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Multiphase Catalytic Reactors
Multiphase CatalyticReactorsTheory Design Manufacturingand Applications
Edited by
Zeynep Ilsen OumlnsanDepartment of Chemical Engineering
Boğaziccedili UniversityIstanbul Turkey
Ahmet Kerim AvciDepartment of Chemical Engineering
Boğaziccedili UniversityIstanbul Turkey
Copyright copy 2016 by John Wiley amp Sons Inc All rights reserved
Published by John Wiley amp Sons Inc Hoboken New Jersey
Published simultaneously in Canada
No part of this publication may be reproduced stored in a retrieval system or transmitted in any form or by any means electronicmechanical photocopying recording scanning or otherwise except as permitted under Section 107 or 108 of the 1976 United StatesCopyright Act without either the prior written permission of the Publisher or authorization through payment of the appropriateper-copy fee to the Copyright Clearance Center Inc 222 Rosewood Drive Danvers MA 01923 (978) 750-8400 fax (978) 750-4470 oron the web at wwwcopyrightcom Requests to the Publisher for permission should be addressed to the Permissions DepartmentJohn Wiley amp Sons Inc 111 River Street Hoboken NJ 07030 (201) 748-6011 fax (201) 748-6008 or online athttpwwwwileycomgopermissions
Limit of LiabilityDisclaimer ofWarranty While the publisher and author have used their best efforts in preparing this book they makeno representations or warranties with respect to the accuracy or completeness of the contents of this book and specifically disclaimany implied warranties of merchantability or fitness for a particular purpose No warranty may be created or extended by salesrepresentatives or written sales materials The advice and strategies contained herein may not be suitable for your situation You shouldconsult with a professional where appropriate Neither the publisher nor author shall be liable for any loss of profit or any othercommercial damages including but not limited to special incidental consequential or other damages
For general information on our other products and services or for technical support please contact our Customer Care Departmentwithin the United States at (800) 762-2974 outside the United States at (317) 572-3993 or fax (317) 572-4002
Wiley also publishes its books in a variety of electronic formats Some content that appears in print may not be available in electronicformats For more information about Wiley products visit our web site at wwwwileycom
Library of Congress Cataloging-in-Publication Data
Names Oumlnsan Zeynep Ilsen editor | Avci Ahmet Kerim editorTitle Multiphase catalytic reactors theory design manufacturing andapplications edited by Zeynep Ilsen Oumlnsan Ahmet Kerim Avci
Description Hoboken New Jersey John Wiley amp Sons Inc [2016] | Includesbibliographical references and index
Identifiers LCCN 2016009674 | ISBN 9781118115763 (cloth) | ISBN 9781119248477(epub) | ISBN 9781119248460 (epdf)
Subjects LCSH Phase-transfer catalysis | Chemical reactorsClassification LCC TP159C3 M85 2016 | DDC 6602832ndashdc23LC record available at httpslccnlocgov2016009674
Set in 95 12pt Minion by SPi Global Pondicherry India
Printed in the United States of America
10 9 8 7 6 5 4 3 2 1
Contents
List of Contributors x
Preface xii
Part 1 Principles of catalytic reaction engineering
1 Catalytic reactor types and their industrial significance 3Zeynep Ilsen Oumlnsan and Ahmet Kerim Avci
11 Introduction 3
12 Reactors with fixed bed of catalysts 3121 Packed-bed reactors 3122 Monolith reactors 8123 Radial flow reactors 9124 Trickle-bed reactors 9125 Short contact time reactors 10
13 Reactors with moving bed of catalysts 11131 Fluidized-bed reactors 11132 Slurry reactors 13133 Moving-bed reactors 14
14 Reactors without a catalyst bed 14
15 Summary 16
References 16
2 Microkinetic analysis of heterogeneous catalytic systems 17Zeynep Ilsen Oumlnsan
21 Heterogeneous catalytic systems 17211 Chemical and physical characteristics of solid
catalysts 18212 Activity selectivity and stability 21
22 Intrinsic kinetics of heterogeneous reactions 22221 Kinetic models and mechanisms 23222 Analysis and correlation of rate data 27
23 External (interphase) transport processes 32231 External mass transfer Isothermal conditions 33232 External temperature effects 35233 Nonisothermal conditions Multiple steady
states 36234 External effectiveness factors 38
24 Internal (intraparticle) transport processes 39241 Intraparticle mass and heat transfer 39242 Mass transfer with chemical reaction Isothermal
effectiveness 41
243 Heat and mass transfer with chemical reaction 45244 Impact of internal transport limitations
on kinetic studies 47
25 Combination of external and internal transporteffects 48251 Isothermal overall effectiveness 48252 Nonisothermal conditions 49
26 Summary 50
Nomenclature 50
Greek letters 51
References 51
Part 2 Two-phase catalytic reactors
3 Fixed-bed gasndashsolid catalytic reactors 55Joatildeo P Lopes and Aliacuterio E Rodrigues
31 Introduction and outline 55
32 Modeling of fixed-bed reactors 57321 Description of transportndashreaction
phenomena 57322 Mathematical model 59323 Model reduction and selection 61
33 Averaging over the catalyst particle 61331 Chemical regime 64332 Diffusional regime 64
34 Dominant fluidndashsolid mass transfer 66341 Isothermal axial flow bed 67342 Non-isothermal non-adiabatic axial flow bed 70
35 Dominant fluidndashsolid mass and heat transfer 70
36 Negligible mass and thermal dispersion 72
37 Conclusions 73
Nomenclature 74
Greek letters 75
References 75
4 Fluidized-bed catalytic reactors 80John R Grace
41 Introduction 80411 Advantages and disadvantages of fluidized-bed
reactors 80412 Preconditions for successful fluidized-bed
processes 81
v
413 Industrial catalytic processes employingfluidized-bed reactors 82
42 Key hydrodynamic features of gas-fluidized beds 83421 Minimum fluidization velocity 83422 Powder group and minimum bubbling
velocity 84423 Flow regimes and transitions 84424 Bubbling fluidized beds 84425 Turbulent fluidization flow regime 85426 Fast fluidization and dense suspension
upflow 85
43 Key properties affecting reactor performance 86431 Particle mixing 86432 Gas mixing 87433 Heat transfer and temperature uniformity 87434 Mass transfer 88435 Entrainment 88436 Attrition 89437 Wear 89438 Agglomeration and fouling 89439 Electrostatics and other interparticle forces 89
44 Reactor modeling 89441 Basis for reactor modeling 89442 Modeling of bubbling and slugging flow
regimes 90443 Modeling of reactors operating in high-velocity
flow regimes 91
45 Scale-up pilot testing and practical issues 91451 Scale-up issues 91452 Laboratory and pilot testing 91453 Instrumentation 92454 Other practical issues 92
46 Concluding remarks 92
Nomenclature 93
Greek letters 93
References 93
Part 3 Three-phase catalytic reactors
5 Three-phase fixed-bed reactors 97Ion Iliuta and Faiumlccedilal Larachi
51 Introduction 97
52 Hydrodynamic aspects of three-phase fixed-bedreactors 98521 General aspects Flow regimes liquid holdup
two-phase pressure drop and wetting efficiency 98522 Standard two-fluid models for two-phase
downflow and upflow in three-phase fixed-bedreactors 100
523 Nonequilibrium thermomechanical models fortwo-phase flow in three-phase fixed-bedreactors 102
53 Mass and heat transfer in three-phase fixed-bedreactors 104531 Gasndashliquid mass transfer 105532 Liquidndashsolid mass transfer 105533 Heat transfer 106
54 Scale-up and scale-down of trickle-bed reactors 108541 Scaling up of trickle-bed reactors 108542 Scaling down of trickle-bed reactors 109543 Salient conclusions 110
55 Trickle-bed reactorbioreactor modeling 110551 Catalytic hydrodesulfurization and bed
clogging in hydrotreating trickle-bedreactors 110
552 Biomass accumulation and clogging intrickle-bed bioreactors for phenolbiodegradation 115
553 Integrated aqueous-phase glycerol reformingand dimethyl ether synthesis into anallothermal dual-bed reactor 121
Nomenclature 126
Greek letters 127
Subscripts 128
Superscripts 128
Abbreviations 128
References 128
6 Three-phase slurry reactors 132Vivek V Buwa Shantanu Roy and Vivek V Ranade
61 Introduction 132
62 Reactor design scale-up methodology and reactorselection 134621 Practical aspects of reactor design and
scale-up 134622 Transport effects at particle level 139
63 Reactor models for design and scale-up 143631 Lower order models 143632 Tank-in-seriesmixing cell models 144
64 Estimation of transport and hydrodynamicparameters 145641 Estimation of transport parameters 145642 Estimation of hydrodynamic parameters 146
65 Advanced computational fluid dynamics(CFD)-based models 147
66 Summary and closing remarks 149
Acknowledgments 152
Nomenclature 152
Greek letters 153
Subscripts 153
References 153
vi Contents
7 Bioreactors 156Pedro Fernandes and Joaquim MS Cabral
71 Introduction 156
72 Basic concepts configurations and modes ofoperation 156721 Basic concepts 156722 Reactor configurations and modes of
operation 157
73 Mass balances and reactor equations 159731 Operation with enzymes 159732 Operation with living cells 160
74 Immobilized enzymes and cells 164741 Mass transfer effects 164742 Deactivation effects 166
75 Aeration 166
76 Mixing 166
77 Heat transfer 167
78 Scale-up 167
79 Bioreactors for animal cell cultures 167
710 Monitoring and control of bioreactors 168
Nomenclature 168
Greek letters 169
Subscripts 169
References 169
Part 4 Structured reactors
8 Monolith reactors 173Joatildeo P Lopes and Aliacuterio E Rodrigues
81 Introduction 173811 Design concepts 174812 Applications 178
82 Design of wall-coated monolith channels 179821 Flow in monolithic channels 179822 Mass transfer and wall reaction 182823 Reaction and diffusion in the catalytic
washcoat 190824 Nonisothermal operation 194
83 Mapping and evaluation of operatingregimes 197831 Diversity in the operation of a monolith
reactor 197832 Definition of operating regimes 199833 Operating diagrams for linear kinetics 201834 Influence of nonlinear reaction kinetics 202835 Performance evaluation 203
84 Three-phase processes 204
85 Conclusions 207
Nomenclature 207
Greek letters 208
Superscripts 208
Subscripts 208
References 209
9 Microreactors for catalytic reactions 213Evgeny Rebrov and Sourav Chatterjee
91 Introduction 213
92 Single-phase catalytic microreactors 213921 Residence time distribution 213922 Effect of flow maldistribution 214923 Mass transfer 215924 Heat transfer 215
93 Multiphase microreactors 216931 Microstructured packed beds 216932 Microchannel reactors 218
94 Conclusions and outlook 225
Nomenclature 226
Greek letters 227
Subscripts 227
References 228
Part 5 Essential tools of reactor modeling and design
10 Experimental methods for the determination ofparameters 233Rebecca R Fushimi John T Gleaves and GregoryS Yablonsky
101 Introduction 233
102 Consideration of kinetic objectives 234
103 Criteria for collecting kinetic data 234
104 Experimental methods 2341041 Steady-state flow experiments 2351042 Transient flow experiments 2371043 Surface science experiments 238
105 Microkinetic approach to kinetic analysis 241
106 TAP approach to kinetic analysis 2411061 TAP experiment design 2421062 TAP experimental results 244
107 Conclusions 248
References 249
11 Numerical solution techniques 253Ahmet Kerim Avci and Seda Keskin
111 Techniques for the numerical solution of ordinarydifferential equations 2531111 Explicit techniques 2531112 Implicit techniques 254
112 Techniques for the numerical solution of partialdifferential equations 255
Contents vii
113 Computational fluid dynamics techniques 2561131 Methodology of computational fluid
dynamics 2561132 Finite element method 2561133 Finite volume method 258
114 Case studies 2591141 Indirect partial oxidation of methane in a
catalytic tubular reactor 2591142 Hydrocarbon steam reforming in
spatially segregated microchannelreactors 261
115 Summary 265
Nomenclature 266
Greek letters 267
Subscriptssuperscripts 267
References 267
Part 6 Industrial applications of multiphase reactors
12 Reactor approaches for FischerndashTropsch synthesis 271Gary Jacobs and Burtron H Davis
121 Introduction 271
122 Reactors to 1950 272
123 1950ndash1985 period 274
124 1985 to present 2761241 Fixed-bed reactors 2761242 Fluidized-bed reactors 2801243 Slurry bubble column reactors 2811244 Structured packings 2861245 Operation at supercritical conditions(SCF) 288
125 The future 288
References 291
13 Hydrotreating of oil fractions 295Jorge Ancheyta Anton Alvarez-Majmutov andCarolina Leyva
131 Introduction 295
132 The HDT process 2961321 Overview 2961322 Role in petroleum refining 2971323 World outlook and the situation ofMexico 298
133 Fundamentals of HDT 3001331 Chemistry 3001332 Reaction kinetics 3031333 Thermodynamics 3051334 Catalysts 306
134 Process aspects of HDT 3071341 Process variables 307
1342 Reactors for hydroprocessing 3101343 Catalyst activation in commercial
hydrotreaters 316
135 Reactor modeling and simulation 3171351 Process description 3171352 Summary of experiments 3171353 Modeling approach 3191354 Simulation of the bench-scale unit 3201355 Scale-up of bench-unit data 3231356 Simulation of the commercial
unit 324
Nomenclature 326
Greek letters 327
Subscripts 327
Non-SI units 327
References 327
14 Catalytic reactors for fuel processing 330Gunther Kolb
141 IntroductionmdashThe basic reactions of fuelprocessing 330
142 Theoretical aspects advantages and drawbacks offixed beds versus monoliths microreactors andmembrane reactors 331
143 Reactor design and fabrication 3321431 Fixed-bed reactors 3321432 Monolithic reactors 3321433 Microreactors 3321434 Membrane reactors 333
144 Reformers 3331441 Fixed-bed reformers 3361442 Monolithic reformers 3371443 Plate heat exchangers and microstructured
reformers 3421444 Membrane reformers 344
145 Water-gas shift reactors 3481451 Monolithic reactors 3481452 Plate heat exchangers and microstructured
water-gas shift reactors 3481453 Water-gas shift in membrane reactors 350
146 Carbon monoxide fine cleanup Preferential oxidationand selective methanation 3501461 Fixed-bed reactors 3521462 Monolithic reactors 3521463 Plate heat exchangers and microstructured
reactors 353
147 Examples of complete fuel processors 3551471 Monolithic fuel processors 3551472 Plate heat exchanger fuel processors on the
meso- and microscale 357
viii Contents
Nomenclature 359
References 359
15 Modeling of the catalytic deoxygenation of fatty acids in apacked bed reactor 365Teuvo Kilpiouml Paumlivi Maumlki-Arvela Tapio Salmi andDmitry Yu Murzin
151 Introduction 365
152 Experimental data for stearic aciddeoxygenation 366
153 Assumptions 366
154 Model equations 367
155 Evaluation of the adsorption parameters 368
156 Particle diffusion study 369
157 Parameter sensitivity studies 369
158 Parameter identification studies 370
159 Studies concerning the deviation from ideal plug flowconditions 371
1510 Parameter estimation results 372
1511 Scale-up considerations 372
1512 Conclusions 375
Acknowledgments 375
Nomenclature 375
Greek letters 375
References 376
Index 377
Contents ix
List of contributors
Anton Alvarez-MajmutovInstituto Mexicano del Petroacuteleo Management of Products for theTransformation of Crude Oil Mexico City Mexico
Jorge AncheytaInstituto Mexicano del Petroacuteleo Management of Products for theTransformation of Crude Oil Mexico City Mexico
Ahmet Kerim AvciDepartment of Chemical Engineering Boğaziccedili University Istanbul Turkey
Vivek V BuwaDepartment of Chemical EngineeringIndian Institute of Technology-Delhi New Delhi India
Joaquim MS CabralDepartment of Bioengineering and IBB-Institute for Bioengineeringand Biosciences Instituto Superior Teacutecnico Universidade de LisboaLisboa Portugal
Sourav ChatterjeeSchool of Chemistry and Chemical Engineering Queenrsquos University BelfastBelfast UK
Burtron H DavisCenter for Applied Energy Research University of KentuckyLexington KY USA
Pedro FernandesDepartment of Bioengineering and IBB-Institutefor Bioengineering and Biosciences Instituto Superior TeacutecnicoUniversidade de Lisboa Faculdade de EngenhariaUniversidade Lusoacutefona de Humanidadese Tecnologias Lisboa Portugal
Rebecca R FushimiMaterials Science amp Engineering Department Idaho National LaboratoryIdaho Falls ID USA
John T GleavesDepartment of Energy Environmental and Chemical EngineeringWashington University St Louis MO USA
John R GraceDepartment of Chemical and Biological EngineeringThe University of British Columbia VancouverBritish Columbia Canada
Ion IliutaChemical Engineering Department Laval University Queacutebec CityQueacutebec Canada
Gary JacobsCenter for Applied Energy Research University of KentuckyLexington KY USA
Seda KeskinDepartment of Chemical and Biological Engineering Koc UniversityIstanbul Turkey
Teuvo KilpioumlProcess Chemistry Centre Aringbo Akademi University TurkuAringbo Finland
Gunther KolbFraunhofer ICT-IMM Decentralized and Mobile Energy TechnologyDepartment Mainz Germany
Faiumlccedilal LarachiChemical Engineering Department Laval University Queacutebec CityQueacutebec Canada
Carolina LeyvaCentro de Investigacioacuten en Ciencia Aplicada y Tecnologiacutea AvanzadaUnidad Legaria Instituto Politeacutecnico Nacional Mexico City Mexico
Joatildeo P LopesDepartment of Chemical Engineering and BiotechnologyUniversity of Cambridge Cambridge UK
Paumlivi Maumlki-ArvelaProcess Chemistry Centre Aringbo Akademi University TurkuAringbo Finland
Dmitry Yu MurzinProcess Chemistry Centre Aringbo Akademi University TurkuAringbo Finland
Zeynep Ilsen OumlnsanDepartment of Chemical Engineering Boğaziccedili University Istanbul Turkey
Vivek V RanadeChemical Engineering amp Process Development Division National ChemicalLaboratory Pune India
Evgeny RebrovSchool of Engineering University of Warwick Coventry UK
x
Aliacuterio E RodriguesLaboratory of Separation and Reaction EngineeringAssociate Laboratory LSRELCM Department of Chemical EngineeringFaculty of Engineering University of Porto Porto Portugal
Shantanu RoyDepartment of Chemical Engineering Indian Institute of Technology-DelhiNew Delhi India
Tapio SalmiProcess Chemistry Centre Aringbo Akademi UniversityTurkuAringbo Finland
Gregory S YablonskyParks College of Engineering Aviation and TechnologySaint Louis University St Louis MO USA
List of contributors xi
Preface
The single irreplaceable component at the core of a chemicalprocess is the chemical reactor where feed materials are con-verted into desirable products Although the essential variablesby which chemical processes can be controlled are reaction tem-perature pressure feed composition and residence time in thereactor two technological developments of major consequencestarting with 1960s have made possible cost-effective operationunder less severe conditions these are the extensive use of effi-cient catalysts and the introduction of improved or innovativereactor configurations The impact of heterogeneous catalysisis significant in this respect since petroleum refining manufac-turing of chemicals and environmental clean-up which are thethree major areas of the world economy today all requirethe effective use of solid catalysts The challenges involved inthe design of novel solid catalysts and modification of manyexisting ones for higher selectivity and stability have alsoprompted the development of ldquoengineeredrdquo catalysts befittingnovel reactor configurations requiring the use of new supportssuch as monolithic or foam substrates as well as the establish-ment of new techniques for coating surfaces with diverse catalystcomponents in order to ensure longevity particularly in cyclicprocessesIn industrial practice the composition and properties of the
complex feed mixtures that are processed for producing a rangeof valuable chemicals generally necessitate the use of heteroge-neous catalytic reactors Numerous chemical and physical rateprocesses take place in a heterogeneous reactor at differentlength and time scales and frequently in different phasesThe prerequisite for the successful design and operation of cat-alytic reactors is a thorough microkinetic analysis starting fromintrinsic kinetic models of the steady-state chemical activity andleading to global rate expressions obtained by overlaying theeffects of physical rate phenomena occurring at the particlescale Kinetic models of increasing complexity may be requireddepending on the variety of components and number of reac-tions involved The second critical stage in reactor modelingand design is a macrokinetic analysis including the detaileddescription of physical transport phenomena at the reactor scaleand utilizing the global rate expressions of the microkineticanalysis The final catalytic reactor model which integrates theseessential stages can successfully predict the performance anddynamics of plant-scale industrial reactors as well as simulatingtheir start-up shutdown and cyclic operation Taking intoaccount engineered catalysts and new reactor configurations
the modeling and scaling up of reactions conducted at thebench-scale to pilot plant and industrial-scale reactor levels haveto be modified in order to include simultaneous multiscaleapproaches along with the conventional sequential modesMultiphase Catalytic Reactors Theory Design Manufactur-
ing and Applications is a comprehensive up-to-date compila-tion on multiphase catalytic reactors which will serve as anexcellent reference book for graduate students researchersand specialists both in academia and in industry The contentof the book is planned to cover topics starting from the firstprinciples involved in macrokinetic analysis of two- andthree-phase catalytic reactors to their particular industrial appli-cations The main objective is to provide definitive accounts onacademic aspects of multiphase catalytic reactor modeling anddesign along with detailed descriptions of some of the mostrecent industrial applications employing multiphase catalyticreactors in such a way as to balance the academic and industrialcomponents as much as possible Accordingly seven chaptersare included in Parts II III and IV to review the relevantmathematical models and model equations utilized in the fun-damental analysis and macroscopic design of specific reactortypes together with some useful approximations for theirdesign and scale-up from a practical standpoint while the fourchapters in Part VI describe specific industrial applications andcontain pointers that tie in with the modeling and designapproaches presented for the particular multiphase catalyticreactor types discussed in Parts II III and IV Furthermorethe chapters included in Parts I and V of the book containdetailed reviews of the basic principles and essential tools ofcatalytic reaction engineering that are crucial for the successfuldesign and operation of catalytic reactors All chapters ofthe book are contributed by experts distinguished in theirrespective fieldsThe total of 15 chapters included in Multiphase Catalytic
Reactors Theory Design Manufacturing and Applications areorganized in six parts Part I is an overview of the principlesof catalytic reaction engineering embracing Chapter 1 whichis a survey of multiphase catalytic reactor types and their indus-trial significance as well as Chapter 2 on the microkinetic anal-ysis of heterogeneous catalytic systems which surveys theformulation of intrinsic rate equations describing chemical rateprocesses and the construction of global rate expressions thatinclude the effects of physical mass and heat transport phenom-ena occurring at the particle scale Chapters 3 through 9 in
xii
