293-294 Diffusivit \', intraplusc. 'HI
in series, 294-295
COII\TfSioIl, 5~
Cooling methods. interbed C'eI' lme;bed Ebullated-bed reactors, :.!
cooling methods) axial mixillg in, :.'7-1
Corrosion -·Ih.)\\'anu:, 356 des~l"iptioll uf. :!:)(j-~~-,~l
Corrosion resistance requircIllCrltS, :i:")G- process design of. :!~1~j~:~O I

3,,7 EfTcctl\"ent:ss factor. :Hl
Creep, 34~ external. 66

CSTCR (continuous stirred-tank catahtic
, intraphase. (i7
reactor). 323 nonisothennaL t)S
CSTR (see Continuous stirred-tank reac- Emission coeHicicnt. S~
tor) Ergun law. 79
[uler method, modtfled, :2 I
Exam pies, design:
Damkijhler number: for adiabatic fixed-bed gas reactor. 111-
for heat, H6, 92 1:29
for mass, (i(i, 84 for CSTR, 290-:!93
Dangerous reactions, 3~11 for isothermal reac!Or. 102-1 ()(i
Dead man. 326 for r--; 1r\ A F gas reactor, J:l6-J:) 1
Design codes. 3-H for slurry, reactor. 2(17-2'19
Design definitions (vc \!echanical design: for trickle-bed re;HtO!', 21)(1-2:-\0
Process design: Stability stuch of re- laboratory, reactor with backlllixing.
,-
actors) 217-230
Design equations (see Deyelopment of de- plug-,flow industrial l'Cactor, 201-216
sign equations)
Design examples (see Examples. design)
Desorption rate. 52 • Finite difference method, 29
Development of design equatiot!s: Fixed-bed bubble reactor (FBBR). 1-:)7.
for adiabatic gas reactors, i 07 -109 241-247
for CSTRs, 286-290 axial and radial dispersion in, 243
for ebullated-bed reactors. 299-301 gas dispersion in, 243
•
INDEX 369
Fixed-bed bubble reactor (Crml.): Homogeneous catalysis, I

heat transfer in. 243 Homogeneous reactors, 2
mass transfer in. 244 Hooke's law, 343
pressure drop across. 242 Hydrodealkylation of toluene to benzene.
process design of. 245 111-12Y
transport phenolnella in. 24~-245 H ydrodesulfurizat ion, petroleum. design
Fixed-bed gas reanors: of trickle-bed reactor for, 20/J
adiabacic, 106-1:2'1 Hydrogen recycle, purification, and gen-
for exothermic reactions. 109- I I I eration, liS
pressure drop aCf()"'S, 79 Hydrogenation:
Fixed-bed reactors. 2. 77-247 of ethylene to ethane. 102-106
adiabatic. iK of o:-methylstnene.
, , 244, 280
isothermal. 78 Hyperbolic tangent, definition of. 69
Flo'" reactor:
differcnllaI. 58
integral. 61 Iniual-value ODEs. program for solving.
Flow regimes in g-as-liquid-phase fixed 24
beds. I GO Integral analysis, 61
Fluidized-bed reanur, :2 I ntcgra I I1 ow reauo!. "I.
." '.'')3
,
Frculldlich i<;(Jlherll1. 34 Imerbed cooling methods:
Froud: number, Iill. 21i9 in adiabatic gas-liquid reactors. 175
Function Runge, 2f)-~K in adiabatic g'" reacwrs. 109-Ill
Interphase hear. transfer. 86
I merphase heat transport in fixed-bed gas
Calileo number. 1711 reactors. 85-89
r- <'I"0
11 lng. a
va .. Interphase mass transfer. 83
Cas dispersion in FBBRs, ~4:-\ Interphase temperature gradients. 9~
Gas holdup, 269. 270 Interphase transport:
Gas-liquid-phase reactors. :;, 155-:-\04 definition of, 5 I
classification of. 133-158 in fixed-bed gas n:.,ctors, 79-89
definition of. 135 I ntraphase diffusi"it v, 90
C,,,,-liquid systems. Pedet number, for Intraphasc mass transfer, 89
mass in, 167 Intraphase temperature gradients. 91
Cas-phase reactors, :~. 77-1:; I Intraphase transport:
Gasche closures, 3 J 8-319 definition of, 51
in fixed-bcd gas reactors, 89-9-1
Intrinsic reaction rate, 90
Heat transfer: Isothermal fixcd-bed reactors, 78
, e b u 11 ate d -t)e(I reactors,
111 - ()U<1 90-
~O"-_"J Isothermal reactor, 3. 99
in FBBRs, 243 design example for, 102-106
interphase, 93 Iteration techniqucs. 361-363
intra phase. 93
between reactor "all and packed bed.
89 Laboratory, reactors. 317-323
in trickle-bed reactors, 172-176 definition of, 315
HeightJdiameter ratio of reactor. 202 Langmuir- H inshelwood/Hougen- \\'at50n,
Heterogeneous
• cata",is, 2
•
catal,tic
, reaction rate model. 35
Heterogeneous reactors, 2 •
Langmuir isotherm, 54
Heun's method, 20 Liquid holdup in bubble columns, 263
High-severitv reactors. construction of,
L •
Liquid hourly space velocit) (LHS\'j, 207
334 Litol process, 335
Holdup in trickle-bed reactors. 165-171 Low-scveriu• reactors. construction of, 354
•
370 INDEX
Mass transfer; Parallel reactions, handling of several, 41-