Parts II III and IV discuss individual two- and three-phase cat-alytic reactor types and provide design equations and empiricalrelationships that characterize different multiphase reactorsmathematical modeling is an integral part of these chaptersIn Part II two-phase catalytic reactors are grouped as fixed-bed gasndashsolid catalytic reactors (Chapter 3) and fluidized-bedcatalytic reactors (Chapter 4) Part III deals exclusively withthree-phase catalytic reactors and includes Chapter 5 onthree-phase fixed-bed reactors as well as Chapter 6 on three-phase slurry reactors both of which find significant industrialapplications moreover multiphase bioreactors are also includedin Part III as Chapter 7 Part IV is devoted to the discussion ofthe more recent state-of-the-art structured reactors the theoret-ical aspects and examples of structured reactors enabling processintensification in multiphase operation are treated in Chapter 8on monolith reactors and in Chapter 9 on microreactors of dif-ferent configurations including microstructured packed bedsand microchannel reactors Part V of the book is specificallydesigned for surveying the essential tools of catalytic reactormodeling and design and comprises two chapters Chapter 10discusses the recent developments and experimental techniquesinvolved in lab-scale testing of catalytic reactions includingsteady-state and transient flow experiments as well as the micro-kinetic and TAP approaches to kinetic analysis whileChapter 11 surveys the numerical solution techniques that arefrequently used in catalytic reactor analysis and demonstrateswith some case studies The capstone section of the bookPart VI contains four chapters devoted to specific industrialapplications of multiphase catalytic reactors and includes the
recent developments and practices in FischerndashTropsch technol-ogies (Chapter 12) a thorough discussion of reactor modelingsimulation and scale-up approaches involved in the hydrotreat-ing of oil fractions (Chapter 13) a detailed assessment of theperformances of various reactor configurations used for fuelprocessing (Chapter 14) and a comprehensive discussion ofcatalytic deoxygenation of fatty acids in a packed-bed reactoras case study in production of biofuels (Chapter 15)
It is indeed a pleasure to thank all of the contributors whohave made this challenging task achievable The editors are sin-cerely grateful for their willingness to devote their valuable timeand effort to this project for their readiness in sharing theirvision knowledge years of experience and know-how and alsofor their patience in tolerating various expected or unexpectedextensions arising from the busy schedules of different contribu-tors It has definitely been a privilege to work with the authorscoauthors and reviewers involved in this book The editorswould also like to extend their thanks to Wiley-Blackwell fortheir commitment to this project and to Michael Leventhalfor his organization andmanagement of the publication process
On a more personal note the editors would like to take thisopportunity to express their sincere gratitude to the late Profes-sor David L Trimm who has inspired their research in catalysisand catalytic reaction engineering through many years as super-visor mentor colleague and friend
Zeynep Ilsen OumlnsanAhmet Kerim Avci
Istanbul October 2015
Preface xiii
Multiphase Catalytic Reactors
Multiphase CatalyticReactorsTheory Design Manufacturingand Applications
Edited by
Zeynep Ilsen OumlnsanDepartment of Chemical Engineering
Boğaziccedili UniversityIstanbul Turkey
Ahmet Kerim AvciDepartment of Chemical Engineering
Boğaziccedili UniversityIstanbul Turkey
Copyright copy 2016 by John Wiley amp Sons Inc All rights reserved
Published by John Wiley amp Sons Inc Hoboken New Jersey
Published simultaneously in Canada
No part of this publication may be reproduced stored in a retrieval system or transmitted in any form or by any means electronicmechanical photocopying recording scanning or otherwise except as permitted under Section 107 or 108 of the 1976 United StatesCopyright Act without either the prior written permission of the Publisher or authorization through payment of the appropriateper-copy fee to the Copyright Clearance Center Inc 222 Rosewood Drive Danvers MA 01923 (978) 750-8400 fax (978) 750-4470 oron the web at wwwcopyrightcom Requests to the Publisher for permission should be addressed to the Permissions DepartmentJohn Wiley amp Sons Inc 111 River Street Hoboken NJ 07030 (201) 748-6011 fax (201) 748-6008 or online athttpwwwwileycomgopermissions
Limit of LiabilityDisclaimer ofWarranty While the publisher and author have used their best efforts in preparing this book they makeno representations or warranties with respect to the accuracy or completeness of the contents of this book and specifically disclaimany implied warranties of merchantability or fitness for a particular purpose No warranty may be created or extended by salesrepresentatives or written sales materials The advice and strategies contained herein may not be suitable for your situation You shouldconsult with a professional where appropriate Neither the publisher nor author shall be liable for any loss of profit or any othercommercial damages including but not limited to special incidental consequential or other damages
For general information on our other products and services or for technical support please contact our Customer Care Departmentwithin the United States at (800) 762-2974 outside the United States at (317) 572-3993 or fax (317) 572-4002
Wiley also publishes its books in a variety of electronic formats Some content that appears in print may not be available in electronicformats For more information about Wiley products visit our web site at wwwwileycom
Library of Congress Cataloging-in-Publication Data
Names Oumlnsan Zeynep Ilsen editor | Avci Ahmet Kerim editorTitle Multiphase catalytic reactors theory design manufacturing andapplications edited by Zeynep Ilsen Oumlnsan Ahmet Kerim Avci
Description Hoboken New Jersey John Wiley amp Sons Inc [2016] | Includesbibliographical references and index
Identifiers LCCN 2016009674 | ISBN 9781118115763 (cloth) | ISBN 9781119248477(epub) | ISBN 9781119248460 (epdf)
Subjects LCSH Phase-transfer catalysis | Chemical reactorsClassification LCC TP159C3 M85 2016 | DDC 6602832ndashdc23LC record available at httpslccnlocgov2016009674
Set in 95 12pt Minion by SPi Global Pondicherry India
Printed in the United States of America
10 9 8 7 6 5 4 3 2 1
Contents
List of Contributors x
Preface xii
Part 1 Principles of catalytic reaction engineering
1 Catalytic reactor types and their industrial significance 3Zeynep Ilsen Oumlnsan and Ahmet Kerim Avci
11 Introduction 3
12 Reactors with fixed bed of catalysts 3121 Packed-bed reactors 3122 Monolith reactors 8123 Radial flow reactors 9124 Trickle-bed reactors 9125 Short contact time reactors 10
13 Reactors with moving bed of catalysts 11131 Fluidized-bed reactors 11132 Slurry reactors 13133 Moving-bed reactors 14
14 Reactors without a catalyst bed 14
15 Summary 16
References 16
2 Microkinetic analysis of heterogeneous catalytic systems 17Zeynep Ilsen Oumlnsan
21 Heterogeneous catalytic systems 17211 Chemical and physical characteristics of solid
catalysts 18212 Activity selectivity and stability 21
22 Intrinsic kinetics of heterogeneous reactions 22221 Kinetic models and mechanisms 23222 Analysis and correlation of rate data 27
23 External (interphase) transport processes 32231 External mass transfer Isothermal conditions 33232 External temperature effects 35233 Nonisothermal conditions Multiple steady
states 36234 External effectiveness factors 38
24 Internal (intraparticle) transport processes 39241 Intraparticle mass and heat transfer 39242 Mass transfer with chemical reaction Isothermal
effectiveness 41
243 Heat and mass transfer with chemical reaction 45244 Impact of internal transport limitations
on kinetic studies 47
25 Combination of external and internal transporteffects 48251 Isothermal overall effectiveness 48252 Nonisothermal conditions 49
26 Summary 50
Nomenclature 50
Greek letters 51
References 51
Part 2 Two-phase catalytic reactors
3 Fixed-bed gasndashsolid catalytic reactors 55Joatildeo P Lopes and Aliacuterio E Rodrigues
31 Introduction and outline 55
32 Modeling of fixed-bed reactors 57321 Description of transportndashreaction
phenomena 57322 Mathematical model 59323 Model reduction and selection 61
33 Averaging over the catalyst particle 61331 Chemical regime 64332 Diffusional regime 64
34 Dominant fluidndashsolid mass transfer 66341 Isothermal axial flow bed 67342 Non-isothermal non-adiabatic axial flow bed 70
35 Dominant fluidndashsolid mass and heat transfer 70
36 Negligible mass and thermal dispersion 72
37 Conclusions 73
Nomenclature 74
Greek letters 75
References 75
4 Fluidized-bed catalytic reactors 80John R Grace
41 Introduction 80411 Advantages and disadvantages of fluidized-bed
reactors 80412 Preconditions for successful fluidized-bed
processes 81
v
413 Industrial catalytic processes employingfluidized-bed reactors 82
42 Key hydrodynamic features of gas-fluidized beds 83421 Minimum fluidization velocity 83422 Powder group and minimum bubbling
velocity 84423 Flow regimes and transitions 84424 Bubbling fluidized beds 84425 Turbulent fluidization flow regime 85426 Fast fluidization and dense suspension
upflow 85
43 Key properties affecting reactor performance 86431 Particle mixing 86432 Gas mixing 87433 Heat transfer and temperature uniformity 87434 Mass transfer 88435 Entrainment 88436 Attrition 89437 Wear 89438 Agglomeration and fouling 89439 Electrostatics and other interparticle forces 89
44 Reactor modeling 89441 Basis for reactor modeling 89442 Modeling of bubbling and slugging flow
regimes 90443 Modeling of reactors operating in high-velocity
flow regimes 91
45 Scale-up pilot testing and practical issues 91451 Scale-up issues 91452 Laboratory and pilot testing 91453 Instrumentation 92454 Other practical issues 92
46 Concluding remarks 92
Nomenclature 93
Greek letters 93
References 93
Part 3 Three-phase catalytic reactors
5 Three-phase fixed-bed reactors 97Ion Iliuta and Faiumlccedilal Larachi
51 Introduction 97
52 Hydrodynamic aspects of three-phase fixed-bedreactors 98521 General aspects Flow regimes liquid holdup
two-phase pressure drop and wetting efficiency 98522 Standard two-fluid models for two-phase
downflow and upflow in three-phase fixed-bedreactors 100
523 Nonequilibrium thermomechanical models fortwo-phase flow in three-phase fixed-bedreactors 102
53 Mass and heat transfer in three-phase fixed-bedreactors 104531 Gasndashliquid mass transfer 105532 Liquidndashsolid mass transfer 105533 Heat transfer 106
54 Scale-up and scale-down of trickle-bed reactors 108541 Scaling up of trickle-bed reactors 108542 Scaling down of trickle-bed reactors 109543 Salient conclusions 110
55 Trickle-bed reactorbioreactor modeling 110551 Catalytic hydrodesulfurization and bed
clogging in hydrotreating trickle-bedreactors 110
552 Biomass accumulation and clogging intrickle-bed bioreactors for phenolbiodegradation 115
553 Integrated aqueous-phase glycerol reformingand dimethyl ether synthesis into anallothermal dual-bed reactor 121
Nomenclature 126
Greek letters 127
Subscripts 128
Superscripts 128
Abbreviations 128
References 128
6 Three-phase slurry reactors 132Vivek V Buwa Shantanu Roy and Vivek V Ranade
61 Introduction 132
62 Reactor design scale-up methodology and reactorselection 134621 Practical aspects of reactor design and
scale-up 134622 Transport effects at particle level 139
63 Reactor models for design and scale-up 143631 Lower order models 143632 Tank-in-seriesmixing cell models 144
64 Estimation of transport and hydrodynamicparameters 145641 Estimation of transport parameters 145642 Estimation of hydrodynamic parameters 146
65 Advanced computational fluid dynamics(CFD)-based models 147
66 Summary and closing remarks 149
Acknowledgments 152
Nomenclature 152
Greek letters 153
Subscripts 153
References 153
vi Contents
7 Bioreactors 156Pedro Fernandes and Joaquim MS Cabral
71 Introduction 156
72 Basic concepts configurations and modes ofoperation 156721 Basic concepts 156722 Reactor configurations and modes of
operation 157
73 Mass balances and reactor equations 159731 Operation with enzymes 159732 Operation with living cells 160
74 Immobilized enzymes and cells 164741 Mass transfer effects 164742 Deactivation effects 166
75 Aeration 166
76 Mixing 166
77 Heat transfer 167
78 Scale-up 167
79 Bioreactors for animal cell cultures 167
710 Monitoring and control of bioreactors 168
Nomenclature 168
Greek letters 169
Subscripts 169
References 169
Part 4 Structured reactors
8 Monolith reactors 173Joatildeo P Lopes and Aliacuterio E Rodrigues
81 Introduction 173811 Design concepts 174812 Applications 178
82 Design of wall-coated monolith channels 179821 Flow in monolithic channels 179822 Mass transfer and wall reaction 182823 Reaction and diffusion in the catalytic
washcoat 190824 Nonisothermal operation 194
83 Mapping and evaluation of operatingregimes 197831 Diversity in the operation of a monolith
reactor 197832 Definition of operating regimes 199833 Operating diagrams for linear kinetics 201834 Influence of nonlinear reaction kinetics 202835 Performance evaluation 203
84 Three-phase processes 204
85 Conclusions 207
Nomenclature 207
Greek letters 208
Superscripts 208
Subscripts 208
References 209
9 Microreactors for catalytic reactions 213Evgeny Rebrov and Sourav Chatterjee
91 Introduction 213
92 Single-phase catalytic microreactors 213921 Residence time distribution 213922 Effect of flow maldistribution 214923 Mass transfer 215924 Heat transfer 215
93 Multiphase microreactors 216931 Microstructured packed beds 216932 Microchannel reactors 218
94 Conclusions and outlook 225
Nomenclature 226
Greek letters 227
Subscripts 227
References 228
Part 5 Essential tools of reactor modeling and design
10 Experimental methods for the determination ofparameters 233Rebecca R Fushimi John T Gleaves and GregoryS Yablonsky
101 Introduction 233
102 Consideration of kinetic objectives 234
103 Criteria for collecting kinetic data 234
104 Experimental methods 2341041 Steady-state flow experiments 2351042 Transient flow experiments 2371043 Surface science experiments 238
105 Microkinetic approach to kinetic analysis 241
106 TAP approach to kinetic analysis 2411061 TAP experiment design 2421062 TAP experimental results 244
107 Conclusions 248
References 249
11 Numerical solution techniques 253Ahmet Kerim Avci and Seda Keskin
111 Techniques for the numerical solution of ordinarydifferential equations 2531111 Explicit techniques 2531112 Implicit techniques 254
112 Techniques for the numerical solution of partialdifferential equations 255
Contents vii
113 Computational fluid dynamics techniques 2561131 Methodology of computational fluid
dynamics 2561132 Finite element method 2561133 Finite volume method 258
114 Case studies 2591141 Indirect partial oxidation of methane in a
catalytic tubular reactor 2591142 Hydrocarbon steam reforming in
spatially segregated microchannelreactors 261
115 Summary 265
Nomenclature 266
Greek letters 267
Subscriptssuperscripts 267
References 267
Part 6 Industrial applications of multiphase reactors
12 Reactor approaches for FischerndashTropsch synthesis 271Gary Jacobs and Burtron H Davis
121 Introduction 271
122 Reactors to 1950 272
123 1950ndash1985 period 274
124 1985 to present 2761241 Fixed-bed reactors 2761242 Fluidized-bed reactors 2801243 Slurry bubble column reactors 2811244 Structured packings 2861245 Operation at supercritical conditions(SCF) 288
125 The future 288
References 291
13 Hydrotreating of oil fractions 295Jorge Ancheyta Anton Alvarez-Majmutov andCarolina Leyva
131 Introduction 295
132 The HDT process 2961321 Overview 2961322 Role in petroleum refining 2971323 World outlook and the situation ofMexico 298
133 Fundamentals of HDT 3001331 Chemistry 3001332 Reaction kinetics 3031333 Thermodynamics 3051334 Catalysts 306
134 Process aspects of HDT 3071341 Process variables 307
1342 Reactors for hydroprocessing 3101343 Catalyst activation in commercial
hydrotreaters 316
135 Reactor modeling and simulation 3171351 Process description 3171352 Summary of experiments 3171353 Modeling approach 3191354 Simulation of the bench-scale unit 3201355 Scale-up of bench-unit data 3231356 Simulation of the commercial
unit 324
Nomenclature 326
Greek letters 327
Subscripts 327
Non-SI units 327
References 327
14 Catalytic reactors for fuel processing 330Gunther Kolb
141 IntroductionmdashThe basic reactions of fuelprocessing 330
142 Theoretical aspects advantages and drawbacks offixed beds versus monoliths microreactors andmembrane reactors 331
143 Reactor design and fabrication 3321431 Fixed-bed reactors 3321432 Monolithic reactors 3321433 Microreactors 3321434 Membrane reactors 333
144 Reformers 3331441 Fixed-bed reformers 3361442 Monolithic reformers 3371443 Plate heat exchangers and microstructured
reformers 3421444 Membrane reformers 344
145 Water-gas shift reactors 3481451 Monolithic reactors 3481452 Plate heat exchangers and microstructured
water-gas shift reactors 3481453 Water-gas shift in membrane reactors 350
146 Carbon monoxide fine cleanup Preferential oxidationand selective methanation 3501461 Fixed-bed reactors 3521462 Monolithic reactors 3521463 Plate heat exchangers and microstructured
reactors 353
147 Examples of complete fuel processors 3551471 Monolithic fuel processors 3551472 Plate heat exchanger fuel processors on the
meso- and microscale 357
viii Contents
Nomenclature 359
References 359
15 Modeling of the catalytic deoxygenation of fatty acids in apacked bed reactor 365Teuvo Kilpiouml Paumlivi Maumlki-Arvela Tapio Salmi andDmitry Yu Murzin
151 Introduction 365
152 Experimental data for stearic aciddeoxygenation 366
153 Assumptions 366
154 Model equations 367
155 Evaluation of the adsorption parameters 368
156 Particle diffusion study 369
157 Parameter sensitivity studies 369
158 Parameter identification studies 370
159 Studies concerning the deviation from ideal plug flowconditions 371
1510 Parameter estimation results 372
1511 Scale-up considerations 372
1512 Conclusions 375
Acknowledgments 375
Nomenclature 375
Greek letters 375
References 376
Index 377
Contents ix
List of contributors
Anton Alvarez-MajmutovInstituto Mexicano del Petroacuteleo Management of Products for theTransformation of Crude Oil Mexico City Mexico
Jorge AncheytaInstituto Mexicano del Petroacuteleo Management of Products for theTransformation of Crude Oil Mexico City Mexico
Ahmet Kerim AvciDepartment of Chemical Engineering Boğaziccedili University Istanbul Turkey
Vivek V BuwaDepartment of Chemical EngineeringIndian Institute of Technology-Delhi New Delhi India
Joaquim MS CabralDepartment of Bioengineering and IBB-Institute for Bioengineeringand Biosciences Instituto Superior Teacutecnico Universidade de LisboaLisboa Portugal
Sourav ChatterjeeSchool of Chemistry and Chemical Engineering Queenrsquos University BelfastBelfast UK
Burtron H DavisCenter for Applied Energy Research University of KentuckyLexington KY USA
Pedro FernandesDepartment of Bioengineering and IBB-Institutefor Bioengineering and Biosciences Instituto Superior TeacutecnicoUniversidade de Lisboa Faculdade de EngenhariaUniversidade Lusoacutefona de Humanidadese Tecnologias Lisboa Portugal
Rebecca R FushimiMaterials Science amp Engineering Department Idaho National LaboratoryIdaho Falls ID USA
John T GleavesDepartment of Energy Environmental and Chemical EngineeringWashington University St Louis MO USA
John R GraceDepartment of Chemical and Biological EngineeringThe University of British Columbia VancouverBritish Columbia Canada
Ion IliutaChemical Engineering Department Laval University Queacutebec CityQueacutebec Canada
Gary JacobsCenter for Applied Energy Research University of KentuckyLexington KY USA
Seda KeskinDepartment of Chemical and Biological Engineering Koc UniversityIstanbul Turkey
Teuvo KilpioumlProcess Chemistry Centre Aringbo Akademi University TurkuAringbo Finland
Gunther KolbFraunhofer ICT-IMM Decentralized and Mobile Energy TechnologyDepartment Mainz Germany
Faiumlccedilal LarachiChemical Engineering Department Laval University Queacutebec CityQueacutebec Canada
Carolina LeyvaCentro de Investigacioacuten en Ciencia Aplicada y Tecnologiacutea AvanzadaUnidad Legaria Instituto Politeacutecnico Nacional Mexico City Mexico
Joatildeo P LopesDepartment of Chemical Engineering and BiotechnologyUniversity of Cambridge Cambridge UK
Paumlivi Maumlki-ArvelaProcess Chemistry Centre Aringbo Akademi University TurkuAringbo Finland
Dmitry Yu MurzinProcess Chemistry Centre Aringbo Akademi University TurkuAringbo Finland
Zeynep Ilsen OumlnsanDepartment of Chemical Engineering Boğaziccedili University Istanbul Turkey
Vivek V RanadeChemical Engineering amp Process Development Division National ChemicalLaboratory Pune India
Evgeny RebrovSchool of Engineering University of Warwick Coventry UK
x
Aliacuterio E RodriguesLaboratory of Separation and Reaction EngineeringAssociate Laboratory LSRELCM Department of Chemical EngineeringFaculty of Engineering University of Porto Porto Portugal
Shantanu RoyDepartment of Chemical Engineering Indian Institute of Technology-DelhiNew Delhi India
Tapio SalmiProcess Chemistry Centre Aringbo Akademi UniversityTurkuAringbo Finland
Gregory S YablonskyParks College of Engineering Aviation and TechnologySaint Louis University St Louis MO USA
List of contributors xi
Preface
The single irreplaceable component at the core of a chemicalprocess is the chemical reactor where feed materials are con-verted into desirable products Although the essential variablesby which chemical processes can be controlled are reaction tem-perature pressure feed composition and residence time in thereactor two technological developments of major consequencestarting with 1960s have made possible cost-effective operationunder less severe conditions these are the extensive use of effi-cient catalysts and the introduction of improved or innovativereactor configurations The impact of heterogeneous catalysisis significant in this respect since petroleum refining manufac-turing of chemicals and environmental clean-up which are thethree major areas of the world economy today all requirethe effective use of solid catalysts The challenges involved inthe design of novel solid catalysts and modification of manyexisting ones for higher selectivity and stability have alsoprompted the development of ldquoengineeredrdquo catalysts befittingnovel reactor configurations requiring the use of new supportssuch as monolithic or foam substrates as well as the establish-ment of new techniques for coating surfaces with diverse catalystcomponents in order to ensure longevity particularly in cyclicprocessesIn industrial practice the composition and properties of the
complex feed mixtures that are processed for producing a rangeof valuable chemicals generally necessitate the use of heteroge-neous catalytic reactors Numerous chemical and physical rateprocesses take place in a heterogeneous reactor at differentlength and time scales and frequently in different phasesThe prerequisite for the successful design and operation of cat-alytic reactors is a thorough microkinetic analysis starting fromintrinsic kinetic models of the steady-state chemical activity andleading to global rate expressions obtained by overlaying theeffects of physical rate phenomena occurring at the particlescale Kinetic models of increasing complexity may be requireddepending on the variety of components and number of reac-tions involved The second critical stage in reactor modelingand design is a macrokinetic analysis including the detaileddescription of physical transport phenomena at the reactor scaleand utilizing the global rate expressions of the microkineticanalysis The final catalytic reactor model which integrates theseessential stages can successfully predict the performance anddynamics of plant-scale industrial reactors as well as simulatingtheir start-up shutdown and cyclic operation Taking intoaccount engineered catalysts and new reactor configurations
the modeling and scaling up of reactions conducted at thebench-scale to pilot plant and industrial-scale reactor levels haveto be modified in order to include simultaneous multiscaleapproaches along with the conventional sequential modesMultiphase Catalytic Reactors Theory Design Manufactur-
ing and Applications is a comprehensive up-to-date compila-tion on multiphase catalytic reactors which will serve as anexcellent reference book for graduate students researchersand specialists both in academia and in industry The contentof the book is planned to cover topics starting from the firstprinciples involved in macrokinetic analysis of two- andthree-phase catalytic reactors to their particular industrial appli-cations The main objective is to provide definitive accounts onacademic aspects of multiphase catalytic reactor modeling anddesign along with detailed descriptions of some of the mostrecent industrial applications employing multiphase catalyticreactors in such a way as to balance the academic and industrialcomponents as much as possible Accordingly seven chaptersare included in Parts II III and IV to review the relevantmathematical models and model equations utilized in the fun-damental analysis and macroscopic design of specific reactortypes together with some useful approximations for theirdesign and scale-up from a practical standpoint while the fourchapters in Part VI describe specific industrial applications andcontain pointers that tie in with the modeling and designapproaches presented for the particular multiphase catalyticreactor types discussed in Parts II III and IV Furthermorethe chapters included in Parts I and V of the book containdetailed reviews of the basic principles and essential tools ofcatalytic reaction engineering that are crucial for the successfuldesign and operation of catalytic reactors All chapters ofthe book are contributed by experts distinguished in theirrespective fieldsThe total of 15 chapters included in Multiphase Catalytic
Reactors Theory Design Manufacturing and Applications areorganized in six parts Part I is an overview of the principlesof catalytic reaction engineering embracing Chapter 1 whichis a survey of multiphase catalytic reactor types and their indus-trial significance as well as Chapter 2 on the microkinetic anal-ysis of heterogeneous catalytic systems which surveys theformulation of intrinsic rate equations describing chemical rateprocesses and the construction of global rate expressions thatinclude the effects of physical mass and heat transport phenom-ena occurring at the particle scale Chapters 3 through 9 in
xii
Parts II III and IV discuss individual two- and three-phase cat-alytic reactor types and provide design equations and empiricalrelationships that characterize different multiphase reactorsmathematical modeling is an integral part of these chaptersIn Part II two-phase catalytic reactors are grouped as fixed-bed gasndashsolid catalytic reactors (Chapter 3) and fluidized-bedcatalytic reactors (Chapter 4) Part III deals exclusively withthree-phase catalytic reactors and includes Chapter 5 onthree-phase fixed-bed reactors as well as Chapter 6 on three-phase slurry reactors both of which find significant industrialapplications moreover multiphase bioreactors are also includedin Part III as Chapter 7 Part IV is devoted to the discussion ofthe more recent state-of-the-art structured reactors the theoret-ical aspects and examples of structured reactors enabling processintensification in multiphase operation are treated in Chapter 8on monolith reactors and in Chapter 9 on microreactors of dif-ferent configurations including microstructured packed bedsand microchannel reactors Part V of the book is specificallydesigned for surveying the essential tools of catalytic reactormodeling and design and comprises two chapters Chapter 10discusses the recent developments and experimental techniquesinvolved in lab-scale testing of catalytic reactions includingsteady-state and transient flow experiments as well as the micro-kinetic and TAP approaches to kinetic analysis whileChapter 11 surveys the numerical solution techniques that arefrequently used in catalytic reactor analysis and demonstrateswith some case studies The capstone section of the bookPart VI contains four chapters devoted to specific industrialapplications of multiphase catalytic reactors and includes the
recent developments and practices in FischerndashTropsch technol-ogies (Chapter 12) a thorough discussion of reactor modelingsimulation and scale-up approaches involved in the hydrotreat-ing of oil fractions (Chapter 13) a detailed assessment of theperformances of various reactor configurations used for fuelprocessing (Chapter 14) and a comprehensive discussion ofcatalytic deoxygenation of fatty acids in a packed-bed reactoras case study in production of biofuels (Chapter 15)
It is indeed a pleasure to thank all of the contributors whohave made this challenging task achievable The editors are sin-cerely grateful for their willingness to devote their valuable timeand effort to this project for their readiness in sharing theirvision knowledge years of experience and know-how and alsofor their patience in tolerating various expected or unexpectedextensions arising from the busy schedules of different contribu-tors It has definitely been a privilege to work with the authorscoauthors and reviewers involved in this book The editorswould also like to extend their thanks to Wiley-Blackwell fortheir commitment to this project and to Michael Leventhalfor his organization andmanagement of the publication process
On a more personal note the editors would like to take thisopportunity to express their sincere gratitude to the late Profes-sor David L Trimm who has inspired their research in catalysisand catalytic reaction engineering through many years as super-visor mentor colleague and friend
Zeynep Ilsen OumlnsanAhmet Kerim Avci
Istanbul October 2015
Preface xiii
Multiphase CatalyticReactorsTheory Design Manufacturingand Applications
Edited by
Zeynep Ilsen OumlnsanDepartment of Chemical Engineering
Boğaziccedili UniversityIstanbul Turkey
Ahmet Kerim AvciDepartment of Chemical Engineering
Boğaziccedili UniversityIstanbul Turkey
Copyright copy 2016 by John Wiley amp Sons Inc All rights reserved
Published by John Wiley amp Sons Inc Hoboken New Jersey
Published simultaneously in Canada
No part of this publication may be reproduced stored in a retrieval system or transmitted in any form or by any means electronicmechanical photocopying recording scanning or otherwise except as permitted under Section 107 or 108 of the 1976 United StatesCopyright Act without either the prior written permission of the Publisher or authorization through payment of the appropriateper-copy fee to the Copyright Clearance Center Inc 222 Rosewood Drive Danvers MA 01923 (978) 750-8400 fax (978) 750-4470 oron the web at wwwcopyrightcom Requests to the Publisher for permission should be addressed to the Permissions DepartmentJohn Wiley amp Sons Inc 111 River Street Hoboken NJ 07030 (201) 748-6011 fax (201) 748-6008 or online athttpwwwwileycomgopermissions
Limit of LiabilityDisclaimer ofWarranty While the publisher and author have used their best efforts in preparing this book they makeno representations or warranties with respect to the accuracy or completeness of the contents of this book and specifically disclaimany implied warranties of merchantability or fitness for a particular purpose No warranty may be created or extended by salesrepresentatives or written sales materials The advice and strategies contained herein may not be suitable for your situation You shouldconsult with a professional where appropriate Neither the publisher nor author shall be liable for any loss of profit or any othercommercial damages including but not limited to special incidental consequential or other damages
For general information on our other products and services or for technical support please contact our Customer Care Departmentwithin the United States at (800) 762-2974 outside the United States at (317) 572-3993 or fax (317) 572-4002
Wiley also publishes its books in a variety of electronic formats Some content that appears in print may not be available in electronicformats For more information about Wiley products visit our web site at wwwwileycom
Library of Congress Cataloging-in-Publication Data
Names Oumlnsan Zeynep Ilsen editor | Avci Ahmet Kerim editorTitle Multiphase catalytic reactors theory design manufacturing andapplications edited by Zeynep Ilsen Oumlnsan Ahmet Kerim Avci
Description Hoboken New Jersey John Wiley amp Sons Inc [2016] | Includesbibliographical references and index
Identifiers LCCN 2016009674 | ISBN 9781118115763 (cloth) | ISBN 9781119248477(epub) | ISBN 9781119248460 (epdf)
Subjects LCSH Phase-transfer catalysis | Chemical reactorsClassification LCC TP159C3 M85 2016 | DDC 6602832ndashdc23LC record available at httpslccnlocgov2016009674
Set in 95 12pt Minion by SPi Global Pondicherry India
Printed in the United States of America
10 9 8 7 6 5 4 3 2 1
Contents
List of Contributors x
Preface xii
Part 1 Principles of catalytic reaction engineering
1 Catalytic reactor types and their industrial significance 3Zeynep Ilsen Oumlnsan and Ahmet Kerim Avci
11 Introduction 3
12 Reactors with fixed bed of catalysts 3121 Packed-bed reactors 3122 Monolith reactors 8123 Radial flow reactors 9124 Trickle-bed reactors 9125 Short contact time reactors 10
13 Reactors with moving bed of catalysts 11131 Fluidized-bed reactors 11132 Slurry reactors 13133 Moving-bed reactors 14
14 Reactors without a catalyst bed 14
15 Summary 16
References 16
2 Microkinetic analysis of heterogeneous catalytic systems 17Zeynep Ilsen Oumlnsan
21 Heterogeneous catalytic systems 17211 Chemical and physical characteristics of solid
catalysts 18212 Activity selectivity and stability 21
22 Intrinsic kinetics of heterogeneous reactions 22221 Kinetic models and mechanisms 23222 Analysis and correlation of rate data 27
23 External (interphase) transport processes 32231 External mass transfer Isothermal conditions 33232 External temperature effects 35233 Nonisothermal conditions Multiple steady
states 36234 External effectiveness factors 38
24 Internal (intraparticle) transport processes 39241 Intraparticle mass and heat transfer 39242 Mass transfer with chemical reaction Isothermal
effectiveness 41
243 Heat and mass transfer with chemical reaction 45244 Impact of internal transport limitations
on kinetic studies 47
25 Combination of external and internal transporteffects 48251 Isothermal overall effectiveness 48252 Nonisothermal conditions 49
26 Summary 50
Nomenclature 50
Greek letters 51
References 51
Part 2 Two-phase catalytic reactors
3 Fixed-bed gasndashsolid catalytic reactors 55Joatildeo P Lopes and Aliacuterio E Rodrigues
31 Introduction and outline 55
32 Modeling of fixed-bed reactors 57321 Description of transportndashreaction
phenomena 57322 Mathematical model 59323 Model reduction and selection 61
33 Averaging over the catalyst particle 61331 Chemical regime 64332 Diffusional regime 64
34 Dominant fluidndashsolid mass transfer 66341 Isothermal axial flow bed 67342 Non-isothermal non-adiabatic axial flow bed 70
35 Dominant fluidndashsolid mass and heat transfer 70
36 Negligible mass and thermal dispersion 72
37 Conclusions 73
Nomenclature 74
Greek letters 75
References 75
4 Fluidized-bed catalytic reactors 80John R Grace
41 Introduction 80411 Advantages and disadvantages of fluidized-bed
reactors 80412 Preconditions for successful fluidized-bed
processes 81
v
413 Industrial catalytic processes employingfluidized-bed reactors 82
42 Key hydrodynamic features of gas-fluidized beds 83421 Minimum fluidization velocity 83422 Powder group and minimum bubbling
velocity 84423 Flow regimes and transitions 84424 Bubbling fluidized beds 84425 Turbulent fluidization flow regime 85426 Fast fluidization and dense suspension
upflow 85
43 Key properties affecting reactor performance 86431 Particle mixing 86432 Gas mixing 87433 Heat transfer and temperature uniformity 87434 Mass transfer 88435 Entrainment 88436 Attrition 89437 Wear 89438 Agglomeration and fouling 89439 Electrostatics and other interparticle forces 89
44 Reactor modeling 89441 Basis for reactor modeling 89442 Modeling of bubbling and slugging flow
regimes 90443 Modeling of reactors operating in high-velocity
flow regimes 91
45 Scale-up pilot testing and practical issues 91451 Scale-up issues 91452 Laboratory and pilot testing 91453 Instrumentation 92454 Other practical issues 92
46 Concluding remarks 92
Nomenclature 93
Greek letters 93
References 93
Part 3 Three-phase catalytic reactors
5 Three-phase fixed-bed reactors 97Ion Iliuta and Faiumlccedilal Larachi
51 Introduction 97
52 Hydrodynamic aspects of three-phase fixed-bedreactors 98521 General aspects Flow regimes liquid holdup
two-phase pressure drop and wetting efficiency 98522 Standard two-fluid models for two-phase
downflow and upflow in three-phase fixed-bedreactors 100
523 Nonequilibrium thermomechanical models fortwo-phase flow in three-phase fixed-bedreactors 102
53 Mass and heat transfer in three-phase fixed-bedreactors 104531 Gasndashliquid mass transfer 105532 Liquidndashsolid mass transfer 105533 Heat transfer 106
54 Scale-up and scale-down of trickle-bed reactors 108541 Scaling up of trickle-bed reactors 108542 Scaling down of trickle-bed reactors 109543 Salient conclusions 110
55 Trickle-bed reactorbioreactor modeling 110551 Catalytic hydrodesulfurization and bed
clogging in hydrotreating trickle-bedreactors 110
552 Biomass accumulation and clogging intrickle-bed bioreactors for phenolbiodegradation 115
553 Integrated aqueous-phase glycerol reformingand dimethyl ether synthesis into anallothermal dual-bed reactor 121
Nomenclature 126
Greek letters 127
Subscripts 128
Superscripts 128
Abbreviations 128
References 128
6 Three-phase slurry reactors 132Vivek V Buwa Shantanu Roy and Vivek V Ranade
61 Introduction 132
62 Reactor design scale-up methodology and reactorselection 134621 Practical aspects of reactor design and
scale-up 134622 Transport effects at particle level 139
63 Reactor models for design and scale-up 143631 Lower order models 143632 Tank-in-seriesmixing cell models 144
64 Estimation of transport and hydrodynamicparameters 145641 Estimation of transport parameters 145642 Estimation of hydrodynamic parameters 146
65 Advanced computational fluid dynamics(CFD)-based models 147
66 Summary and closing remarks 149
Acknowledgments 152
Nomenclature 152
Greek letters 153
Subscripts 153
References 153
vi Contents
7 Bioreactors 156Pedro Fernandes and Joaquim MS Cabral
71 Introduction 156
72 Basic concepts configurations and modes ofoperation 156721 Basic concepts 156722 Reactor configurations and modes of
operation 157
73 Mass balances and reactor equations 159731 Operation with enzymes 159732 Operation with living cells 160
74 Immobilized enzymes and cells 164741 Mass transfer effects 164742 Deactivation effects 166
75 Aeration 166
76 Mixing 166
77 Heat transfer 167
78 Scale-up 167
79 Bioreactors for animal cell cultures 167
710 Monitoring and control of bioreactors 168
Nomenclature 168
Greek letters 169
Subscripts 169
References 169
Part 4 Structured reactors
8 Monolith reactors 173Joatildeo P Lopes and Aliacuterio E Rodrigues
81 Introduction 173811 Design concepts 174812 Applications 178
82 Design of wall-coated monolith channels 179821 Flow in monolithic channels 179822 Mass transfer and wall reaction 182823 Reaction and diffusion in the catalytic
washcoat 190824 Nonisothermal operation 194
83 Mapping and evaluation of operatingregimes 197831 Diversity in the operation of a monolith
reactor 197832 Definition of operating regimes 199833 Operating diagrams for linear kinetics 201834 Influence of nonlinear reaction kinetics 202835 Performance evaluation 203
84 Three-phase processes 204
85 Conclusions 207
Nomenclature 207
Greek letters 208
Superscripts 208
Subscripts 208
References 209
9 Microreactors for catalytic reactions 213Evgeny Rebrov and Sourav Chatterjee
91 Introduction 213
92 Single-phase catalytic microreactors 213921 Residence time distribution 213922 Effect of flow maldistribution 214923 Mass transfer 215924 Heat transfer 215
93 Multiphase microreactors 216931 Microstructured packed beds 216932 Microchannel reactors 218
94 Conclusions and outlook 225
Nomenclature 226
Greek letters 227
Subscripts 227
References 228
Part 5 Essential tools of reactor modeling and design
10 Experimental methods for the determination ofparameters 233Rebecca R Fushimi John T Gleaves and GregoryS Yablonsky
101 Introduction 233
102 Consideration of kinetic objectives 234
103 Criteria for collecting kinetic data 234
104 Experimental methods 2341041 Steady-state flow experiments 2351042 Transient flow experiments 2371043 Surface science experiments 238
105 Microkinetic approach to kinetic analysis 241
106 TAP approach to kinetic analysis 2411061 TAP experiment design 2421062 TAP experimental results 244
107 Conclusions 248
References 249
11 Numerical solution techniques 253Ahmet Kerim Avci and Seda Keskin
111 Techniques for the numerical solution of ordinarydifferential equations 2531111 Explicit techniques 2531112 Implicit techniques 254
112 Techniques for the numerical solution of partialdifferential equations 255
Contents vii
113 Computational fluid dynamics techniques 2561131 Methodology of computational fluid
dynamics 2561132 Finite element method 2561133 Finite volume method 258
114 Case studies 2591141 Indirect partial oxidation of methane in a
catalytic tubular reactor 2591142 Hydrocarbon steam reforming in
spatially segregated microchannelreactors 261
115 Summary 265
Nomenclature 266
Greek letters 267
Subscriptssuperscripts 267
References 267
Part 6 Industrial applications of multiphase reactors
12 Reactor approaches for FischerndashTropsch synthesis 271Gary Jacobs and Burtron H Davis
121 Introduction 271
122 Reactors to 1950 272
123 1950ndash1985 period 274
124 1985 to present 2761241 Fixed-bed reactors 2761242 Fluidized-bed reactors 2801243 Slurry bubble column reactors 2811244 Structured packings 2861245 Operation at supercritical conditions(SCF) 288
125 The future 288
References 291
13 Hydrotreating of oil fractions 295Jorge Ancheyta Anton Alvarez-Majmutov andCarolina Leyva
131 Introduction 295
132 The HDT process 2961321 Overview 2961322 Role in petroleum refining 2971323 World outlook and the situation ofMexico 298
133 Fundamentals of HDT 3001331 Chemistry 3001332 Reaction kinetics 3031333 Thermodynamics 3051334 Catalysts 306
134 Process aspects of HDT 3071341 Process variables 307
1342 Reactors for hydroprocessing 3101343 Catalyst activation in commercial
hydrotreaters 316
135 Reactor modeling and simulation 3171351 Process description 3171352 Summary of experiments 3171353 Modeling approach 3191354 Simulation of the bench-scale unit 3201355 Scale-up of bench-unit data 3231356 Simulation of the commercial
unit 324
Nomenclature 326
Greek letters 327
Subscripts 327
Non-SI units 327
References 327
14 Catalytic reactors for fuel processing 330Gunther Kolb
141 IntroductionmdashThe basic reactions of fuelprocessing 330
142 Theoretical aspects advantages and drawbacks offixed beds versus monoliths microreactors andmembrane reactors 331
143 Reactor design and fabrication 3321431 Fixed-bed reactors 3321432 Monolithic reactors 3321433 Microreactors 3321434 Membrane reactors 333
144 Reformers 3331441 Fixed-bed reformers 3361442 Monolithic reformers 3371443 Plate heat exchangers and microstructured
reformers 3421444 Membrane reformers 344
145 Water-gas shift reactors 3481451 Monolithic reactors 3481452 Plate heat exchangers and microstructured
water-gas shift reactors 3481453 Water-gas shift in membrane reactors 350
146 Carbon monoxide fine cleanup Preferential oxidationand selective methanation 3501461 Fixed-bed reactors 3521462 Monolithic reactors 3521463 Plate heat exchangers and microstructured
reactors 353
147 Examples of complete fuel processors 3551471 Monolithic fuel processors 3551472 Plate heat exchanger fuel processors on the
meso- and microscale 357
viii Contents
Nomenclature 359
References 359
15 Modeling of the catalytic deoxygenation of fatty acids in apacked bed reactor 365Teuvo Kilpiouml Paumlivi Maumlki-Arvela Tapio Salmi andDmitry Yu Murzin
151 Introduction 365
152 Experimental data for stearic aciddeoxygenation 366
153 Assumptions 366
154 Model equations 367
155 Evaluation of the adsorption parameters 368
156 Particle diffusion study 369
157 Parameter sensitivity studies 369
158 Parameter identification studies 370
159 Studies concerning the deviation from ideal plug flowconditions 371
1510 Parameter estimation results 372
1511 Scale-up considerations 372
1512 Conclusions 375
Acknowledgments 375
Nomenclature 375
Greek letters 375
References 376
Index 377
Contents ix
List of contributors
Anton Alvarez-MajmutovInstituto Mexicano del Petroacuteleo Management of Products for theTransformation of Crude Oil Mexico City Mexico
Jorge AncheytaInstituto Mexicano del Petroacuteleo Management of Products for theTransformation of Crude Oil Mexico City Mexico
Ahmet Kerim AvciDepartment of Chemical Engineering Boğaziccedili University Istanbul Turkey
Vivek V BuwaDepartment of Chemical EngineeringIndian Institute of Technology-Delhi New Delhi India
Joaquim MS CabralDepartment of Bioengineering and IBB-Institute for Bioengineeringand Biosciences Instituto Superior Teacutecnico Universidade de LisboaLisboa Portugal
Sourav ChatterjeeSchool of Chemistry and Chemical Engineering Queenrsquos University BelfastBelfast UK
Burtron H DavisCenter for Applied Energy Research University of KentuckyLexington KY USA
Pedro FernandesDepartment of Bioengineering and IBB-Institutefor Bioengineering and Biosciences Instituto Superior TeacutecnicoUniversidade de Lisboa Faculdade de EngenhariaUniversidade Lusoacutefona de Humanidadese Tecnologias Lisboa Portugal
Rebecca R FushimiMaterials Science amp Engineering Department Idaho National LaboratoryIdaho Falls ID USA
John T GleavesDepartment of Energy Environmental and Chemical EngineeringWashington University St Louis MO USA
John R GraceDepartment of Chemical and Biological EngineeringThe University of British Columbia VancouverBritish Columbia Canada
Ion IliutaChemical Engineering Department Laval University Queacutebec CityQueacutebec Canada
Gary JacobsCenter for Applied Energy Research University of KentuckyLexington KY USA
Seda KeskinDepartment of Chemical and Biological Engineering Koc UniversityIstanbul Turkey
Teuvo KilpioumlProcess Chemistry Centre Aringbo Akademi University TurkuAringbo Finland
Gunther KolbFraunhofer ICT-IMM Decentralized and Mobile Energy TechnologyDepartment Mainz Germany
Faiumlccedilal LarachiChemical Engineering Department Laval University Queacutebec CityQueacutebec Canada
Carolina LeyvaCentro de Investigacioacuten en Ciencia Aplicada y Tecnologiacutea AvanzadaUnidad Legaria Instituto Politeacutecnico Nacional Mexico City Mexico
Joatildeo P LopesDepartment of Chemical Engineering and BiotechnologyUniversity of Cambridge Cambridge UK
Paumlivi Maumlki-ArvelaProcess Chemistry Centre Aringbo Akademi University TurkuAringbo Finland
Dmitry Yu MurzinProcess Chemistry Centre Aringbo Akademi University TurkuAringbo Finland
Zeynep Ilsen OumlnsanDepartment of Chemical Engineering Boğaziccedili University Istanbul Turkey
Vivek V RanadeChemical Engineering amp Process Development Division National ChemicalLaboratory Pune India
Evgeny RebrovSchool of Engineering University of Warwick Coventry UK
x
Aliacuterio E RodriguesLaboratory of Separation and Reaction EngineeringAssociate Laboratory LSRELCM Department of Chemical EngineeringFaculty of Engineering University of Porto Porto Portugal
Shantanu RoyDepartment of Chemical Engineering Indian Institute of Technology-DelhiNew Delhi India
Tapio SalmiProcess Chemistry Centre Aringbo Akademi UniversityTurkuAringbo Finland
Gregory S YablonskyParks College of Engineering Aviation and TechnologySaint Louis University St Louis MO USA
List of contributors xi
Preface
The single irreplaceable component at the core of a chemicalprocess is the chemical reactor where feed materials are con-verted into desirable products Although the essential variablesby which chemical processes can be controlled are reaction tem-perature pressure feed composition and residence time in thereactor two technological developments of major consequencestarting with 1960s have made possible cost-effective operationunder less severe conditions these are the extensive use of effi-cient catalysts and the introduction of improved or innovativereactor configurations The impact of heterogeneous catalysisis significant in this respect since petroleum refining manufac-turing of chemicals and environmental clean-up which are thethree major areas of the world economy today all requirethe effective use of solid catalysts The challenges involved inthe design of novel solid catalysts and modification of manyexisting ones for higher selectivity and stability have alsoprompted the development of ldquoengineeredrdquo catalysts befittingnovel reactor configurations requiring the use of new supportssuch as monolithic or foam substrates as well as the establish-ment of new techniques for coating surfaces with diverse catalystcomponents in order to ensure longevity particularly in cyclicprocessesIn industrial practice the composition and properties of the