coefficient, 65 44
in FBBRs, 244 Parametric sensitivity, 332-334
in fixed-bed gas reactors, 81-85, 89-91 in NINAF reactors, 332-333
in suspended-bed reactors, 276-283 Partial differenrial equations (PDE), 14
in trickle-bed reactors, 176-181 algorithms for solving, 37-41
Maximum allowable stress, 347 Pedet number:
Mears' limit to axial dispersion, 168 for heat: and two-phase axial disper-
Mechanical design, 9 sion. 199
of commercial reactors, 343-:~5 i and two-phase Row, 220
definition of, 4, 343 for mass: in gas-liquid systems, 167
Metastable steady states, 335
,
in gas systems, 82
Microreactor system, 322
,
Phase fraction, definition of. 191
"'1odeling: Phthalic anhvdride, air-oxidation of naph-
accuracy in t\[t\Af reactor design, im- thalene to, 136-151
portance of, 339-340 Picard's iteration, 361
an ey isting plant, 6 P1'l ot reactors. °1- "9- 32-/
Cl J, Cl_"-
of reactors, 6 mechanical design of. 326
Models: Poisoning of catalvst, 54
of catalnic
, reaction rate, 55 Poisson's law, 346
of t\ 1:\ A F gas reactors, 130 Poisson's ratio, 346
"'fodulus of c;asticity, 345 Porositv• of catalyst, 54
•
1\loying-bed reactor, 2 Power la\\', 55

Multiple steady states, 334 Prandtl number. 85
Predictor-corrector methud, 2 I
Pressure drop:
National Association nf Corrosion Engi-
across FBBRs, 242
neers (NAC"'), 357
acrOss fixed-bed gas reactors, 79
Newton-Raphson algorithm, 38
across suspended-bed reactors, 262
Ne\\'ton-Raphson iteration, 361
across trickle-bed reactors, 162-165
Nlt\Af gas reactors, 78,129-151
Pressure vessel code of the AS;,!E, 344
design example for, 136-151
Process control problems; 331
importance of modeling accuracy in de-
Process design:
sign of, 33-340
definition of, 4
Nonadiabatic reactor, 3 .
of fBBRs, 245
(See aLm NE\AF gas reactors)
of fixed-bed gas reactors, 99-151
Nonisothermal, nonadiabatic fixed-bed
of suspended-bed reactors, 286-304
gas reactors (see t\I:\Af gas reac-
of trickle-bed reactors, 189-236
tors)
Proportional limit in metal strength. 345
!'\ onisothermaI reactor, 3
Pulse function input, 166
t\usselt number:
Pulsing flow, 159
for a packed bed, 87
Pulsing-regime reactors, 245
for a single sphere, 87
ODE (see Differential equations, ordinary) Quasilillearizatic:: met;,od, 29