complex feed mixtures that are processed for producing a rangeof valuable chemicals generally necessitate the use of heteroge-neous catalytic reactors Numerous chemical and physical rateprocesses take place in a heterogeneous reactor at differentlength and time scales and frequently in different phasesThe prerequisite for the successful design and operation of cat-alytic reactors is a thorough microkinetic analysis starting fromintrinsic kinetic models of the steady-state chemical activity andleading to global rate expressions obtained by overlaying theeffects of physical rate phenomena occurring at the particlescale Kinetic models of increasing complexity may be requireddepending on the variety of components and number of reac-tions involved The second critical stage in reactor modelingand design is a macrokinetic analysis including the detaileddescription of physical transport phenomena at the reactor scaleand utilizing the global rate expressions of the microkineticanalysis The final catalytic reactor model which integrates theseessential stages can successfully predict the performance anddynamics of plant-scale industrial reactors as well as simulatingtheir start-up shutdown and cyclic operation Taking intoaccount engineered catalysts and new reactor configurations
the modeling and scaling up of reactions conducted at thebench-scale to pilot plant and industrial-scale reactor levels haveto be modified in order to include simultaneous multiscaleapproaches along with the conventional sequential modesMultiphase Catalytic Reactors Theory Design Manufactur-
ing and Applications is a comprehensive up-to-date compila-tion on multiphase catalytic reactors which will serve as anexcellent reference book for graduate students researchersand specialists both in academia and in industry The contentof the book is planned to cover topics starting from the firstprinciples involved in macrokinetic analysis of two- andthree-phase catalytic reactors to their particular industrial appli-cations The main objective is to provide definitive accounts onacademic aspects of multiphase catalytic reactor modeling anddesign along with detailed descriptions of some of the mostrecent industrial applications employing multiphase catalyticreactors in such a way as to balance the academic and industrialcomponents as much as possible Accordingly seven chaptersare included in Parts II III and IV to review the relevantmathematical models and model equations utilized in the fun-damental analysis and macroscopic design of specific reactortypes together with some useful approximations for theirdesign and scale-up from a practical standpoint while the fourchapters in Part VI describe specific industrial applications andcontain pointers that tie in with the modeling and designapproaches presented for the particular multiphase catalyticreactor types discussed in Parts II III and IV Furthermorethe chapters included in Parts I and V of the book containdetailed reviews of the basic principles and essential tools ofcatalytic reaction engineering that are crucial for the successfuldesign and operation of catalytic reactors All chapters ofthe book are contributed by experts distinguished in theirrespective fieldsThe total of 15 chapters included in Multiphase Catalytic
Reactors Theory Design Manufacturing and Applications areorganized in six parts Part I is an overview of the principlesof catalytic reaction engineering embracing Chapter 1 whichis a survey of multiphase catalytic reactor types and their indus-trial significance as well as Chapter 2 on the microkinetic anal-ysis of heterogeneous catalytic systems which surveys theformulation of intrinsic rate equations describing chemical rateprocesses and the construction of global rate expressions thatinclude the effects of physical mass and heat transport phenom-ena occurring at the particle scale Chapters 3 through 9 in
xii
Parts II III and IV discuss individual two- and three-phase cat-alytic reactor types and provide design equations and empiricalrelationships that characterize different multiphase reactorsmathematical modeling is an integral part of these chaptersIn Part II two-phase catalytic reactors are grouped as fixed-bed gasndashsolid catalytic reactors (Chapter 3) and fluidized-bedcatalytic reactors (Chapter 4) Part III deals exclusively withthree-phase catalytic reactors and includes Chapter 5 onthree-phase fixed-bed reactors as well as Chapter 6 on three-phase slurry reactors both of which find significant industrialapplications moreover multiphase bioreactors are also includedin Part III as Chapter 7 Part IV is devoted to the discussion ofthe more recent state-of-the-art structured reactors the theoret-ical aspects and examples of structured reactors enabling processintensification in multiphase operation are treated in Chapter 8on monolith reactors and in Chapter 9 on microreactors of dif-ferent configurations including microstructured packed bedsand microchannel reactors Part V of the book is specificallydesigned for surveying the essential tools of catalytic reactormodeling and design and comprises two chapters Chapter 10discusses the recent developments and experimental techniquesinvolved in lab-scale testing of catalytic reactions includingsteady-state and transient flow experiments as well as the micro-kinetic and TAP approaches to kinetic analysis whileChapter 11 surveys the numerical solution techniques that arefrequently used in catalytic reactor analysis and demonstrateswith some case studies The capstone section of the bookPart VI contains four chapters devoted to specific industrialapplications of multiphase catalytic reactors and includes the
recent developments and practices in FischerndashTropsch technol-ogies (Chapter 12) a thorough discussion of reactor modelingsimulation and scale-up approaches involved in the hydrotreat-ing of oil fractions (Chapter 13) a detailed assessment of theperformances of various reactor configurations used for fuelprocessing (Chapter 14) and a comprehensive discussion ofcatalytic deoxygenation of fatty acids in a packed-bed reactoras case study in production of biofuels (Chapter 15)
It is indeed a pleasure to thank all of the contributors whohave made this challenging task achievable The editors are sin-cerely grateful for their willingness to devote their valuable timeand effort to this project for their readiness in sharing theirvision knowledge years of experience and know-how and alsofor their patience in tolerating various expected or unexpectedextensions arising from the busy schedules of different contribu-tors It has definitely been a privilege to work with the authorscoauthors and reviewers involved in this book The editorswould also like to extend their thanks to Wiley-Blackwell fortheir commitment to this project and to Michael Leventhalfor his organization andmanagement of the publication process
On a more personal note the editors would like to take thisopportunity to express their sincere gratitude to the late Profes-sor David L Trimm who has inspired their research in catalysisand catalytic reaction engineering through many years as super-visor mentor colleague and friend
Zeynep Ilsen OumlnsanAhmet Kerim Avci
Istanbul October 2015
Preface xiii
Copyright copy 2016 by John Wiley amp Sons Inc All rights reserved
Published by John Wiley amp Sons Inc Hoboken New Jersey
Published simultaneously in Canada
No part of this publication may be reproduced stored in a retrieval system or transmitted in any form or by any means electronicmechanical photocopying recording scanning or otherwise except as permitted under Section 107 or 108 of the 1976 United StatesCopyright Act without either the prior written permission of the Publisher or authorization through payment of the appropriateper-copy fee to the Copyright Clearance Center Inc 222 Rosewood Drive Danvers MA 01923 (978) 750-8400 fax (978) 750-4470 oron the web at wwwcopyrightcom Requests to the Publisher for permission should be addressed to the Permissions DepartmentJohn Wiley amp Sons Inc 111 River Street Hoboken NJ 07030 (201) 748-6011 fax (201) 748-6008 or online athttpwwwwileycomgopermissions
Limit of LiabilityDisclaimer ofWarranty While the publisher and author have used their best efforts in preparing this book they makeno representations or warranties with respect to the accuracy or completeness of the contents of this book and specifically disclaimany implied warranties of merchantability or fitness for a particular purpose No warranty may be created or extended by salesrepresentatives or written sales materials The advice and strategies contained herein may not be suitable for your situation You shouldconsult with a professional where appropriate Neither the publisher nor author shall be liable for any loss of profit or any othercommercial damages including but not limited to special incidental consequential or other damages
For general information on our other products and services or for technical support please contact our Customer Care Departmentwithin the United States at (800) 762-2974 outside the United States at (317) 572-3993 or fax (317) 572-4002
Wiley also publishes its books in a variety of electronic formats Some content that appears in print may not be available in electronicformats For more information about Wiley products visit our web site at wwwwileycom
Library of Congress Cataloging-in-Publication Data
Names Oumlnsan Zeynep Ilsen editor | Avci Ahmet Kerim editorTitle Multiphase catalytic reactors theory design manufacturing andapplications edited by Zeynep Ilsen Oumlnsan Ahmet Kerim Avci
Description Hoboken New Jersey John Wiley amp Sons Inc [2016] | Includesbibliographical references and index
Identifiers LCCN 2016009674 | ISBN 9781118115763 (cloth) | ISBN 9781119248477(epub) | ISBN 9781119248460 (epdf)
Subjects LCSH Phase-transfer catalysis | Chemical reactorsClassification LCC TP159C3 M85 2016 | DDC 6602832ndashdc23LC record available at httpslccnlocgov2016009674
Set in 95 12pt Minion by SPi Global Pondicherry India
Printed in the United States of America
10 9 8 7 6 5 4 3 2 1
Contents
List of Contributors x
Preface xii
Part 1 Principles of catalytic reaction engineering
1 Catalytic reactor types and their industrial significance 3Zeynep Ilsen Oumlnsan and Ahmet Kerim Avci
11 Introduction 3
12 Reactors with fixed bed of catalysts 3121 Packed-bed reactors 3122 Monolith reactors 8123 Radial flow reactors 9124 Trickle-bed reactors 9125 Short contact time reactors 10
13 Reactors with moving bed of catalysts 11131 Fluidized-bed reactors 11132 Slurry reactors 13133 Moving-bed reactors 14
14 Reactors without a catalyst bed 14
15 Summary 16
References 16
2 Microkinetic analysis of heterogeneous catalytic systems 17Zeynep Ilsen Oumlnsan
21 Heterogeneous catalytic systems 17211 Chemical and physical characteristics of solid
catalysts 18212 Activity selectivity and stability 21
22 Intrinsic kinetics of heterogeneous reactions 22221 Kinetic models and mechanisms 23222 Analysis and correlation of rate data 27
23 External (interphase) transport processes 32231 External mass transfer Isothermal conditions 33232 External temperature effects 35233 Nonisothermal conditions Multiple steady
states 36234 External effectiveness factors 38
24 Internal (intraparticle) transport processes 39241 Intraparticle mass and heat transfer 39242 Mass transfer with chemical reaction Isothermal
effectiveness 41
243 Heat and mass transfer with chemical reaction 45244 Impact of internal transport limitations
on kinetic studies 47
25 Combination of external and internal transporteffects 48251 Isothermal overall effectiveness 48252 Nonisothermal conditions 49
26 Summary 50
Nomenclature 50
Greek letters 51
References 51
Part 2 Two-phase catalytic reactors
3 Fixed-bed gasndashsolid catalytic reactors 55Joatildeo P Lopes and Aliacuterio E Rodrigues
31 Introduction and outline 55
32 Modeling of fixed-bed reactors 57321 Description of transportndashreaction
phenomena 57322 Mathematical model 59323 Model reduction and selection 61
33 Averaging over the catalyst particle 61331 Chemical regime 64332 Diffusional regime 64
34 Dominant fluidndashsolid mass transfer 66341 Isothermal axial flow bed 67342 Non-isothermal non-adiabatic axial flow bed 70
35 Dominant fluidndashsolid mass and heat transfer 70
36 Negligible mass and thermal dispersion 72
37 Conclusions 73
Nomenclature 74
Greek letters 75
References 75
4 Fluidized-bed catalytic reactors 80John R Grace
41 Introduction 80411 Advantages and disadvantages of fluidized-bed
reactors 80412 Preconditions for successful fluidized-bed
processes 81
v
413 Industrial catalytic processes employingfluidized-bed reactors 82
42 Key hydrodynamic features of gas-fluidized beds 83421 Minimum fluidization velocity 83422 Powder group and minimum bubbling
velocity 84423 Flow regimes and transitions 84424 Bubbling fluidized beds 84425 Turbulent fluidization flow regime 85426 Fast fluidization and dense suspension
upflow 85
43 Key properties affecting reactor performance 86431 Particle mixing 86432 Gas mixing 87433 Heat transfer and temperature uniformity 87434 Mass transfer 88435 Entrainment 88436 Attrition 89437 Wear 89438 Agglomeration and fouling 89439 Electrostatics and other interparticle forces 89
44 Reactor modeling 89441 Basis for reactor modeling 89442 Modeling of bubbling and slugging flow
regimes 90443 Modeling of reactors operating in high-velocity
flow regimes 91
45 Scale-up pilot testing and practical issues 91451 Scale-up issues 91452 Laboratory and pilot testing 91453 Instrumentation 92454 Other practical issues 92
46 Concluding remarks 92
Nomenclature 93
Greek letters 93
References 93
Part 3 Three-phase catalytic reactors
5 Three-phase fixed-bed reactors 97Ion Iliuta and Faiumlccedilal Larachi
51 Introduction 97
52 Hydrodynamic aspects of three-phase fixed-bedreactors 98521 General aspects Flow regimes liquid holdup
two-phase pressure drop and wetting efficiency 98522 Standard two-fluid models for two-phase
downflow and upflow in three-phase fixed-bedreactors 100
523 Nonequilibrium thermomechanical models fortwo-phase flow in three-phase fixed-bedreactors 102
53 Mass and heat transfer in three-phase fixed-bedreactors 104531 Gasndashliquid mass transfer 105532 Liquidndashsolid mass transfer 105533 Heat transfer 106
54 Scale-up and scale-down of trickle-bed reactors 108541 Scaling up of trickle-bed reactors 108542 Scaling down of trickle-bed reactors 109543 Salient conclusions 110
55 Trickle-bed reactorbioreactor modeling 110551 Catalytic hydrodesulfurization and bed
clogging in hydrotreating trickle-bedreactors 110
552 Biomass accumulation and clogging intrickle-bed bioreactors for phenolbiodegradation 115
553 Integrated aqueous-phase glycerol reformingand dimethyl ether synthesis into anallothermal dual-bed reactor 121
Nomenclature 126
Greek letters 127
Subscripts 128
Superscripts 128
Abbreviations 128
References 128
6 Three-phase slurry reactors 132Vivek V Buwa Shantanu Roy and Vivek V Ranade
61 Introduction 132
62 Reactor design scale-up methodology and reactorselection 134621 Practical aspects of reactor design and
scale-up 134622 Transport effects at particle level 139
63 Reactor models for design and scale-up 143631 Lower order models 143632 Tank-in-seriesmixing cell models 144
64 Estimation of transport and hydrodynamicparameters 145641 Estimation of transport parameters 145642 Estimation of hydrodynamic parameters 146
65 Advanced computational fluid dynamics(CFD)-based models 147
66 Summary and closing remarks 149
Acknowledgments 152
Nomenclature 152
Greek letters 153
Subscripts 153
References 153
vi Contents
7 Bioreactors 156Pedro Fernandes and Joaquim MS Cabral
71 Introduction 156
72 Basic concepts configurations and modes ofoperation 156721 Basic concepts 156722 Reactor configurations and modes of
operation 157
73 Mass balances and reactor equations 159731 Operation with enzymes 159732 Operation with living cells 160
74 Immobilized enzymes and cells 164741 Mass transfer effects 164742 Deactivation effects 166
75 Aeration 166
76 Mixing 166
77 Heat transfer 167
78 Scale-up 167
79 Bioreactors for animal cell cultures 167
710 Monitoring and control of bioreactors 168
Nomenclature 168
Greek letters 169
Subscripts 169
References 169
Part 4 Structured reactors
8 Monolith reactors 173Joatildeo P Lopes and Aliacuterio E Rodrigues
81 Introduction 173811 Design concepts 174812 Applications 178
82 Design of wall-coated monolith channels 179821 Flow in monolithic channels 179822 Mass transfer and wall reaction 182823 Reaction and diffusion in the catalytic
washcoat 190824 Nonisothermal operation 194
83 Mapping and evaluation of operatingregimes 197831 Diversity in the operation of a monolith
reactor 197832 Definition of operating regimes 199833 Operating diagrams for linear kinetics 201834 Influence of nonlinear reaction kinetics 202835 Performance evaluation 203
84 Three-phase processes 204
85 Conclusions 207
Nomenclature 207
Greek letters 208
Superscripts 208
Subscripts 208
References 209
9 Microreactors for catalytic reactions 213Evgeny Rebrov and Sourav Chatterjee
91 Introduction 213
92 Single-phase catalytic microreactors 213921 Residence time distribution 213922 Effect of flow maldistribution 214923 Mass transfer 215924 Heat transfer 215
93 Multiphase microreactors 216931 Microstructured packed beds 216932 Microchannel reactors 218
94 Conclusions and outlook 225
Nomenclature 226
Greek letters 227
Subscripts 227
References 228
Part 5 Essential tools of reactor modeling and design
10 Experimental methods for the determination ofparameters 233Rebecca R Fushimi John T Gleaves and GregoryS Yablonsky
101 Introduction 233
102 Consideration of kinetic objectives 234
103 Criteria for collecting kinetic data 234
104 Experimental methods 2341041 Steady-state flow experiments 2351042 Transient flow experiments 2371043 Surface science experiments 238
105 Microkinetic approach to kinetic analysis 241
106 TAP approach to kinetic analysis 2411061 TAP experiment design 2421062 TAP experimental results 244
107 Conclusions 248
References 249
11 Numerical solution techniques 253Ahmet Kerim Avci and Seda Keskin
111 Techniques for the numerical solution of ordinarydifferential equations 2531111 Explicit techniques 2531112 Implicit techniques 254
112 Techniques for the numerical solution of partialdifferential equations 255
Contents vii
113 Computational fluid dynamics techniques 2561131 Methodology of computational fluid
dynamics 2561132 Finite element method 2561133 Finite volume method 258
114 Case studies 2591141 Indirect partial oxidation of methane in a
catalytic tubular reactor 2591142 Hydrocarbon steam reforming in
spatially segregated microchannelreactors 261
115 Summary 265
Nomenclature 266
Greek letters 267
Subscriptssuperscripts 267
References 267
Part 6 Industrial applications of multiphase reactors
12 Reactor approaches for FischerndashTropsch synthesis 271Gary Jacobs and Burtron H Davis
121 Introduction 271
122 Reactors to 1950 272
123 1950ndash1985 period 274
124 1985 to present 2761241 Fixed-bed reactors 2761242 Fluidized-bed reactors 2801243 Slurry bubble column reactors 2811244 Structured packings 2861245 Operation at supercritical conditions(SCF) 288
125 The future 288
References 291
13 Hydrotreating of oil fractions 295Jorge Ancheyta Anton Alvarez-Majmutov andCarolina Leyva
131 Introduction 295
132 The HDT process 2961321 Overview 2961322 Role in petroleum refining 2971323 World outlook and the situation ofMexico 298
133 Fundamentals of HDT 3001331 Chemistry 3001332 Reaction kinetics 3031333 Thermodynamics 3051334 Catalysts 306
134 Process aspects of HDT 3071341 Process variables 307
1342 Reactors for hydroprocessing 3101343 Catalyst activation in commercial
hydrotreaters 316
135 Reactor modeling and simulation 3171351 Process description 3171352 Summary of experiments 3171353 Modeling approach 3191354 Simulation of the bench-scale unit 3201355 Scale-up of bench-unit data 3231356 Simulation of the commercial
unit 324
Nomenclature 326
Greek letters 327
Subscripts 327
Non-SI units 327
References 327
14 Catalytic reactors for fuel processing 330Gunther Kolb
141 IntroductionmdashThe basic reactions of fuelprocessing 330
142 Theoretical aspects advantages and drawbacks offixed beds versus monoliths microreactors andmembrane reactors 331
143 Reactor design and fabrication 3321431 Fixed-bed reactors 3321432 Monolithic reactors 3321433 Microreactors 3321434 Membrane reactors 333
144 Reformers 3331441 Fixed-bed reformers 3361442 Monolithic reformers 3371443 Plate heat exchangers and microstructured
reformers 3421444 Membrane reformers 344
145 Water-gas shift reactors 3481451 Monolithic reactors 3481452 Plate heat exchangers and microstructured
water-gas shift reactors 3481453 Water-gas shift in membrane reactors 350
146 Carbon monoxide fine cleanup Preferential oxidationand selective methanation 3501461 Fixed-bed reactors 3521462 Monolithic reactors 3521463 Plate heat exchangers and microstructured
reactors 353
147 Examples of complete fuel processors 3551471 Monolithic fuel processors 3551472 Plate heat exchanger fuel processors on the
meso- and microscale 357
viii Contents
Nomenclature 359
References 359
15 Modeling of the catalytic deoxygenation of fatty acids in apacked bed reactor 365Teuvo Kilpiouml Paumlivi Maumlki-Arvela Tapio Salmi andDmitry Yu Murzin
151 Introduction 365
152 Experimental data for stearic aciddeoxygenation 366
153 Assumptions 366
154 Model equations 367
155 Evaluation of the adsorption parameters 368
156 Particle diffusion study 369
157 Parameter sensitivity studies 369
158 Parameter identification studies 370
159 Studies concerning the deviation from ideal plug flowconditions 371
1510 Parameter estimation results 372
1511 Scale-up considerations 372
1512 Conclusions 375
Acknowledgments 375
Nomenclature 375
Greek letters 375
References 376
Index 377
Contents ix
List of contributors
Anton Alvarez-MajmutovInstituto Mexicano del Petroacuteleo Management of Products for theTransformation of Crude Oil Mexico City Mexico
Jorge AncheytaInstituto Mexicano del Petroacuteleo Management of Products for theTransformation of Crude Oil Mexico City Mexico
Ahmet Kerim AvciDepartment of Chemical Engineering Boğaziccedili University Istanbul Turkey
Vivek V BuwaDepartment of Chemical EngineeringIndian Institute of Technology-Delhi New Delhi India
Joaquim MS CabralDepartment of Bioengineering and IBB-Institute for Bioengineeringand Biosciences Instituto Superior Teacutecnico Universidade de LisboaLisboa Portugal
Sourav ChatterjeeSchool of Chemistry and Chemical Engineering Queenrsquos University BelfastBelfast UK
Burtron H DavisCenter for Applied Energy Research University of KentuckyLexington KY USA
Pedro FernandesDepartment of Bioengineering and IBB-Institutefor Bioengineering and Biosciences Instituto Superior TeacutecnicoUniversidade de Lisboa Faculdade de EngenhariaUniversidade Lusoacutefona de Humanidadese Tecnologias Lisboa Portugal
Rebecca R FushimiMaterials Science amp Engineering Department Idaho National LaboratoryIdaho Falls ID USA
John T GleavesDepartment of Energy Environmental and Chemical EngineeringWashington University St Louis MO USA
John R GraceDepartment of Chemical and Biological EngineeringThe University of British Columbia VancouverBritish Columbia Canada
Ion IliutaChemical Engineering Department Laval University Queacutebec CityQueacutebec Canada
Gary JacobsCenter for Applied Energy Research University of KentuckyLexington KY USA
Seda KeskinDepartment of Chemical and Biological Engineering Koc UniversityIstanbul Turkey
Teuvo KilpioumlProcess Chemistry Centre Aringbo Akademi University TurkuAringbo Finland
Gunther KolbFraunhofer ICT-IMM Decentralized and Mobile Energy TechnologyDepartment Mainz Germany
Faiumlccedilal LarachiChemical Engineering Department Laval University Queacutebec CityQueacutebec Canada
Carolina LeyvaCentro de Investigacioacuten en Ciencia Aplicada y Tecnologiacutea AvanzadaUnidad Legaria Instituto Politeacutecnico Nacional Mexico City Mexico
Joatildeo P LopesDepartment of Chemical Engineering and BiotechnologyUniversity of Cambridge Cambridge UK
Paumlivi Maumlki-ArvelaProcess Chemistry Centre Aringbo Akademi University TurkuAringbo Finland
Dmitry Yu MurzinProcess Chemistry Centre Aringbo Akademi University TurkuAringbo Finland
Zeynep Ilsen OumlnsanDepartment of Chemical Engineering Boğaziccedili University Istanbul Turkey
Vivek V RanadeChemical Engineering amp Process Development Division National ChemicalLaboratory Pune India
Evgeny RebrovSchool of Engineering University of Warwick Coventry UK
x
Aliacuterio E RodriguesLaboratory of Separation and Reaction EngineeringAssociate Laboratory LSRELCM Department of Chemical EngineeringFaculty of Engineering University of Porto Porto Portugal
Shantanu RoyDepartment of Chemical Engineering Indian Institute of Technology-DelhiNew Delhi India
Tapio SalmiProcess Chemistry Centre Aringbo Akademi UniversityTurkuAringbo Finland
Gregory S YablonskyParks College of Engineering Aviation and TechnologySaint Louis University St Louis MO USA
List of contributors xi
Preface
The single irreplaceable component at the core of a chemicalprocess is the chemical reactor where feed materials are con-verted into desirable products Although the essential variablesby which chemical processes can be controlled are reaction tem-perature pressure feed composition and residence time in thereactor two technological developments of major consequencestarting with 1960s have made possible cost-effective operationunder less severe conditions these are the extensive use of effi-cient catalysts and the introduction of improved or innovativereactor configurations The impact of heterogeneous catalysisis significant in this respect since petroleum refining manufac-turing of chemicals and environmental clean-up which are thethree major areas of the world economy today all requirethe effective use of solid catalysts The challenges involved inthe design of novel solid catalysts and modification of manyexisting ones for higher selectivity and stability have alsoprompted the development of ldquoengineeredrdquo catalysts befittingnovel reactor configurations requiring the use of new supportssuch as monolithic or foam substrates as well as the establish-ment of new techniques for coating surfaces with diverse catalystcomponents in order to ensure longevity particularly in cyclicprocessesIn industrial practice the composition and properties of the
complex feed mixtures that are processed for producing a rangeof valuable chemicals generally necessitate the use of heteroge-neous catalytic reactors Numerous chemical and physical rateprocesses take place in a heterogeneous reactor at differentlength and time scales and frequently in different phasesThe prerequisite for the successful design and operation of cat-alytic reactors is a thorough microkinetic analysis starting fromintrinsic kinetic models of the steady-state chemical activity andleading to global rate expressions obtained by overlaying theeffects of physical rate phenomena occurring at the particlescale Kinetic models of increasing complexity may be requireddepending on the variety of components and number of reac-tions involved The second critical stage in reactor modelingand design is a macrokinetic analysis including the detaileddescription of physical transport phenomena at the reactor scaleand utilizing the global rate expressions of the microkineticanalysis The final catalytic reactor model which integrates theseessential stages can successfully predict the performance anddynamics of plant-scale industrial reactors as well as simulatingtheir start-up shutdown and cyclic operation Taking intoaccount engineered catalysts and new reactor configurations
the modeling and scaling up of reactions conducted at thebench-scale to pilot plant and industrial-scale reactor levels haveto be modified in order to include simultaneous multiscaleapproaches along with the conventional sequential modesMultiphase Catalytic Reactors Theory Design Manufactur-
ing and Applications is a comprehensive up-to-date compila-tion on multiphase catalytic reactors which will serve as anexcellent reference book for graduate students researchersand specialists both in academia and in industry The contentof the book is planned to cover topics starting from the firstprinciples involved in macrokinetic analysis of two- andthree-phase catalytic reactors to their particular industrial appli-cations The main objective is to provide definitive accounts onacademic aspects of multiphase catalytic reactor modeling anddesign along with detailed descriptions of some of the mostrecent industrial applications employing multiphase catalyticreactors in such a way as to balance the academic and industrialcomponents as much as possible Accordingly seven chaptersare included in Parts II III and IV to review the relevantmathematical models and model equations utilized in the fun-damental analysis and macroscopic design of specific reactortypes together with some useful approximations for theirdesign and scale-up from a practical standpoint while the fourchapters in Part VI describe specific industrial applications andcontain pointers that tie in with the modeling and designapproaches presented for the particular multiphase catalyticreactor types discussed in Parts II III and IV Furthermorethe chapters included in Parts I and V of the book containdetailed reviews of the basic principles and essential tools ofcatalytic reaction engineering that are crucial for the successfuldesign and operation of catalytic reactors All chapters ofthe book are contributed by experts distinguished in theirrespective fieldsThe total of 15 chapters included in Multiphase Catalytic
Reactors Theory Design Manufacturing and Applications areorganized in six parts Part I is an overview of the principlesof catalytic reaction engineering embracing Chapter 1 whichis a survey of multiphase catalytic reactor types and their indus-trial significance as well as Chapter 2 on the microkinetic anal-ysis of heterogeneous catalytic systems which surveys theformulation of intrinsic rate equations describing chemical rateprocesses and the construction of global rate expressions thatinclude the effects of physical mass and heat transport phenom-ena occurring at the particle scale Chapters 3 through 9 in
xii
Parts II III and IV discuss individual two- and three-phase cat-alytic reactor types and provide design equations and empiricalrelationships that characterize different multiphase reactorsmathematical modeling is an integral part of these chaptersIn Part II two-phase catalytic reactors are grouped as fixed-bed gasndashsolid catalytic reactors (Chapter 3) and fluidized-bedcatalytic reactors (Chapter 4) Part III deals exclusively withthree-phase catalytic reactors and includes Chapter 5 onthree-phase fixed-bed reactors as well as Chapter 6 on three-phase slurry reactors both of which find significant industrialapplications moreover multiphase bioreactors are also includedin Part III as Chapter 7 Part IV is devoted to the discussion ofthe more recent state-of-the-art structured reactors the theoret-ical aspects and examples of structured reactors enabling processintensification in multiphase operation are treated in Chapter 8on monolith reactors and in Chapter 9 on microreactors of dif-ferent configurations including microstructured packed bedsand microchannel reactors Part V of the book is specificallydesigned for surveying the essential tools of catalytic reactormodeling and design and comprises two chapters Chapter 10discusses the recent developments and experimental techniquesinvolved in lab-scale testing of catalytic reactions includingsteady-state and transient flow experiments as well as the micro-kinetic and TAP approaches to kinetic analysis whileChapter 11 surveys the numerical solution techniques that arefrequently used in catalytic reactor analysis and demonstrateswith some case studies The capstone section of the bookPart VI contains four chapters devoted to specific industrialapplications of multiphase catalytic reactors and includes the
recent developments and practices in FischerndashTropsch technol-ogies (Chapter 12) a thorough discussion of reactor modelingsimulation and scale-up approaches involved in the hydrotreat-ing of oil fractions (Chapter 13) a detailed assessment of theperformances of various reactor configurations used for fuelprocessing (Chapter 14) and a comprehensive discussion ofcatalytic deoxygenation of fatty acids in a packed-bed reactoras case study in production of biofuels (Chapter 15)
It is indeed a pleasure to thank all of the contributors whohave made this challenging task achievable The editors are sin-cerely grateful for their willingness to devote their valuable timeand effort to this project for their readiness in sharing theirvision knowledge years of experience and know-how and alsofor their patience in tolerating various expected or unexpectedextensions arising from the busy schedules of different contribu-tors It has definitely been a privilege to work with the authorscoauthors and reviewers involved in this book The editorswould also like to extend their thanks to Wiley-Blackwell fortheir commitment to this project and to Michael Leventhalfor his organization andmanagement of the publication process
On a more personal note the editors would like to take thisopportunity to express their sincere gratitude to the late Profes-sor David L Trimm who has inspired their research in catalysisand catalytic reaction engineering through many years as super-visor mentor colleague and friend
Zeynep Ilsen OumlnsanAhmet Kerim Avci
Istanbul October 2015
Preface xiii
Contents
List of Contributors x
Preface xii
Part 1 Principles of catalytic reaction engineering
1 Catalytic reactor types and their industrial significance 3Zeynep Ilsen Oumlnsan and Ahmet Kerim Avci
11 Introduction 3
12 Reactors with fixed bed of catalysts 3121 Packed-bed reactors 3122 Monolith reactors 8123 Radial flow reactors 9124 Trickle-bed reactors 9125 Short contact time reactors 10
13 Reactors with moving bed of catalysts 11131 Fluidized-bed reactors 11132 Slurry reactors 13133 Moving-bed reactors 14
14 Reactors without a catalyst bed 14
15 Summary 16
References 16
2 Microkinetic analysis of heterogeneous catalytic systems 17Zeynep Ilsen Oumlnsan
21 Heterogeneous catalytic systems 17211 Chemical and physical characteristics of solid
catalysts 18212 Activity selectivity and stability 21
22 Intrinsic kinetics of heterogeneous reactions 22221 Kinetic models and mechanisms 23222 Analysis and correlation of rate data 27
23 External (interphase) transport processes 32231 External mass transfer Isothermal conditions 33232 External temperature effects 35233 Nonisothermal conditions Multiple steady
states 36234 External effectiveness factors 38
24 Internal (intraparticle) transport processes 39241 Intraparticle mass and heat transfer 39242 Mass transfer with chemical reaction Isothermal
effectiveness 41
243 Heat and mass transfer with chemical reaction 45244 Impact of internal transport limitations
on kinetic studies 47
25 Combination of external and internal transporteffects 48251 Isothermal overall effectiveness 48252 Nonisothermal conditions 49
26 Summary 50
Nomenclature 50
Greek letters 51
References 51
Part 2 Two-phase catalytic reactors
3 Fixed-bed gasndashsolid catalytic reactors 55Joatildeo P Lopes and Aliacuterio E Rodrigues
31 Introduction and outline 55
32 Modeling of fixed-bed reactors 57321 Description of transportndashreaction
phenomena 57322 Mathematical model 59323 Model reduction and selection 61
33 Averaging over the catalyst particle 61331 Chemical regime 64332 Diffusional regime 64
34 Dominant fluidndashsolid mass transfer 66341 Isothermal axial flow bed 67342 Non-isothermal non-adiabatic axial flow bed 70
35 Dominant fluidndashsolid mass and heat transfer 70
36 Negligible mass and thermal dispersion 72
37 Conclusions 73
Nomenclature 74
Greek letters 75
References 75
4 Fluidized-bed catalytic reactors 80John R Grace
41 Introduction 80411 Advantages and disadvantages of fluidized-bed
reactors 80412 Preconditions for successful fluidized-bed
processes 81
v
413 Industrial catalytic processes employingfluidized-bed reactors 82
42 Key hydrodynamic features of gas-fluidized beds 83421 Minimum fluidization velocity 83422 Powder group and minimum bubbling
velocity 84423 Flow regimes and transitions 84424 Bubbling fluidized beds 84425 Turbulent fluidization flow regime 85426 Fast fluidization and dense suspension
upflow 85
43 Key properties affecting reactor performance 86431 Particle mixing 86432 Gas mixing 87433 Heat transfer and temperature uniformity 87434 Mass transfer 88435 Entrainment 88436 Attrition 89437 Wear 89438 Agglomeration and fouling 89439 Electrostatics and other interparticle forces 89
44 Reactor modeling 89441 Basis for reactor modeling 89442 Modeling of bubbling and slugging flow
regimes 90443 Modeling of reactors operating in high-velocity
flow regimes 91
45 Scale-up pilot testing and practical issues 91451 Scale-up issues 91452 Laboratory and pilot testing 91453 Instrumentation 92454 Other practical issues 92
46 Concluding remarks 92
Nomenclature 93
Greek letters 93
References 93
Part 3 Three-phase catalytic reactors
5 Three-phase fixed-bed reactors 97Ion Iliuta and Faiumlccedilal Larachi
51 Introduction 97
52 Hydrodynamic aspects of three-phase fixed-bedreactors 98521 General aspects Flow regimes liquid holdup
two-phase pressure drop and wetting efficiency 98522 Standard two-fluid models for two-phase
downflow and upflow in three-phase fixed-bedreactors 100
523 Nonequilibrium thermomechanical models fortwo-phase flow in three-phase fixed-bedreactors 102
53 Mass and heat transfer in three-phase fixed-bedreactors 104531 Gasndashliquid mass transfer 105532 Liquidndashsolid mass transfer 105533 Heat transfer 106
54 Scale-up and scale-down of trickle-bed reactors 108541 Scaling up of trickle-bed reactors 108542 Scaling down of trickle-bed reactors 109543 Salient conclusions 110
55 Trickle-bed reactorbioreactor modeling 110551 Catalytic hydrodesulfurization and bed
clogging in hydrotreating trickle-bedreactors 110
552 Biomass accumulation and clogging intrickle-bed bioreactors for phenolbiodegradation 115
553 Integrated aqueous-phase glycerol reformingand dimethyl ether synthesis into anallothermal dual-bed reactor 121
Nomenclature 126
Greek letters 127
Subscripts 128
Superscripts 128
Abbreviations 128
References 128
6 Three-phase slurry reactors 132Vivek V Buwa Shantanu Roy and Vivek V Ranade
61 Introduction 132
62 Reactor design scale-up methodology and reactorselection 134621 Practical aspects of reactor design and
scale-up 134622 Transport effects at particle level 139
63 Reactor models for design and scale-up 143631 Lower order models 143632 Tank-in-seriesmixing cell models 144
64 Estimation of transport and hydrodynamicparameters 145641 Estimation of transport parameters 145642 Estimation of hydrodynamic parameters 146
65 Advanced computational fluid dynamics(CFD)-based models 147
66 Summary and closing remarks 149
Acknowledgments 152
Nomenclature 152
Greek letters 153
Subscripts 153
References 153
vi Contents
7 Bioreactors 156Pedro Fernandes and Joaquim MS Cabral
71 Introduction 156
72 Basic concepts configurations and modes ofoperation 156721 Basic concepts 156722 Reactor configurations and modes of
operation 157
73 Mass balances and reactor equations 159731 Operation with enzymes 159732 Operation with living cells 160
74 Immobilized enzymes and cells 164741 Mass transfer effects 164742 Deactivation effects 166
75 Aeration 166
76 Mixing 166
77 Heat transfer 167
78 Scale-up 167
79 Bioreactors for animal cell cultures 167
710 Monitoring and control of bioreactors 168
Nomenclature 168
Greek letters 169
Subscripts 169
References 169
Part 4 Structured reactors
8 Monolith reactors 173Joatildeo P Lopes and Aliacuterio E Rodrigues
81 Introduction 173811 Design concepts 174812 Applications 178
82 Design of wall-coated monolith channels 179821 Flow in monolithic channels 179822 Mass transfer and wall reaction 182823 Reaction and diffusion in the catalytic
washcoat 190824 Nonisothermal operation 194
83 Mapping and evaluation of operatingregimes 197831 Diversity in the operation of a monolith
reactor 197832 Definition of operating regimes 199833 Operating diagrams for linear kinetics 201834 Influence of nonlinear reaction kinetics 202835 Performance evaluation 203
84 Three-phase processes 204
85 Conclusions 207
Nomenclature 207
Greek letters 208
Superscripts 208
Subscripts 208
References 209
9 Microreactors for catalytic reactions 213Evgeny Rebrov and Sourav Chatterjee
91 Introduction 213
92 Single-phase catalytic microreactors 213921 Residence time distribution 213922 Effect of flow maldistribution 214923 Mass transfer 215924 Heat transfer 215
93 Multiphase microreactors 216931 Microstructured packed beds 216932 Microchannel reactors 218
94 Conclusions and outlook 225
Nomenclature 226
Greek letters 227
Subscripts 227
References 228
Part 5 Essential tools of reactor modeling and design
10 Experimental methods for the determination ofparameters 233Rebecca R Fushimi John T Gleaves and GregoryS Yablonsky
101 Introduction 233
102 Consideration of kinetic objectives 234
103 Criteria for collecting kinetic data 234
104 Experimental methods 2341041 Steady-state flow experiments 2351042 Transient flow experiments 2371043 Surface science experiments 238
105 Microkinetic approach to kinetic analysis 241
106 TAP approach to kinetic analysis 2411061 TAP experiment design 2421062 TAP experimental results 244
107 Conclusions 248
References 249
11 Numerical solution techniques 253Ahmet Kerim Avci and Seda Keskin
111 Techniques for the numerical solution of ordinarydifferential equations 2531111 Explicit techniques 2531112 Implicit techniques 254
112 Techniques for the numerical solution of partialdifferential equations 255
Contents vii
113 Computational fluid dynamics techniques 2561131 Methodology of computational fluid
dynamics 2561132 Finite element method 2561133 Finite volume method 258
114 Case studies 2591141 Indirect partial oxidation of methane in a
catalytic tubular reactor 2591142 Hydrocarbon steam reforming in
spatially segregated microchannelreactors 261
115 Summary 265
Nomenclature 266
Greek letters 267
Subscriptssuperscripts 267
References 267
Part 6 Industrial applications of multiphase reactors
12 Reactor approaches for FischerndashTropsch synthesis 271Gary Jacobs and Burtron H Davis
121 Introduction 271
122 Reactors to 1950 272
123 1950ndash1985 period 274
124 1985 to present 2761241 Fixed-bed reactors 2761242 Fluidized-bed reactors 2801243 Slurry bubble column reactors 2811244 Structured packings 2861245 Operation at supercritical conditions(SCF) 288
125 The future 288
References 291
13 Hydrotreating of oil fractions 295Jorge Ancheyta Anton Alvarez-Majmutov andCarolina Leyva
131 Introduction 295
132 The HDT process 2961321 Overview 2961322 Role in petroleum refining 2971323 World outlook and the situation ofMexico 298
133 Fundamentals of HDT 3001331 Chemistry 3001332 Reaction kinetics 3031333 Thermodynamics 3051334 Catalysts 306
134 Process aspects of HDT 3071341 Process variables 307
1342 Reactors for hydroprocessing 3101343 Catalyst activation in commercial
hydrotreaters 316
135 Reactor modeling and simulation 3171351 Process description 3171352 Summary of experiments 3171353 Modeling approach 3191354 Simulation of the bench-scale unit 3201355 Scale-up of bench-unit data 3231356 Simulation of the commercial
unit 324
Nomenclature 326
Greek letters 327
Subscripts 327
Non-SI units 327
References 327
14 Catalytic reactors for fuel processing 330Gunther Kolb
141 IntroductionmdashThe basic reactions of fuelprocessing 330
142 Theoretical aspects advantages and drawbacks offixed beds versus monoliths microreactors andmembrane reactors 331
143 Reactor design and fabrication 3321431 Fixed-bed reactors 3321432 Monolithic reactors 3321433 Microreactors 3321434 Membrane reactors 333
144 Reformers 3331441 Fixed-bed reformers 3361442 Monolithic reformers 3371443 Plate heat exchangers and microstructured
reformers 3421444 Membrane reformers 344
145 Water-gas shift reactors 3481451 Monolithic reactors 3481452 Plate heat exchangers and microstructured
water-gas shift reactors 3481453 Water-gas shift in membrane reactors 350
146 Carbon monoxide fine cleanup Preferential oxidationand selective methanation 3501461 Fixed-bed reactors 3521462 Monolithic reactors 3521463 Plate heat exchangers and microstructured
reactors 353
147 Examples of complete fuel processors 3551471 Monolithic fuel processors 3551472 Plate heat exchanger fuel processors on the
meso- and microscale 357
viii Contents
Nomenclature 359
References 359
15 Modeling of the catalytic deoxygenation of fatty acids in apacked bed reactor 365Teuvo Kilpiouml Paumlivi Maumlki-Arvela Tapio Salmi andDmitry Yu Murzin
151 Introduction 365
152 Experimental data for stearic aciddeoxygenation 366
153 Assumptions 366
154 Model equations 367
155 Evaluation of the adsorption parameters 368
156 Particle diffusion study 369
157 Parameter sensitivity studies 369
158 Parameter identification studies 370
159 Studies concerning the deviation from ideal plug flowconditions 371
1510 Parameter estimation results 372
1511 Scale-up considerations 372
1512 Conclusions 375
Acknowledgments 375
Nomenclature 375
Greek letters 375
References 376
Index 377
Contents ix
List of contributors
Anton Alvarez-MajmutovInstituto Mexicano del Petroacuteleo Management of Products for theTransformation of Crude Oil Mexico City Mexico
Jorge AncheytaInstituto Mexicano del Petroacuteleo Management of Products for theTransformation of Crude Oil Mexico City Mexico
Ahmet Kerim AvciDepartment of Chemical Engineering Boğaziccedili University Istanbul Turkey
Vivek V BuwaDepartment of Chemical EngineeringIndian Institute of Technology-Delhi New Delhi India
Joaquim MS CabralDepartment of Bioengineering and IBB-Institute for Bioengineeringand Biosciences Instituto Superior Teacutecnico Universidade de LisboaLisboa Portugal
Sourav ChatterjeeSchool of Chemistry and Chemical Engineering Queenrsquos University BelfastBelfast UK
Burtron H DavisCenter for Applied Energy Research University of KentuckyLexington KY USA
Pedro FernandesDepartment of Bioengineering and IBB-Institutefor Bioengineering and Biosciences Instituto Superior TeacutecnicoUniversidade de Lisboa Faculdade de EngenhariaUniversidade Lusoacutefona de Humanidadese Tecnologias Lisboa Portugal
Rebecca R FushimiMaterials Science amp Engineering Department Idaho National LaboratoryIdaho Falls ID USA
John T GleavesDepartment of Energy Environmental and Chemical EngineeringWashington University St Louis MO USA
John R GraceDepartment of Chemical and Biological EngineeringThe University of British Columbia VancouverBritish Columbia Canada
Ion IliutaChemical Engineering Department Laval University Queacutebec CityQueacutebec Canada
Gary JacobsCenter for Applied Energy Research University of KentuckyLexington KY USA
Seda KeskinDepartment of Chemical and Biological Engineering Koc UniversityIstanbul Turkey
Teuvo KilpioumlProcess Chemistry Centre Aringbo Akademi University TurkuAringbo Finland
Gunther KolbFraunhofer ICT-IMM Decentralized and Mobile Energy TechnologyDepartment Mainz Germany
Faiumlccedilal LarachiChemical Engineering Department Laval University Queacutebec CityQueacutebec Canada
Carolina LeyvaCentro de Investigacioacuten en Ciencia Aplicada y Tecnologiacutea AvanzadaUnidad Legaria Instituto Politeacutecnico Nacional Mexico City Mexico
Joatildeo P LopesDepartment of Chemical Engineering and BiotechnologyUniversity of Cambridge Cambridge UK