One-dimensional plug-Row model for adi- Quenching between two catalyst beds,
a batic reactor design, 107 110,113-114
Operating considerations, 331
Order of reaction, 56
•
Ordinary differential e<tLlations (see Differ- Radial dispersion:
enti:!1 equations, ordinary) of heat, 85
Oscillati:1g reactions, 33 i of mass, 82
INDEX 371
Radial dispersion (Coni.): Reactor(s), design of. methods of

in trickle-bed reactors, 171-172 (erml.):
Radial Pedet numbn: traditional, 4
for gas-phase heat flow, H5, 134 needs for, 10
for gas-phase mass flow, H~, 134 phases of, 'i
Radiant heat transfer', 87 modcling of. (;
Radiation passag-e IH1Illbcj-, HH sa f·Cl"• 0 f'•."')') ""')
-' ..... -~J~l_
Reaction kinetics. 'j:J-7'2 stability, of. :'1:H-:-l4()
efleets of p()n' structure on. 64-72 definition of. :l:H
Reaction c:"{lcr. :>(-) Recvde reactor, (;:,-64. 3~4
•
detennin'll.on of. 59-60 Regeneration:
Reaction rate: cata!>'st L.iiure during. 330
constant. 56 thermal excursion during, :1:10
experimental. 65 Residence time distrihution, I (is
Arrhcnius plot f(lr. 68. 72 ReY/lolds
•
number. 8:,. 170, 2()"
intrinsic. 6'i
dctcrraination of. :;H-64
glob,t1. SI. b4 Safety, factor. 34'/
imrimic. ,-, I. ~jO S a f·ety () f' reanors, .",_.
•
'2'1-."I ."~'
,_
models. 'i:, Sauter diameter. mean. 26

Reactions: Schmidt number, 1'4
U)llSeCLlliH~. in for the liquid, 2')~1
Silllult'Ull'OUS. 70 Selectivitv, , definition of. 70
Rl'auor(s): Shaking aUlOcl.i\·e. 3!-:
c1assifica,ion of. I. 71'. 155-15S. 251- Sherwood nUInber, ~7~
();" <...'
--.)<) SimuLmeolls reactions. 70
adiabatic. :\. 10(i-129 Slug flow. 1.~9
I) UI1 ,) ')C' ')-b- ')nc 9"q
) ) Ie. ~, ... ,)1"-_J ,_:1.)-_:1, .SI llrn, . react.Jr.
. , ')_, 9;' ')-6 ,_99-J-_999
_,,"'-_J
(See (!Lw Slurn reactor) backmixing of phases in, 271
continuous stirred-tank (CSTR). 2. description of. 254-256
c')
\) .... , _:1')-1 -_J""!.
')c., '){'~ ) U ' 9q-
_ L . '_Qb-_~ ~J dispersion of the gas in, 263
ebullated-bed. 2. 2'i(i-259, 299-30 I Space time, 59
f·lXCCI I )eeI • 'J_. -i -/-_')4-,
~ Spray flow. 159
fluidized-bed. 2 Spray-regime reactors. 2~.')
gas-liquid-phase. 3. 155-304 Stability of algorithms. 19
gas-piJa,e. 3. 77-151 Stability study of reactors. 4. 334-
isothermal. :-1. :)9-106 340
1110yiIlg--bed. 2 Stable stead\', states. 335
••
nonadiabatic. 3 Stead\'-state multiplicit\·:
(Set "/.'0 :\ I:\A.f gas reac[(ns) at catalyst pellet leYe!. 337
non isothermal. :l in CSTRs. :137
(.'irl' ailO :\1:\Af gas reactors) due to nonadiabaticity. 336 •
S I Ut ".
1\. g gc,
_ ...... 0-~
)""t-_Ju. 0"- ')qD
_;:1.:J-_~ :J Stead" states:
• •
'lIspended-bed. ~. 251-304 metastable, 33.')