Paumlivi Maumlki-ArvelaProcess Chemistry Centre Aringbo Akademi University TurkuAringbo Finland
Dmitry Yu MurzinProcess Chemistry Centre Aringbo Akademi University TurkuAringbo Finland
Zeynep Ilsen OumlnsanDepartment of Chemical Engineering Boğaziccedili University Istanbul Turkey
Vivek V RanadeChemical Engineering amp Process Development Division National ChemicalLaboratory Pune India
Evgeny RebrovSchool of Engineering University of Warwick Coventry UK
x
Aliacuterio E RodriguesLaboratory of Separation and Reaction EngineeringAssociate Laboratory LSRELCM Department of Chemical EngineeringFaculty of Engineering University of Porto Porto Portugal
Shantanu RoyDepartment of Chemical Engineering Indian Institute of Technology-DelhiNew Delhi India
Tapio SalmiProcess Chemistry Centre Aringbo Akademi UniversityTurkuAringbo Finland
Gregory S YablonskyParks College of Engineering Aviation and TechnologySaint Louis University St Louis MO USA
List of contributors xi
Preface
The single irreplaceable component at the core of a chemicalprocess is the chemical reactor where feed materials are con-verted into desirable products Although the essential variablesby which chemical processes can be controlled are reaction tem-perature pressure feed composition and residence time in thereactor two technological developments of major consequencestarting with 1960s have made possible cost-effective operationunder less severe conditions these are the extensive use of effi-cient catalysts and the introduction of improved or innovativereactor configurations The impact of heterogeneous catalysisis significant in this respect since petroleum refining manufac-turing of chemicals and environmental clean-up which are thethree major areas of the world economy today all requirethe effective use of solid catalysts The challenges involved inthe design of novel solid catalysts and modification of manyexisting ones for higher selectivity and stability have alsoprompted the development of ldquoengineeredrdquo catalysts befittingnovel reactor configurations requiring the use of new supportssuch as monolithic or foam substrates as well as the establish-ment of new techniques for coating surfaces with diverse catalystcomponents in order to ensure longevity particularly in cyclicprocessesIn industrial practice the composition and properties of the
complex feed mixtures that are processed for producing a rangeof valuable chemicals generally necessitate the use of heteroge-neous catalytic reactors Numerous chemical and physical rateprocesses take place in a heterogeneous reactor at differentlength and time scales and frequently in different phasesThe prerequisite for the successful design and operation of cat-alytic reactors is a thorough microkinetic analysis starting fromintrinsic kinetic models of the steady-state chemical activity andleading to global rate expressions obtained by overlaying theeffects of physical rate phenomena occurring at the particlescale Kinetic models of increasing complexity may be requireddepending on the variety of components and number of reac-tions involved The second critical stage in reactor modelingand design is a macrokinetic analysis including the detaileddescription of physical transport phenomena at the reactor scaleand utilizing the global rate expressions of the microkineticanalysis The final catalytic reactor model which integrates theseessential stages can successfully predict the performance anddynamics of plant-scale industrial reactors as well as simulatingtheir start-up shutdown and cyclic operation Taking intoaccount engineered catalysts and new reactor configurations
the modeling and scaling up of reactions conducted at thebench-scale to pilot plant and industrial-scale reactor levels haveto be modified in order to include simultaneous multiscaleapproaches along with the conventional sequential modesMultiphase Catalytic Reactors Theory Design Manufactur-
ing and Applications is a comprehensive up-to-date compila-tion on multiphase catalytic reactors which will serve as anexcellent reference book for graduate students researchersand specialists both in academia and in industry The contentof the book is planned to cover topics starting from the firstprinciples involved in macrokinetic analysis of two- andthree-phase catalytic reactors to their particular industrial appli-cations The main objective is to provide definitive accounts onacademic aspects of multiphase catalytic reactor modeling anddesign along with detailed descriptions of some of the mostrecent industrial applications employing multiphase catalyticreactors in such a way as to balance the academic and industrialcomponents as much as possible Accordingly seven chaptersare included in Parts II III and IV to review the relevantmathematical models and model equations utilized in the fun-damental analysis and macroscopic design of specific reactortypes together with some useful approximations for theirdesign and scale-up from a practical standpoint while the fourchapters in Part VI describe specific industrial applications andcontain pointers that tie in with the modeling and designapproaches presented for the particular multiphase catalyticreactor types discussed in Parts II III and IV Furthermorethe chapters included in Parts I and V of the book containdetailed reviews of the basic principles and essential tools ofcatalytic reaction engineering that are crucial for the successfuldesign and operation of catalytic reactors All chapters ofthe book are contributed by experts distinguished in theirrespective fieldsThe total of 15 chapters included in Multiphase Catalytic
Reactors Theory Design Manufacturing and Applications areorganized in six parts Part I is an overview of the principlesof catalytic reaction engineering embracing Chapter 1 whichis a survey of multiphase catalytic reactor types and their indus-trial significance as well as Chapter 2 on the microkinetic anal-ysis of heterogeneous catalytic systems which surveys theformulation of intrinsic rate equations describing chemical rateprocesses and the construction of global rate expressions thatinclude the effects of physical mass and heat transport phenom-ena occurring at the particle scale Chapters 3 through 9 in
xii
Parts II III and IV discuss individual two- and three-phase cat-alytic reactor types and provide design equations and empiricalrelationships that characterize different multiphase reactorsmathematical modeling is an integral part of these chaptersIn Part II two-phase catalytic reactors are grouped as fixed-bed gasndashsolid catalytic reactors (Chapter 3) and fluidized-bedcatalytic reactors (Chapter 4) Part III deals exclusively withthree-phase catalytic reactors and includes Chapter 5 onthree-phase fixed-bed reactors as well as Chapter 6 on three-phase slurry reactors both of which find significant industrialapplications moreover multiphase bioreactors are also includedin Part III as Chapter 7 Part IV is devoted to the discussion ofthe more recent state-of-the-art structured reactors the theoret-ical aspects and examples of structured reactors enabling processintensification in multiphase operation are treated in Chapter 8on monolith reactors and in Chapter 9 on microreactors of dif-ferent configurations including microstructured packed bedsand microchannel reactors Part V of the book is specificallydesigned for surveying the essential tools of catalytic reactormodeling and design and comprises two chapters Chapter 10discusses the recent developments and experimental techniquesinvolved in lab-scale testing of catalytic reactions includingsteady-state and transient flow experiments as well as the micro-kinetic and TAP approaches to kinetic analysis whileChapter 11 surveys the numerical solution techniques that arefrequently used in catalytic reactor analysis and demonstrateswith some case studies The capstone section of the bookPart VI contains four chapters devoted to specific industrialapplications of multiphase catalytic reactors and includes the
recent developments and practices in FischerndashTropsch technol-ogies (Chapter 12) a thorough discussion of reactor modelingsimulation and scale-up approaches involved in the hydrotreat-ing of oil fractions (Chapter 13) a detailed assessment of theperformances of various reactor configurations used for fuelprocessing (Chapter 14) and a comprehensive discussion ofcatalytic deoxygenation of fatty acids in a packed-bed reactoras case study in production of biofuels (Chapter 15)
It is indeed a pleasure to thank all of the contributors whohave made this challenging task achievable The editors are sin-cerely grateful for their willingness to devote their valuable timeand effort to this project for their readiness in sharing theirvision knowledge years of experience and know-how and alsofor their patience in tolerating various expected or unexpectedextensions arising from the busy schedules of different contribu-tors It has definitely been a privilege to work with the authorscoauthors and reviewers involved in this book The editorswould also like to extend their thanks to Wiley-Blackwell fortheir commitment to this project and to Michael Leventhalfor his organization andmanagement of the publication process
On a more personal note the editors would like to take thisopportunity to express their sincere gratitude to the late Profes-sor David L Trimm who has inspired their research in catalysisand catalytic reaction engineering through many years as super-visor mentor colleague and friend
Zeynep Ilsen OumlnsanAhmet Kerim Avci
Istanbul October 2015
Preface xiii
413 Industrial catalytic processes employingfluidized-bed reactors 82
42 Key hydrodynamic features of gas-fluidized beds 83421 Minimum fluidization velocity 83422 Powder group and minimum bubbling
velocity 84423 Flow regimes and transitions 84424 Bubbling fluidized beds 84425 Turbulent fluidization flow regime 85426 Fast fluidization and dense suspension
upflow 85
43 Key properties affecting reactor performance 86431 Particle mixing 86432 Gas mixing 87433 Heat transfer and temperature uniformity 87434 Mass transfer 88435 Entrainment 88436 Attrition 89437 Wear 89438 Agglomeration and fouling 89439 Electrostatics and other interparticle forces 89
44 Reactor modeling 89441 Basis for reactor modeling 89442 Modeling of bubbling and slugging flow
regimes 90443 Modeling of reactors operating in high-velocity
flow regimes 91
45 Scale-up pilot testing and practical issues 91451 Scale-up issues 91452 Laboratory and pilot testing 91453 Instrumentation 92454 Other practical issues 92
46 Concluding remarks 92
Nomenclature 93
Greek letters 93
References 93
Part 3 Three-phase catalytic reactors
5 Three-phase fixed-bed reactors 97Ion Iliuta and Faiumlccedilal Larachi
51 Introduction 97
52 Hydrodynamic aspects of three-phase fixed-bedreactors 98521 General aspects Flow regimes liquid holdup
two-phase pressure drop and wetting efficiency 98522 Standard two-fluid models for two-phase
downflow and upflow in three-phase fixed-bedreactors 100
523 Nonequilibrium thermomechanical models fortwo-phase flow in three-phase fixed-bedreactors 102
53 Mass and heat transfer in three-phase fixed-bedreactors 104531 Gasndashliquid mass transfer 105532 Liquidndashsolid mass transfer 105533 Heat transfer 106
54 Scale-up and scale-down of trickle-bed reactors 108541 Scaling up of trickle-bed reactors 108542 Scaling down of trickle-bed reactors 109543 Salient conclusions 110
55 Trickle-bed reactorbioreactor modeling 110551 Catalytic hydrodesulfurization and bed
clogging in hydrotreating trickle-bedreactors 110
552 Biomass accumulation and clogging intrickle-bed bioreactors for phenolbiodegradation 115
553 Integrated aqueous-phase glycerol reformingand dimethyl ether synthesis into anallothermal dual-bed reactor 121
Nomenclature 126
Greek letters 127
Subscripts 128
Superscripts 128
Abbreviations 128
References 128
6 Three-phase slurry reactors 132Vivek V Buwa Shantanu Roy and Vivek V Ranade
61 Introduction 132
62 Reactor design scale-up methodology and reactorselection 134621 Practical aspects of reactor design and
scale-up 134622 Transport effects at particle level 139
63 Reactor models for design and scale-up 143631 Lower order models 143632 Tank-in-seriesmixing cell models 144
64 Estimation of transport and hydrodynamicparameters 145641 Estimation of transport parameters 145642 Estimation of hydrodynamic parameters 146
65 Advanced computational fluid dynamics(CFD)-based models 147
66 Summary and closing remarks 149
Acknowledgments 152
Nomenclature 152
Greek letters 153
Subscripts 153
References 153
vi Contents
7 Bioreactors 156Pedro Fernandes and Joaquim MS Cabral
71 Introduction 156
72 Basic concepts configurations and modes ofoperation 156721 Basic concepts 156722 Reactor configurations and modes of
operation 157
73 Mass balances and reactor equations 159731 Operation with enzymes 159732 Operation with living cells 160
74 Immobilized enzymes and cells 164741 Mass transfer effects 164742 Deactivation effects 166
75 Aeration 166
76 Mixing 166
77 Heat transfer 167
78 Scale-up 167
79 Bioreactors for animal cell cultures 167
710 Monitoring and control of bioreactors 168
Nomenclature 168
Greek letters 169
Subscripts 169
References 169
Part 4 Structured reactors
8 Monolith reactors 173Joatildeo P Lopes and Aliacuterio E Rodrigues
81 Introduction 173811 Design concepts 174812 Applications 178
82 Design of wall-coated monolith channels 179821 Flow in monolithic channels 179822 Mass transfer and wall reaction 182823 Reaction and diffusion in the catalytic
washcoat 190824 Nonisothermal operation 194
83 Mapping and evaluation of operatingregimes 197831 Diversity in the operation of a monolith
reactor 197832 Definition of operating regimes 199833 Operating diagrams for linear kinetics 201834 Influence of nonlinear reaction kinetics 202835 Performance evaluation 203
84 Three-phase processes 204
85 Conclusions 207
Nomenclature 207
Greek letters 208
Superscripts 208
Subscripts 208
References 209
9 Microreactors for catalytic reactions 213Evgeny Rebrov and Sourav Chatterjee
91 Introduction 213
92 Single-phase catalytic microreactors 213921 Residence time distribution 213922 Effect of flow maldistribution 214923 Mass transfer 215924 Heat transfer 215
93 Multiphase microreactors 216931 Microstructured packed beds 216932 Microchannel reactors 218
94 Conclusions and outlook 225
Nomenclature 226
Greek letters 227
Subscripts 227
References 228
Part 5 Essential tools of reactor modeling and design
10 Experimental methods for the determination ofparameters 233Rebecca R Fushimi John T Gleaves and GregoryS Yablonsky
101 Introduction 233
102 Consideration of kinetic objectives 234
103 Criteria for collecting kinetic data 234
104 Experimental methods 2341041 Steady-state flow experiments 2351042 Transient flow experiments 2371043 Surface science experiments 238
105 Microkinetic approach to kinetic analysis 241
106 TAP approach to kinetic analysis 2411061 TAP experiment design 2421062 TAP experimental results 244
107 Conclusions 248
References 249
11 Numerical solution techniques 253Ahmet Kerim Avci and Seda Keskin
111 Techniques for the numerical solution of ordinarydifferential equations 2531111 Explicit techniques 2531112 Implicit techniques 254
112 Techniques for the numerical solution of partialdifferential equations 255
Contents vii
113 Computational fluid dynamics techniques 2561131 Methodology of computational fluid
dynamics 2561132 Finite element method 2561133 Finite volume method 258
114 Case studies 2591141 Indirect partial oxidation of methane in a
catalytic tubular reactor 2591142 Hydrocarbon steam reforming in
spatially segregated microchannelreactors 261
115 Summary 265
Nomenclature 266
Greek letters 267
Subscriptssuperscripts 267
References 267
Part 6 Industrial applications of multiphase reactors
12 Reactor approaches for FischerndashTropsch synthesis 271Gary Jacobs and Burtron H Davis
121 Introduction 271
122 Reactors to 1950 272
123 1950ndash1985 period 274
124 1985 to present 2761241 Fixed-bed reactors 2761242 Fluidized-bed reactors 2801243 Slurry bubble column reactors 2811244 Structured packings 2861245 Operation at supercritical conditions(SCF) 288
125 The future 288
References 291
13 Hydrotreating of oil fractions 295Jorge Ancheyta Anton Alvarez-Majmutov andCarolina Leyva
131 Introduction 295
132 The HDT process 2961321 Overview 2961322 Role in petroleum refining 2971323 World outlook and the situation ofMexico 298
133 Fundamentals of HDT 3001331 Chemistry 3001332 Reaction kinetics 3031333 Thermodynamics 3051334 Catalysts 306
134 Process aspects of HDT 3071341 Process variables 307
1342 Reactors for hydroprocessing 3101343 Catalyst activation in commercial
hydrotreaters 316
135 Reactor modeling and simulation 3171351 Process description 3171352 Summary of experiments 3171353 Modeling approach 3191354 Simulation of the bench-scale unit 3201355 Scale-up of bench-unit data 3231356 Simulation of the commercial
unit 324
Nomenclature 326
Greek letters 327
Subscripts 327
Non-SI units 327
References 327
14 Catalytic reactors for fuel processing 330Gunther Kolb
141 IntroductionmdashThe basic reactions of fuelprocessing 330
142 Theoretical aspects advantages and drawbacks offixed beds versus monoliths microreactors andmembrane reactors 331
143 Reactor design and fabrication 3321431 Fixed-bed reactors 3321432 Monolithic reactors 3321433 Microreactors 3321434 Membrane reactors 333
144 Reformers 3331441 Fixed-bed reformers 3361442 Monolithic reformers 3371443 Plate heat exchangers and microstructured
reformers 3421444 Membrane reformers 344
145 Water-gas shift reactors 3481451 Monolithic reactors 3481452 Plate heat exchangers and microstructured
water-gas shift reactors 3481453 Water-gas shift in membrane reactors 350
146 Carbon monoxide fine cleanup Preferential oxidationand selective methanation 3501461 Fixed-bed reactors 3521462 Monolithic reactors 3521463 Plate heat exchangers and microstructured
reactors 353
147 Examples of complete fuel processors 3551471 Monolithic fuel processors 3551472 Plate heat exchanger fuel processors on the
meso- and microscale 357
viii Contents
Nomenclature 359
References 359
15 Modeling of the catalytic deoxygenation of fatty acids in apacked bed reactor 365Teuvo Kilpiouml Paumlivi Maumlki-Arvela Tapio Salmi andDmitry Yu Murzin
151 Introduction 365
152 Experimental data for stearic aciddeoxygenation 366
153 Assumptions 366
154 Model equations 367
155 Evaluation of the adsorption parameters 368
156 Particle diffusion study 369
157 Parameter sensitivity studies 369
158 Parameter identification studies 370
159 Studies concerning the deviation from ideal plug flowconditions 371
1510 Parameter estimation results 372
1511 Scale-up considerations 372
1512 Conclusions 375
Acknowledgments 375
Nomenclature 375
Greek letters 375
References 376
Index 377
Contents ix
List of contributors
Anton Alvarez-MajmutovInstituto Mexicano del Petroacuteleo Management of Products for theTransformation of Crude Oil Mexico City Mexico
Jorge AncheytaInstituto Mexicano del Petroacuteleo Management of Products for theTransformation of Crude Oil Mexico City Mexico
Ahmet Kerim AvciDepartment of Chemical Engineering Boğaziccedili University Istanbul Turkey
Vivek V BuwaDepartment of Chemical EngineeringIndian Institute of Technology-Delhi New Delhi India
Joaquim MS CabralDepartment of Bioengineering and IBB-Institute for Bioengineeringand Biosciences Instituto Superior Teacutecnico Universidade de LisboaLisboa Portugal
Sourav ChatterjeeSchool of Chemistry and Chemical Engineering Queenrsquos University BelfastBelfast UK
Burtron H DavisCenter for Applied Energy Research University of KentuckyLexington KY USA
Pedro FernandesDepartment of Bioengineering and IBB-Institutefor Bioengineering and Biosciences Instituto Superior TeacutecnicoUniversidade de Lisboa Faculdade de EngenhariaUniversidade Lusoacutefona de Humanidadese Tecnologias Lisboa Portugal
Rebecca R FushimiMaterials Science amp Engineering Department Idaho National LaboratoryIdaho Falls ID USA
John T GleavesDepartment of Energy Environmental and Chemical EngineeringWashington University St Louis MO USA
John R GraceDepartment of Chemical and Biological EngineeringThe University of British Columbia VancouverBritish Columbia Canada
Ion IliutaChemical Engineering Department Laval University Queacutebec CityQueacutebec Canada
Gary JacobsCenter for Applied Energy Research University of KentuckyLexington KY USA
Seda KeskinDepartment of Chemical and Biological Engineering Koc UniversityIstanbul Turkey
Teuvo KilpioumlProcess Chemistry Centre Aringbo Akademi University TurkuAringbo Finland
Gunther KolbFraunhofer ICT-IMM Decentralized and Mobile Energy TechnologyDepartment Mainz Germany
Faiumlccedilal LarachiChemical Engineering Department Laval University Queacutebec CityQueacutebec Canada
Carolina LeyvaCentro de Investigacioacuten en Ciencia Aplicada y Tecnologiacutea AvanzadaUnidad Legaria Instituto Politeacutecnico Nacional Mexico City Mexico
Joatildeo P LopesDepartment of Chemical Engineering and BiotechnologyUniversity of Cambridge Cambridge UK
Paumlivi Maumlki-ArvelaProcess Chemistry Centre Aringbo Akademi University TurkuAringbo Finland
Dmitry Yu MurzinProcess Chemistry Centre Aringbo Akademi University TurkuAringbo Finland
Zeynep Ilsen OumlnsanDepartment of Chemical Engineering Boğaziccedili University Istanbul Turkey
Vivek V RanadeChemical Engineering amp Process Development Division National ChemicalLaboratory Pune India
Evgeny RebrovSchool of Engineering University of Warwick Coventry UK
x
Aliacuterio E RodriguesLaboratory of Separation and Reaction EngineeringAssociate Laboratory LSRELCM Department of Chemical EngineeringFaculty of Engineering University of Porto Porto Portugal
Shantanu RoyDepartment of Chemical Engineering Indian Institute of Technology-DelhiNew Delhi India
Tapio SalmiProcess Chemistry Centre Aringbo Akademi UniversityTurkuAringbo Finland
Gregory S YablonskyParks College of Engineering Aviation and TechnologySaint Louis University St Louis MO USA
List of contributors xi
Preface
The single irreplaceable component at the core of a chemicalprocess is the chemical reactor where feed materials are con-verted into desirable products Although the essential variablesby which chemical processes can be controlled are reaction tem-perature pressure feed composition and residence time in thereactor two technological developments of major consequencestarting with 1960s have made possible cost-effective operationunder less severe conditions these are the extensive use of effi-cient catalysts and the introduction of improved or innovativereactor configurations The impact of heterogeneous catalysisis significant in this respect since petroleum refining manufac-turing of chemicals and environmental clean-up which are thethree major areas of the world economy today all requirethe effective use of solid catalysts The challenges involved inthe design of novel solid catalysts and modification of manyexisting ones for higher selectivity and stability have alsoprompted the development of ldquoengineeredrdquo catalysts befittingnovel reactor configurations requiring the use of new supportssuch as monolithic or foam substrates as well as the establish-ment of new techniques for coating surfaces with diverse catalystcomponents in order to ensure longevity particularly in cyclicprocessesIn industrial practice the composition and properties of the
complex feed mixtures that are processed for producing a rangeof valuable chemicals generally necessitate the use of heteroge-neous catalytic reactors Numerous chemical and physical rateprocesses take place in a heterogeneous reactor at differentlength and time scales and frequently in different phasesThe prerequisite for the successful design and operation of cat-alytic reactors is a thorough microkinetic analysis starting fromintrinsic kinetic models of the steady-state chemical activity andleading to global rate expressions obtained by overlaying theeffects of physical rate phenomena occurring at the particlescale Kinetic models of increasing complexity may be requireddepending on the variety of components and number of reac-tions involved The second critical stage in reactor modelingand design is a macrokinetic analysis including the detaileddescription of physical transport phenomena at the reactor scaleand utilizing the global rate expressions of the microkineticanalysis The final catalytic reactor model which integrates theseessential stages can successfully predict the performance anddynamics of plant-scale industrial reactors as well as simulatingtheir start-up shutdown and cyclic operation Taking intoaccount engineered catalysts and new reactor configurations
the modeling and scaling up of reactions conducted at thebench-scale to pilot plant and industrial-scale reactor levels haveto be modified in order to include simultaneous multiscaleapproaches along with the conventional sequential modesMultiphase Catalytic Reactors Theory Design Manufactur-
ing and Applications is a comprehensive up-to-date compila-tion on multiphase catalytic reactors which will serve as anexcellent reference book for graduate students researchersand specialists both in academia and in industry The contentof the book is planned to cover topics starting from the firstprinciples involved in macrokinetic analysis of two- andthree-phase catalytic reactors to their particular industrial appli-cations The main objective is to provide definitive accounts onacademic aspects of multiphase catalytic reactor modeling anddesign along with detailed descriptions of some of the mostrecent industrial applications employing multiphase catalyticreactors in such a way as to balance the academic and industrialcomponents as much as possible Accordingly seven chaptersare included in Parts II III and IV to review the relevantmathematical models and model equations utilized in the fun-damental analysis and macroscopic design of specific reactortypes together with some useful approximations for theirdesign and scale-up from a practical standpoint while the fourchapters in Part VI describe specific industrial applications andcontain pointers that tie in with the modeling and designapproaches presented for the particular multiphase catalyticreactor types discussed in Parts II III and IV Furthermorethe chapters included in Parts I and V of the book containdetailed reviews of the basic principles and essential tools ofcatalytic reaction engineering that are crucial for the successfuldesign and operation of catalytic reactors All chapters ofthe book are contributed by experts distinguished in theirrespective fieldsThe total of 15 chapters included in Multiphase Catalytic
Reactors Theory Design Manufacturing and Applications areorganized in six parts Part I is an overview of the principlesof catalytic reaction engineering embracing Chapter 1 whichis a survey of multiphase catalytic reactor types and their indus-trial significance as well as Chapter 2 on the microkinetic anal-ysis of heterogeneous catalytic systems which surveys theformulation of intrinsic rate equations describing chemical rateprocesses and the construction of global rate expressions thatinclude the effects of physical mass and heat transport phenom-ena occurring at the particle scale Chapters 3 through 9 in
xii
Parts II III and IV discuss individual two- and three-phase cat-alytic reactor types and provide design equations and empiricalrelationships that characterize different multiphase reactorsmathematical modeling is an integral part of these chaptersIn Part II two-phase catalytic reactors are grouped as fixed-bed gasndashsolid catalytic reactors (Chapter 3) and fluidized-bedcatalytic reactors (Chapter 4) Part III deals exclusively withthree-phase catalytic reactors and includes Chapter 5 onthree-phase fixed-bed reactors as well as Chapter 6 on three-phase slurry reactors both of which find significant industrialapplications moreover multiphase bioreactors are also includedin Part III as Chapter 7 Part IV is devoted to the discussion ofthe more recent state-of-the-art structured reactors the theoret-ical aspects and examples of structured reactors enabling processintensification in multiphase operation are treated in Chapter 8on monolith reactors and in Chapter 9 on microreactors of dif-ferent configurations including microstructured packed bedsand microchannel reactors Part V of the book is specificallydesigned for surveying the essential tools of catalytic reactormodeling and design and comprises two chapters Chapter 10discusses the recent developments and experimental techniquesinvolved in lab-scale testing of catalytic reactions includingsteady-state and transient flow experiments as well as the micro-kinetic and TAP approaches to kinetic analysis whileChapter 11 surveys the numerical solution techniques that arefrequently used in catalytic reactor analysis and demonstrateswith some case studies The capstone section of the bookPart VI contains four chapters devoted to specific industrialapplications of multiphase catalytic reactors and includes the
recent developments and practices in FischerndashTropsch technol-ogies (Chapter 12) a thorough discussion of reactor modelingsimulation and scale-up approaches involved in the hydrotreat-ing of oil fractions (Chapter 13) a detailed assessment of theperformances of various reactor configurations used for fuelprocessing (Chapter 14) and a comprehensive discussion ofcatalytic deoxygenation of fatty acids in a packed-bed reactoras case study in production of biofuels (Chapter 15)
It is indeed a pleasure to thank all of the contributors whohave made this challenging task achievable The editors are sin-cerely grateful for their willingness to devote their valuable timeand effort to this project for their readiness in sharing theirvision knowledge years of experience and know-how and alsofor their patience in tolerating various expected or unexpectedextensions arising from the busy schedules of different contribu-tors It has definitely been a privilege to work with the authorscoauthors and reviewers involved in this book The editorswould also like to extend their thanks to Wiley-Blackwell fortheir commitment to this project and to Michael Leventhalfor his organization andmanagement of the publication process
On a more personal note the editors would like to take thisopportunity to express their sincere gratitude to the late Profes-sor David L Trimm who has inspired their research in catalysisand catalytic reaction engineering through many years as super-visor mentor colleague and friend
Zeynep Ilsen OumlnsanAhmet Kerim Avci
Istanbul October 2015
Preface xiii
7 Bioreactors 156Pedro Fernandes and Joaquim MS Cabral
71 Introduction 156
72 Basic concepts configurations and modes ofoperation 156721 Basic concepts 156722 Reactor configurations and modes of
operation 157
73 Mass balances and reactor equations 159731 Operation with enzymes 159732 Operation with living cells 160
74 Immobilized enzymes and cells 164741 Mass transfer effects 164742 Deactivation effects 166
75 Aeration 166
76 Mixing 166
77 Heat transfer 167
78 Scale-up 167
79 Bioreactors for animal cell cultures 167
710 Monitoring and control of bioreactors 168
Nomenclature 168
Greek letters 169
Subscripts 169
References 169
Part 4 Structured reactors
8 Monolith reactors 173Joatildeo P Lopes and Aliacuterio E Rodrigues
81 Introduction 173811 Design concepts 174812 Applications 178
82 Design of wall-coated monolith channels 179821 Flow in monolithic channels 179822 Mass transfer and wall reaction 182823 Reaction and diffusion in the catalytic
washcoat 190824 Nonisothermal operation 194
83 Mapping and evaluation of operatingregimes 197831 Diversity in the operation of a monolith
reactor 197832 Definition of operating regimes 199833 Operating diagrams for linear kinetics 201834 Influence of nonlinear reaction kinetics 202835 Performance evaluation 203
84 Three-phase processes 204
85 Conclusions 207
Nomenclature 207
Greek letters 208
Superscripts 208
Subscripts 208
References 209
9 Microreactors for catalytic reactions 213Evgeny Rebrov and Sourav Chatterjee
91 Introduction 213
92 Single-phase catalytic microreactors 213921 Residence time distribution 213922 Effect of flow maldistribution 214923 Mass transfer 215924 Heat transfer 215
93 Multiphase microreactors 216931 Microstructured packed beds 216932 Microchannel reactors 218
94 Conclusions and outlook 225
Nomenclature 226
Greek letters 227
Subscripts 227
References 228
Part 5 Essential tools of reactor modeling and design
10 Experimental methods for the determination ofparameters 233Rebecca R Fushimi John T Gleaves and GregoryS Yablonsky
101 Introduction 233
102 Consideration of kinetic objectives 234
103 Criteria for collecting kinetic data 234
104 Experimental methods 2341041 Steady-state flow experiments 2351042 Transient flow experiments 2371043 Surface science experiments 238
105 Microkinetic approach to kinetic analysis 241
106 TAP approach to kinetic analysis 2411061 TAP experiment design 2421062 TAP experimental results 244
107 Conclusions 248
References 249
11 Numerical solution techniques 253Ahmet Kerim Avci and Seda Keskin
111 Techniques for the numerical solution of ordinarydifferential equations 2531111 Explicit techniques 2531112 Implicit techniques 254
112 Techniques for the numerical solution of partialdifferential equations 255
Contents vii
113 Computational fluid dynamics techniques 2561131 Methodology of computational fluid
dynamics 2561132 Finite element method 2561133 Finite volume method 258
114 Case studies 2591141 Indirect partial oxidation of methane in a
catalytic tubular reactor 2591142 Hydrocarbon steam reforming in
spatially segregated microchannelreactors 261
115 Summary 265
Nomenclature 266
Greek letters 267
Subscriptssuperscripts 267
References 267
Part 6 Industrial applications of multiphase reactors
12 Reactor approaches for FischerndashTropsch synthesis 271Gary Jacobs and Burtron H Davis
121 Introduction 271
122 Reactors to 1950 272
123 1950ndash1985 period 274
124 1985 to present 2761241 Fixed-bed reactors 2761242 Fluidized-bed reactors 2801243 Slurry bubble column reactors 2811244 Structured packings 2861245 Operation at supercritical conditions(SCF) 288
125 The future 288
References 291
13 Hydrotreating of oil fractions 295Jorge Ancheyta Anton Alvarez-Majmutov andCarolina Leyva
131 Introduction 295
132 The HDT process 2961321 Overview 2961322 Role in petroleum refining 2971323 World outlook and the situation ofMexico 298
133 Fundamentals of HDT 3001331 Chemistry 3001332 Reaction kinetics 3031333 Thermodynamics 3051334 Catalysts 306
134 Process aspects of HDT 3071341 Process variables 307
1342 Reactors for hydroprocessing 3101343 Catalyst activation in commercial
hydrotreaters 316
135 Reactor modeling and simulation 3171351 Process description 3171352 Summary of experiments 3171353 Modeling approach 3191354 Simulation of the bench-scale unit 3201355 Scale-up of bench-unit data 3231356 Simulation of the commercial
unit 324
Nomenclature 326
Greek letters 327
Subscripts 327
Non-SI units 327
References 327
14 Catalytic reactors for fuel processing 330Gunther Kolb
141 IntroductionmdashThe basic reactions of fuelprocessing 330
142 Theoretical aspects advantages and drawbacks offixed beds versus monoliths microreactors andmembrane reactors 331
143 Reactor design and fabrication 3321431 Fixed-bed reactors 3321432 Monolithic reactors 3321433 Microreactors 3321434 Membrane reactors 333
144 Reformers 3331441 Fixed-bed reformers 3361442 Monolithic reformers 3371443 Plate heat exchangers and microstructured
reformers 3421444 Membrane reformers 344
145 Water-gas shift reactors 3481451 Monolithic reactors 3481452 Plate heat exchangers and microstructured
water-gas shift reactors 3481453 Water-gas shift in membrane reactors 350
146 Carbon monoxide fine cleanup Preferential oxidationand selective methanation 3501461 Fixed-bed reactors 3521462 Monolithic reactors 3521463 Plate heat exchangers and microstructured
reactors 353
147 Examples of complete fuel processors 3551471 Monolithic fuel processors 3551472 Plate heat exchanger fuel processors on the
meso- and microscale 357
viii Contents
Nomenclature 359
References 359
15 Modeling of the catalytic deoxygenation of fatty acids in apacked bed reactor 365Teuvo Kilpiouml Paumlivi Maumlki-Arvela Tapio Salmi andDmitry Yu Murzin
151 Introduction 365
152 Experimental data for stearic aciddeoxygenation 366
153 Assumptions 366
154 Model equations 367
155 Evaluation of the adsorption parameters 368
156 Particle diffusion study 369
157 Parameter sensitivity studies 369
158 Parameter identification studies 370
159 Studies concerning the deviation from ideal plug flowconditions 371
1510 Parameter estimation results 372
1511 Scale-up considerations 372
1512 Conclusions 375
Acknowledgments 375
Nomenclature 375
Greek letters 375
References 376
Index 377
Contents ix
List of contributors
Anton Alvarez-MajmutovInstituto Mexicano del Petroacuteleo Management of Products for theTransformation of Crude Oil Mexico City Mexico
Jorge AncheytaInstituto Mexicano del Petroacuteleo Management of Products for theTransformation of Crude Oil Mexico City Mexico
Ahmet Kerim AvciDepartment of Chemical Engineering Boğaziccedili University Istanbul Turkey
Vivek V BuwaDepartment of Chemical EngineeringIndian Institute of Technology-Delhi New Delhi India
Joaquim MS CabralDepartment of Bioengineering and IBB-Institute for Bioengineeringand Biosciences Instituto Superior Teacutecnico Universidade de LisboaLisboa Portugal
Sourav ChatterjeeSchool of Chemistry and Chemical Engineering Queenrsquos University BelfastBelfast UK
Burtron H DavisCenter for Applied Energy Research University of KentuckyLexington KY USA
Pedro FernandesDepartment of Bioengineering and IBB-Institutefor Bioengineering and Biosciences Instituto Superior TeacutecnicoUniversidade de Lisboa Faculdade de EngenhariaUniversidade Lusoacutefona de Humanidadese Tecnologias Lisboa Portugal
Rebecca R FushimiMaterials Science amp Engineering Department Idaho National LaboratoryIdaho Falls ID USA
John T GleavesDepartment of Energy Environmental and Chemical EngineeringWashington University St Louis MO USA
John R GraceDepartment of Chemical and Biological EngineeringThe University of British Columbia VancouverBritish Columbia Canada
Ion IliutaChemical Engineering Department Laval University Queacutebec CityQueacutebec Canada
Gary JacobsCenter for Applied Energy Research University of KentuckyLexington KY USA
Seda KeskinDepartment of Chemical and Biological Engineering Koc UniversityIstanbul Turkey
Teuvo KilpioumlProcess Chemistry Centre Aringbo Akademi University TurkuAringbo Finland
Gunther KolbFraunhofer ICT-IMM Decentralized and Mobile Energy TechnologyDepartment Mainz Germany
Faiumlccedilal LarachiChemical Engineering Department Laval University Queacutebec CityQueacutebec Canada
Carolina LeyvaCentro de Investigacioacuten en Ciencia Aplicada y Tecnologiacutea AvanzadaUnidad Legaria Instituto Politeacutecnico Nacional Mexico City Mexico
Joatildeo P LopesDepartment of Chemical Engineering and BiotechnologyUniversity of Cambridge Cambridge UK
Paumlivi Maumlki-ArvelaProcess Chemistry Centre Aringbo Akademi University TurkuAringbo Finland
Dmitry Yu MurzinProcess Chemistry Centre Aringbo Akademi University TurkuAringbo Finland
Zeynep Ilsen OumlnsanDepartment of Chemical Engineering Boğaziccedili University Istanbul Turkey
Vivek V RanadeChemical Engineering amp Process Development Division National ChemicalLaboratory Pune India
Evgeny RebrovSchool of Engineering University of Warwick Coventry UK
x
Aliacuterio E RodriguesLaboratory of Separation and Reaction EngineeringAssociate Laboratory LSRELCM Department of Chemical EngineeringFaculty of Engineering University of Porto Porto Portugal
Shantanu RoyDepartment of Chemical Engineering Indian Institute of Technology-DelhiNew Delhi India
Tapio SalmiProcess Chemistry Centre Aringbo Akademi UniversityTurkuAringbo Finland
Gregory S YablonskyParks College of Engineering Aviation and TechnologySaint Louis University St Louis MO USA
List of contributors xi
Preface
The single irreplaceable component at the core of a chemicalprocess is the chemical reactor where feed materials are con-verted into desirable products Although the essential variablesby which chemical processes can be controlled are reaction tem-perature pressure feed composition and residence time in thereactor two technological developments of major consequencestarting with 1960s have made possible cost-effective operationunder less severe conditions these are the extensive use of effi-cient catalysts and the introduction of improved or innovativereactor configurations The impact of heterogeneous catalysisis significant in this respect since petroleum refining manufac-turing of chemicals and environmental clean-up which are thethree major areas of the world economy today all requirethe effective use of solid catalysts The challenges involved inthe design of novel solid catalysts and modification of manyexisting ones for higher selectivity and stability have alsoprompted the development of ldquoengineeredrdquo catalysts befittingnovel reactor configurations requiring the use of new supportssuch as monolithic or foam substrates as well as the establish-ment of new techniques for coating surfaces with diverse catalystcomponents in order to ensure longevity particularly in cyclicprocessesIn industrial practice the composition and properties of the
complex feed mixtures that are processed for producing a rangeof valuable chemicals generally necessitate the use of heteroge-neous catalytic reactors Numerous chemical and physical rateprocesses take place in a heterogeneous reactor at differentlength and time scales and frequently in different phasesThe prerequisite for the successful design and operation of cat-alytic reactors is a thorough microkinetic analysis starting fromintrinsic kinetic models of the steady-state chemical activity andleading to global rate expressions obtained by overlaying theeffects of physical rate phenomena occurring at the particlescale Kinetic models of increasing complexity may be requireddepending on the variety of components and number of reac-tions involved The second critical stage in reactor modelingand design is a macrokinetic analysis including the detaileddescription of physical transport phenomena at the reactor scaleand utilizing the global rate expressions of the microkineticanalysis The final catalytic reactor model which integrates theseessential stages can successfully predict the performance anddynamics of plant-scale industrial reactors as well as simulatingtheir start-up shutdown and cyclic operation Taking intoaccount engineered catalysts and new reactor configurations
the modeling and scaling up of reactions conducted at thebench-scale to pilot plant and industrial-scale reactor levels haveto be modified in order to include simultaneous multiscaleapproaches along with the conventional sequential modesMultiphase Catalytic Reactors Theory Design Manufactur-
ing and Applications is a comprehensive up-to-date compila-tion on multiphase catalytic reactors which will serve as anexcellent reference book for graduate students researchersand specialists both in academia and in industry The contentof the book is planned to cover topics starting from the firstprinciples involved in macrokinetic analysis of two- andthree-phase catalytic reactors to their particular industrial appli-cations The main objective is to provide definitive accounts onacademic aspects of multiphase catalytic reactor modeling anddesign along with detailed descriptions of some of the mostrecent industrial applications employing multiphase catalyticreactors in such a way as to balance the academic and industrialcomponents as much as possible Accordingly seven chaptersare included in Parts II III and IV to review the relevantmathematical models and model equations utilized in the fun-damental analysis and macroscopic design of specific reactortypes together with some useful approximations for theirdesign and scale-up from a practical standpoint while the fourchapters in Part VI describe specific industrial applications andcontain pointers that tie in with the modeling and designapproaches presented for the particular multiphase catalyticreactor types discussed in Parts II III and IV Furthermorethe chapters included in Parts I and V of the book containdetailed reviews of the basic principles and essential tools ofcatalytic reaction engineering that are crucial for the successfuldesign and operation of catalytic reactors All chapters ofthe book are contributed by experts distinguished in theirrespective fieldsThe total of 15 chapters included in Multiphase Catalytic
Reactors Theory Design Manufacturing and Applications areorganized in six parts Part I is an overview of the principlesof catalytic reaction engineering embracing Chapter 1 whichis a survey of multiphase catalytic reactor types and their indus-trial significance as well as Chapter 2 on the microkinetic anal-ysis of heterogeneous catalytic systems which surveys theformulation of intrinsic rate equations describing chemical rateprocesses and the construction of global rate expressions thatinclude the effects of physical mass and heat transport phenom-ena occurring at the particle scale Chapters 3 through 9 in
xii
Parts II III and IV discuss individual two- and three-phase cat-alytic reactor types and provide design equations and empiricalrelationships that characterize different multiphase reactorsmathematical modeling is an integral part of these chaptersIn Part II two-phase catalytic reactors are grouped as fixed-bed gasndashsolid catalytic reactors (Chapter 3) and fluidized-bedcatalytic reactors (Chapter 4) Part III deals exclusively withthree-phase catalytic reactors and includes Chapter 5 onthree-phase fixed-bed reactors as well as Chapter 6 on three-phase slurry reactors both of which find significant industrialapplications moreover multiphase bioreactors are also includedin Part III as Chapter 7 Part IV is devoted to the discussion ofthe more recent state-of-the-art structured reactors the theoret-ical aspects and examples of structured reactors enabling processintensification in multiphase operation are treated in Chapter 8on monolith reactors and in Chapter 9 on microreactors of dif-ferent configurations including microstructured packed bedsand microchannel reactors Part V of the book is specificallydesigned for surveying the essential tools of catalytic reactormodeling and design and comprises two chapters Chapter 10discusses the recent developments and experimental techniquesinvolved in lab-scale testing of catalytic reactions includingsteady-state and transient flow experiments as well as the micro-kinetic and TAP approaches to kinetic analysis whileChapter 11 surveys the numerical solution techniques that arefrequently used in catalytic reactor analysis and demonstrateswith some case studies The capstone section of the bookPart VI contains four chapters devoted to specific industrialapplications of multiphase catalytic reactors and includes the
recent developments and practices in FischerndashTropsch technol-ogies (Chapter 12) a thorough discussion of reactor modelingsimulation and scale-up approaches involved in the hydrotreat-ing of oil fractions (Chapter 13) a detailed assessment of theperformances of various reactor configurations used for fuelprocessing (Chapter 14) and a comprehensive discussion ofcatalytic deoxygenation of fatty acids in a packed-bed reactoras case study in production of biofuels (Chapter 15)
It is indeed a pleasure to thank all of the contributors whohave made this challenging task achievable The editors are sin-cerely grateful for their willingness to devote their valuable timeand effort to this project for their readiness in sharing theirvision knowledge years of experience and know-how and alsofor their patience in tolerating various expected or unexpectedextensions arising from the busy schedules of different contribu-tors It has definitely been a privilege to work with the authorscoauthors and reviewers involved in this book The editorswould also like to extend their thanks to Wiley-Blackwell fortheir commitment to this project and to Michael Leventhalfor his organization andmanagement of the publication process