three-phase transport. 3. 259-261. stable. 335 -
:lO 1-:l04 Step function input. 165
trickle-bed. 3. 156, 165-181. 189-2:16 Stokes' law, '275
(SrI' aiso specif,c ria5sificalioll l'lllri/!s) Strain, 345
construction methods, 353-357 Strength of reactor wall. 344
•
design of: around a model. 7 Stress. :')45
methods of. 4 maximum allowable. 347
. . -
a pnon, :l Surface stirring method, 262
,
372 INDEX
Suspended-bed reactors, 2, 251-304 Transport phenomena (ConI.):

advantages and drawbacks of, 285-286, in fixed-bed gas reactors, 77-97
288 in suspended-bed reactors, 261-
classification of. 251-25R <)8-
~ :J
g-as bubbles and liquid in, 262-275 in trickle-bed reactors, 158-181

heat transfer in, 283-285 Trickle-l>ed 1\ 1:\ A F reactors, 175
Illass transfer in, 276-2K3 Trickle-bed reactors. cl. 1:')6. ItlS-181,
pressure drop across, 262 189-2:·\1;
process design of. 286-304 axial dispns;<Hl ill. j(;:-,-169
suspending the catalyst in, 275-276 desig-n of: 1"":I-..,,,i,,·<I. 1~17-~OO, 217-
transport phenomena in. 259-285 230
Suspending the catalvst in suspended plug-flo\\'. 1'1"-1'1,.2111-216
be d s, 2 _- 9-"
I.'}-_/u heat transfer ill. 172-176
Swagdok reactor. 320 holdu!, in. Itie,-I,I
Symhoil process for coal liquefaction, ltil) mass translt-r in. 17(;-181
pressure drop ill. 1(;:'>-16,-,
process design of. I R<i-2:Hi
'ferllperatulT gradients: radial dispcr:--ioJl ill. 171-17'2
interphase, 92 transport phenomena ill. L-,i'l-181
intrapllasc,91 Tridiagonal cociJlcicllt mall·i". '15
Tensile specimen. 344
'1 ensile strength. :).j.j
Tensile test, :-144

Texture of the liquid phase. 161
Thermal Biot nllmber. '12
-} nennal excursion during Gualysr. regen- \·isc()sit~· of ~a~ 1l11\:{urI'S. lIb
eration, 330 \'oid franioll. I ~II
Thick-wall reactors. design of. 550-553
Thiele modulus, 68-70, 20~
Thill-\\,all reactors. design of. 348-350 \Vall BiOI number. 't:i
Thomas' method, 35 Weight hour" sp"ce \ ('iocit\ (\\'l-JSV).
Three-phase transport reactor (3<jJTR), 3, 207
259-261, 301-3(H \\'ickel process. :\;,1;
'le
descriptiOl' 2,~9-261 \\'orking st ress. :)4-;
process design of, 301-504
TortllosilV• factor. 180
•
Transport phenomena: Yield. definition of. 70

in FBBRs. 242-24.~ Yield point. :~·L'
•
,
ABOUT THE AUTHOR

•
1>.1. OR1L\\: T-\RIlA\:. " chelllical h(,jd" 11; l', S. and {(')reign
<..:nglIlecrlllg cOllsultant.
p.tlC'JlI' . .-\n <tllthorit\, Oil catal:lic react()r design alld Oil the desigll of p,,,kcd-ht'd gdS
puriil( at"!ll l''''I1[S_ he "Iso has had considerable ('xpericnu: ill R&ll \'.01''' on cttahtic
pnJ( t',,,,C\ .
.-\ ndlive of Turkn. •
1>.11'. '[""rh,," sllIdied at the tecillli,al tlninTsitie, ot llarmstadt and
Dresden .-\!Ier emigrating to the Lniled Slales in 19:"1. he bccame a resealch and
Cilclllical projnl engineer at DonIler-lianlla Coke Corporation_ In I'L',S hc-joined
Ikfidchelll SIt'd Corporation as a research engineer. Ill' panicil'aled ill Ihe joillt
dC"'(,I(IPI'IlCIlt 01 the Litol process (a catalytic h~dro-rt.'fitling pnJt-cs,- for cok.t'-O\'CIl
a.r()ln~Hic..;;) that Bethlehenl Steel undertook \'·;ith H.ol1dr~· Procc\:-; (;o1"}J()r;tli(III (11 1 )\\' ~I pan
of .-\ir i'roduct, ;'nd Chemicals, incl. ~1r. Tarhan has ICClured Oil Clla"tl( ICH",r dt',ign
aT Leh!gll C'lli\t:,!sity ~ind ~n contilluing t:ducatioll courses both helt' ;illd ~thro:!d_ lIt'
tCrilt'd !r(,IIl BClldeheol Steel ill 1~~S~ to heC(H1H:;! nJllslJi{(lIII .
311

Catalytic Reactor Design-Orhan Tarhan

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•

l\IlcGraw-HilL Book Company

Library of Congress Cataloging i1l Publicat;"" Data

Includes bibliographies and index .

Copyright © 1983 by McGraw-HiII, lnc. All rights resen·ed

1234567890 KGP/KGP 898765-13

Ordinan' Di fferential Equations 13

2.4 Simultaneous Ordinary Differential Equations

4.3 Interpha~~ Transport in Fixed-Bed Gas Reactors 79

. viii CON I ENTS

Heat Transfer in FBBRs 243

DESIGN OF LABORATORY AND

REACTOR SAl Ell'

Meeting of Corrosion Resistance Requirements 356

overview chapter. This subject was considered too important to be left

pletely valueless results.

selection of excessively large step sizes (in numerical integration) might

Catalytic reactors are vessels or containers in which catalytic chemical re-

which occurs in liquid water of pH I to 6 containing a certain amount •

of ions. The catalvst

2 CATALYTIC REACTOR DESIGN

water vapor at temperatures below 400°C. Above 400°C the reaction

(CSTRs). Of course, as mentioned in th~ preface, this book discusses

3. If the cat<ilyst is suspended in an upflow of liquid, we ha\e an ebullated-

4. If the catalyst is suspended in a flow of liquid and gas strong enough

4 CATALYTIC REACTOR DESIGN

o >0 -~~ 0 -----.;". . •

FIG. 1-2 Ideal scale-up procedure. J (From Vem W. Weekman,jr., by permission.)

Chem. 8 physic. Plont

6 CATALYTIC REACTOR DESIGN

full-scole Chem. a ph ysic. Computer

FIG. 1-4 Modeling of a commercial process.' (From Vent W. Weehman,jr., by

aASStFICATION OF REACTORS AND PHASES OF DESIGN 7

opment (R & D) group until a fitting model is obtained. The steps of

8 CATALYTIC REACTOR DESIGN

seen and calculated. Similarly. various physical and therlIlodynamic

When designing a reactor aJrOund a model, the collection of data is

CLASSIRCATlON OF REACTORS AND PlIASES OF DESIGN 9

10 cATAlYTIC REACTOR DESIGN

WHO NEEDS REACTOR DESIGN?

5. Rutherford Aris, Elementary Chemical Reaction Analysis, Prentice-Hall, Engle-

The design of fixed-bed reactors depends upon the simultaneous so-

Ordinary Differential Equations

pendent variables y (e.g., reaction temperature, fractional conversion,

Partial Diffelential Equations

METHODS OF NUMERICAL COMPUTAllON 15

This may be of interest for spherical coordinates, i.e.,

and x, = Xf) + ih where i'= 0, I, ... n.

..---y(x,l True value of XI

FIG. 2-2 Method of approximating a differential e«Juation.

),,, + 1 = Y" + !()'n, xu) h + En (2-8)

The added terms in the brackets may be called truncation error. If we

The derivative dy/dx can itself be expanded in a Taylor series:

where subscript e denotes "estimated."

which is the essence of the Euler algorithm.

100 FO~MAT (10X.~10.~.10X.FIO.6)

X.t.4Ax = 1.000000 H - (I.olcoeo

MffiIODS OF NUMERICAL COMPUTATION 19

20 CATALYTIC REACTOR DESIGN

FIG. 2-4 Flow diagl am of Euler algorithm.

culations. There have been numerous improvements in the Euler method.

- y" + I = J" It f (x", Y,,) (2-16)

The see:md step uses the equation:

)'n~1 = y" + hf (2-19)