On a more personal note the editors would like to take thisopportunity to express their sincere gratitude to the late Profes-sor David L Trimm who has inspired their research in catalysisand catalytic reaction engineering through many years as super-visor mentor colleague and friend
Zeynep Ilsen OumlnsanAhmet Kerim Avci
Istanbul October 2015
Preface xiii
113 Computational fluid dynamics techniques 2561131 Methodology of computational fluid
dynamics 2561132 Finite element method 2561133 Finite volume method 258
114 Case studies 2591141 Indirect partial oxidation of methane in a
catalytic tubular reactor 2591142 Hydrocarbon steam reforming in
spatially segregated microchannelreactors 261
115 Summary 265
Nomenclature 266
Greek letters 267
Subscriptssuperscripts 267
References 267
Part 6 Industrial applications of multiphase reactors
12 Reactor approaches for FischerndashTropsch synthesis 271Gary Jacobs and Burtron H Davis
121 Introduction 271
122 Reactors to 1950 272
123 1950ndash1985 period 274
124 1985 to present 2761241 Fixed-bed reactors 2761242 Fluidized-bed reactors 2801243 Slurry bubble column reactors 2811244 Structured packings 2861245 Operation at supercritical conditions(SCF) 288
125 The future 288
References 291
13 Hydrotreating of oil fractions 295Jorge Ancheyta Anton Alvarez-Majmutov andCarolina Leyva
131 Introduction 295
132 The HDT process 2961321 Overview 2961322 Role in petroleum refining 2971323 World outlook and the situation ofMexico 298
133 Fundamentals of HDT 3001331 Chemistry 3001332 Reaction kinetics 3031333 Thermodynamics 3051334 Catalysts 306
134 Process aspects of HDT 3071341 Process variables 307
1342 Reactors for hydroprocessing 3101343 Catalyst activation in commercial
hydrotreaters 316
135 Reactor modeling and simulation 3171351 Process description 3171352 Summary of experiments 3171353 Modeling approach 3191354 Simulation of the bench-scale unit 3201355 Scale-up of bench-unit data 3231356 Simulation of the commercial
unit 324
Nomenclature 326
Greek letters 327
Subscripts 327
Non-SI units 327
References 327
14 Catalytic reactors for fuel processing 330Gunther Kolb
141 IntroductionmdashThe basic reactions of fuelprocessing 330
142 Theoretical aspects advantages and drawbacks offixed beds versus monoliths microreactors andmembrane reactors 331
143 Reactor design and fabrication 3321431 Fixed-bed reactors 3321432 Monolithic reactors 3321433 Microreactors 3321434 Membrane reactors 333
144 Reformers 3331441 Fixed-bed reformers 3361442 Monolithic reformers 3371443 Plate heat exchangers and microstructured
reformers 3421444 Membrane reformers 344
145 Water-gas shift reactors 3481451 Monolithic reactors 3481452 Plate heat exchangers and microstructured
water-gas shift reactors 3481453 Water-gas shift in membrane reactors 350
146 Carbon monoxide fine cleanup Preferential oxidationand selective methanation 3501461 Fixed-bed reactors 3521462 Monolithic reactors 3521463 Plate heat exchangers and microstructured
reactors 353
147 Examples of complete fuel processors 3551471 Monolithic fuel processors 3551472 Plate heat exchanger fuel processors on the
meso- and microscale 357
viii Contents
Nomenclature 359
References 359
15 Modeling of the catalytic deoxygenation of fatty acids in apacked bed reactor 365Teuvo Kilpiouml Paumlivi Maumlki-Arvela Tapio Salmi andDmitry Yu Murzin
151 Introduction 365
152 Experimental data for stearic aciddeoxygenation 366
153 Assumptions 366
154 Model equations 367
155 Evaluation of the adsorption parameters 368
156 Particle diffusion study 369
157 Parameter sensitivity studies 369
158 Parameter identification studies 370
159 Studies concerning the deviation from ideal plug flowconditions 371
1510 Parameter estimation results 372
1511 Scale-up considerations 372
1512 Conclusions 375
Acknowledgments 375
Nomenclature 375
Greek letters 375
References 376
Index 377
Contents ix
List of contributors
Anton Alvarez-MajmutovInstituto Mexicano del Petroacuteleo Management of Products for theTransformation of Crude Oil Mexico City Mexico
Jorge AncheytaInstituto Mexicano del Petroacuteleo Management of Products for theTransformation of Crude Oil Mexico City Mexico
Ahmet Kerim AvciDepartment of Chemical Engineering Boğaziccedili University Istanbul Turkey
Vivek V BuwaDepartment of Chemical EngineeringIndian Institute of Technology-Delhi New Delhi India
Joaquim MS CabralDepartment of Bioengineering and IBB-Institute for Bioengineeringand Biosciences Instituto Superior Teacutecnico Universidade de LisboaLisboa Portugal
Sourav ChatterjeeSchool of Chemistry and Chemical Engineering Queenrsquos University BelfastBelfast UK
Burtron H DavisCenter for Applied Energy Research University of KentuckyLexington KY USA
Pedro FernandesDepartment of Bioengineering and IBB-Institutefor Bioengineering and Biosciences Instituto Superior TeacutecnicoUniversidade de Lisboa Faculdade de EngenhariaUniversidade Lusoacutefona de Humanidadese Tecnologias Lisboa Portugal
Rebecca R FushimiMaterials Science amp Engineering Department Idaho National LaboratoryIdaho Falls ID USA
John T GleavesDepartment of Energy Environmental and Chemical EngineeringWashington University St Louis MO USA
John R GraceDepartment of Chemical and Biological EngineeringThe University of British Columbia VancouverBritish Columbia Canada
Ion IliutaChemical Engineering Department Laval University Queacutebec CityQueacutebec Canada
Gary JacobsCenter for Applied Energy Research University of KentuckyLexington KY USA
Seda KeskinDepartment of Chemical and Biological Engineering Koc UniversityIstanbul Turkey
Teuvo KilpioumlProcess Chemistry Centre Aringbo Akademi University TurkuAringbo Finland
Gunther KolbFraunhofer ICT-IMM Decentralized and Mobile Energy TechnologyDepartment Mainz Germany
Faiumlccedilal LarachiChemical Engineering Department Laval University Queacutebec CityQueacutebec Canada
Carolina LeyvaCentro de Investigacioacuten en Ciencia Aplicada y Tecnologiacutea AvanzadaUnidad Legaria Instituto Politeacutecnico Nacional Mexico City Mexico
Joatildeo P LopesDepartment of Chemical Engineering and BiotechnologyUniversity of Cambridge Cambridge UK
Paumlivi Maumlki-ArvelaProcess Chemistry Centre Aringbo Akademi University TurkuAringbo Finland
Dmitry Yu MurzinProcess Chemistry Centre Aringbo Akademi University TurkuAringbo Finland
Zeynep Ilsen OumlnsanDepartment of Chemical Engineering Boğaziccedili University Istanbul Turkey
Vivek V RanadeChemical Engineering amp Process Development Division National ChemicalLaboratory Pune India
Evgeny RebrovSchool of Engineering University of Warwick Coventry UK
x
Aliacuterio E RodriguesLaboratory of Separation and Reaction EngineeringAssociate Laboratory LSRELCM Department of Chemical EngineeringFaculty of Engineering University of Porto Porto Portugal
Shantanu RoyDepartment of Chemical Engineering Indian Institute of Technology-DelhiNew Delhi India
Tapio SalmiProcess Chemistry Centre Aringbo Akademi UniversityTurkuAringbo Finland
Gregory S YablonskyParks College of Engineering Aviation and TechnologySaint Louis University St Louis MO USA
List of contributors xi
Preface
The single irreplaceable component at the core of a chemicalprocess is the chemical reactor where feed materials are con-verted into desirable products Although the essential variablesby which chemical processes can be controlled are reaction tem-perature pressure feed composition and residence time in thereactor two technological developments of major consequencestarting with 1960s have made possible cost-effective operationunder less severe conditions these are the extensive use of effi-cient catalysts and the introduction of improved or innovativereactor configurations The impact of heterogeneous catalysisis significant in this respect since petroleum refining manufac-turing of chemicals and environmental clean-up which are thethree major areas of the world economy today all requirethe effective use of solid catalysts The challenges involved inthe design of novel solid catalysts and modification of manyexisting ones for higher selectivity and stability have alsoprompted the development of ldquoengineeredrdquo catalysts befittingnovel reactor configurations requiring the use of new supportssuch as monolithic or foam substrates as well as the establish-ment of new techniques for coating surfaces with diverse catalystcomponents in order to ensure longevity particularly in cyclicprocessesIn industrial practice the composition and properties of the
complex feed mixtures that are processed for producing a rangeof valuable chemicals generally necessitate the use of heteroge-neous catalytic reactors Numerous chemical and physical rateprocesses take place in a heterogeneous reactor at differentlength and time scales and frequently in different phasesThe prerequisite for the successful design and operation of cat-alytic reactors is a thorough microkinetic analysis starting fromintrinsic kinetic models of the steady-state chemical activity andleading to global rate expressions obtained by overlaying theeffects of physical rate phenomena occurring at the particlescale Kinetic models of increasing complexity may be requireddepending on the variety of components and number of reac-tions involved The second critical stage in reactor modelingand design is a macrokinetic analysis including the detaileddescription of physical transport phenomena at the reactor scaleand utilizing the global rate expressions of the microkineticanalysis The final catalytic reactor model which integrates theseessential stages can successfully predict the performance anddynamics of plant-scale industrial reactors as well as simulatingtheir start-up shutdown and cyclic operation Taking intoaccount engineered catalysts and new reactor configurations
the modeling and scaling up of reactions conducted at thebench-scale to pilot plant and industrial-scale reactor levels haveto be modified in order to include simultaneous multiscaleapproaches along with the conventional sequential modesMultiphase Catalytic Reactors Theory Design Manufactur-
ing and Applications is a comprehensive up-to-date compila-tion on multiphase catalytic reactors which will serve as anexcellent reference book for graduate students researchersand specialists both in academia and in industry The contentof the book is planned to cover topics starting from the firstprinciples involved in macrokinetic analysis of two- andthree-phase catalytic reactors to their particular industrial appli-cations The main objective is to provide definitive accounts onacademic aspects of multiphase catalytic reactor modeling anddesign along with detailed descriptions of some of the mostrecent industrial applications employing multiphase catalyticreactors in such a way as to balance the academic and industrialcomponents as much as possible Accordingly seven chaptersare included in Parts II III and IV to review the relevantmathematical models and model equations utilized in the fun-damental analysis and macroscopic design of specific reactortypes together with some useful approximations for theirdesign and scale-up from a practical standpoint while the fourchapters in Part VI describe specific industrial applications andcontain pointers that tie in with the modeling and designapproaches presented for the particular multiphase catalyticreactor types discussed in Parts II III and IV Furthermorethe chapters included in Parts I and V of the book containdetailed reviews of the basic principles and essential tools ofcatalytic reaction engineering that are crucial for the successfuldesign and operation of catalytic reactors All chapters ofthe book are contributed by experts distinguished in theirrespective fieldsThe total of 15 chapters included in Multiphase Catalytic
Reactors Theory Design Manufacturing and Applications areorganized in six parts Part I is an overview of the principlesof catalytic reaction engineering embracing Chapter 1 whichis a survey of multiphase catalytic reactor types and their indus-trial significance as well as Chapter 2 on the microkinetic anal-ysis of heterogeneous catalytic systems which surveys theformulation of intrinsic rate equations describing chemical rateprocesses and the construction of global rate expressions thatinclude the effects of physical mass and heat transport phenom-ena occurring at the particle scale Chapters 3 through 9 in
xii
Parts II III and IV discuss individual two- and three-phase cat-alytic reactor types and provide design equations and empiricalrelationships that characterize different multiphase reactorsmathematical modeling is an integral part of these chaptersIn Part II two-phase catalytic reactors are grouped as fixed-bed gasndashsolid catalytic reactors (Chapter 3) and fluidized-bedcatalytic reactors (Chapter 4) Part III deals exclusively withthree-phase catalytic reactors and includes Chapter 5 onthree-phase fixed-bed reactors as well as Chapter 6 on three-phase slurry reactors both of which find significant industrialapplications moreover multiphase bioreactors are also includedin Part III as Chapter 7 Part IV is devoted to the discussion ofthe more recent state-of-the-art structured reactors the theoret-ical aspects and examples of structured reactors enabling processintensification in multiphase operation are treated in Chapter 8on monolith reactors and in Chapter 9 on microreactors of dif-ferent configurations including microstructured packed bedsand microchannel reactors Part V of the book is specificallydesigned for surveying the essential tools of catalytic reactormodeling and design and comprises two chapters Chapter 10discusses the recent developments and experimental techniquesinvolved in lab-scale testing of catalytic reactions includingsteady-state and transient flow experiments as well as the micro-kinetic and TAP approaches to kinetic analysis whileChapter 11 surveys the numerical solution techniques that arefrequently used in catalytic reactor analysis and demonstrateswith some case studies The capstone section of the bookPart VI contains four chapters devoted to specific industrialapplications of multiphase catalytic reactors and includes the
recent developments and practices in FischerndashTropsch technol-ogies (Chapter 12) a thorough discussion of reactor modelingsimulation and scale-up approaches involved in the hydrotreat-ing of oil fractions (Chapter 13) a detailed assessment of theperformances of various reactor configurations used for fuelprocessing (Chapter 14) and a comprehensive discussion ofcatalytic deoxygenation of fatty acids in a packed-bed reactoras case study in production of biofuels (Chapter 15)
It is indeed a pleasure to thank all of the contributors whohave made this challenging task achievable The editors are sin-cerely grateful for their willingness to devote their valuable timeand effort to this project for their readiness in sharing theirvision knowledge years of experience and know-how and alsofor their patience in tolerating various expected or unexpectedextensions arising from the busy schedules of different contribu-tors It has definitely been a privilege to work with the authorscoauthors and reviewers involved in this book The editorswould also like to extend their thanks to Wiley-Blackwell fortheir commitment to this project and to Michael Leventhalfor his organization andmanagement of the publication process
On a more personal note the editors would like to take thisopportunity to express their sincere gratitude to the late Profes-sor David L Trimm who has inspired their research in catalysisand catalytic reaction engineering through many years as super-visor mentor colleague and friend
Zeynep Ilsen OumlnsanAhmet Kerim Avci
Istanbul October 2015
Preface xiii
Nomenclature 359
References 359
15 Modeling of the catalytic deoxygenation of fatty acids in apacked bed reactor 365Teuvo Kilpiouml Paumlivi Maumlki-Arvela Tapio Salmi andDmitry Yu Murzin
151 Introduction 365
152 Experimental data for stearic aciddeoxygenation 366
153 Assumptions 366
154 Model equations 367
155 Evaluation of the adsorption parameters 368
156 Particle diffusion study 369
157 Parameter sensitivity studies 369
158 Parameter identification studies 370
159 Studies concerning the deviation from ideal plug flowconditions 371
1510 Parameter estimation results 372
1511 Scale-up considerations 372
1512 Conclusions 375
Acknowledgments 375
Nomenclature 375
Greek letters 375
References 376
Index 377
Contents ix
List of contributors
Anton Alvarez-MajmutovInstituto Mexicano del Petroacuteleo Management of Products for theTransformation of Crude Oil Mexico City Mexico
Jorge AncheytaInstituto Mexicano del Petroacuteleo Management of Products for theTransformation of Crude Oil Mexico City Mexico
Ahmet Kerim AvciDepartment of Chemical Engineering Boğaziccedili University Istanbul Turkey
Vivek V BuwaDepartment of Chemical EngineeringIndian Institute of Technology-Delhi New Delhi India
Joaquim MS CabralDepartment of Bioengineering and IBB-Institute for Bioengineeringand Biosciences Instituto Superior Teacutecnico Universidade de LisboaLisboa Portugal
Sourav ChatterjeeSchool of Chemistry and Chemical Engineering Queenrsquos University BelfastBelfast UK
Burtron H DavisCenter for Applied Energy Research University of KentuckyLexington KY USA
Pedro FernandesDepartment of Bioengineering and IBB-Institutefor Bioengineering and Biosciences Instituto Superior TeacutecnicoUniversidade de Lisboa Faculdade de EngenhariaUniversidade Lusoacutefona de Humanidadese Tecnologias Lisboa Portugal
Rebecca R FushimiMaterials Science amp Engineering Department Idaho National LaboratoryIdaho Falls ID USA
John T GleavesDepartment of Energy Environmental and Chemical EngineeringWashington University St Louis MO USA
John R GraceDepartment of Chemical and Biological EngineeringThe University of British Columbia VancouverBritish Columbia Canada
Ion IliutaChemical Engineering Department Laval University Queacutebec CityQueacutebec Canada
Gary JacobsCenter for Applied Energy Research University of KentuckyLexington KY USA
Seda KeskinDepartment of Chemical and Biological Engineering Koc UniversityIstanbul Turkey
Teuvo KilpioumlProcess Chemistry Centre Aringbo Akademi University TurkuAringbo Finland
Gunther KolbFraunhofer ICT-IMM Decentralized and Mobile Energy TechnologyDepartment Mainz Germany
Faiumlccedilal LarachiChemical Engineering Department Laval University Queacutebec CityQueacutebec Canada
Carolina LeyvaCentro de Investigacioacuten en Ciencia Aplicada y Tecnologiacutea AvanzadaUnidad Legaria Instituto Politeacutecnico Nacional Mexico City Mexico
Joatildeo P LopesDepartment of Chemical Engineering and BiotechnologyUniversity of Cambridge Cambridge UK
Paumlivi Maumlki-ArvelaProcess Chemistry Centre Aringbo Akademi University TurkuAringbo Finland
Dmitry Yu MurzinProcess Chemistry Centre Aringbo Akademi University TurkuAringbo Finland
Zeynep Ilsen OumlnsanDepartment of Chemical Engineering Boğaziccedili University Istanbul Turkey
Vivek V RanadeChemical Engineering amp Process Development Division National ChemicalLaboratory Pune India
Evgeny RebrovSchool of Engineering University of Warwick Coventry UK
x
Aliacuterio E RodriguesLaboratory of Separation and Reaction EngineeringAssociate Laboratory LSRELCM Department of Chemical EngineeringFaculty of Engineering University of Porto Porto Portugal
Shantanu RoyDepartment of Chemical Engineering Indian Institute of Technology-DelhiNew Delhi India
Tapio SalmiProcess Chemistry Centre Aringbo Akademi UniversityTurkuAringbo Finland
Gregory S YablonskyParks College of Engineering Aviation and TechnologySaint Louis University St Louis MO USA
List of contributors xi
Preface
The single irreplaceable component at the core of a chemicalprocess is the chemical reactor where feed materials are con-verted into desirable products Although the essential variablesby which chemical processes can be controlled are reaction tem-perature pressure feed composition and residence time in thereactor two technological developments of major consequencestarting with 1960s have made possible cost-effective operationunder less severe conditions these are the extensive use of effi-cient catalysts and the introduction of improved or innovativereactor configurations The impact of heterogeneous catalysisis significant in this respect since petroleum refining manufac-turing of chemicals and environmental clean-up which are thethree major areas of the world economy today all requirethe effective use of solid catalysts The challenges involved inthe design of novel solid catalysts and modification of manyexisting ones for higher selectivity and stability have alsoprompted the development of ldquoengineeredrdquo catalysts befittingnovel reactor configurations requiring the use of new supportssuch as monolithic or foam substrates as well as the establish-ment of new techniques for coating surfaces with diverse catalystcomponents in order to ensure longevity particularly in cyclicprocessesIn industrial practice the composition and properties of the
complex feed mixtures that are processed for producing a rangeof valuable chemicals generally necessitate the use of heteroge-neous catalytic reactors Numerous chemical and physical rateprocesses take place in a heterogeneous reactor at differentlength and time scales and frequently in different phasesThe prerequisite for the successful design and operation of cat-alytic reactors is a thorough microkinetic analysis starting fromintrinsic kinetic models of the steady-state chemical activity andleading to global rate expressions obtained by overlaying theeffects of physical rate phenomena occurring at the particlescale Kinetic models of increasing complexity may be requireddepending on the variety of components and number of reac-tions involved The second critical stage in reactor modelingand design is a macrokinetic analysis including the detaileddescription of physical transport phenomena at the reactor scaleand utilizing the global rate expressions of the microkineticanalysis The final catalytic reactor model which integrates theseessential stages can successfully predict the performance anddynamics of plant-scale industrial reactors as well as simulatingtheir start-up shutdown and cyclic operation Taking intoaccount engineered catalysts and new reactor configurations
the modeling and scaling up of reactions conducted at thebench-scale to pilot plant and industrial-scale reactor levels haveto be modified in order to include simultaneous multiscaleapproaches along with the conventional sequential modesMultiphase Catalytic Reactors Theory Design Manufactur-
ing and Applications is a comprehensive up-to-date compila-tion on multiphase catalytic reactors which will serve as anexcellent reference book for graduate students researchersand specialists both in academia and in industry The contentof the book is planned to cover topics starting from the firstprinciples involved in macrokinetic analysis of two- andthree-phase catalytic reactors to their particular industrial appli-cations The main objective is to provide definitive accounts onacademic aspects of multiphase catalytic reactor modeling anddesign along with detailed descriptions of some of the mostrecent industrial applications employing multiphase catalyticreactors in such a way as to balance the academic and industrialcomponents as much as possible Accordingly seven chaptersare included in Parts II III and IV to review the relevantmathematical models and model equations utilized in the fun-damental analysis and macroscopic design of specific reactortypes together with some useful approximations for theirdesign and scale-up from a practical standpoint while the fourchapters in Part VI describe specific industrial applications andcontain pointers that tie in with the modeling and designapproaches presented for the particular multiphase catalyticreactor types discussed in Parts II III and IV Furthermorethe chapters included in Parts I and V of the book containdetailed reviews of the basic principles and essential tools ofcatalytic reaction engineering that are crucial for the successfuldesign and operation of catalytic reactors All chapters ofthe book are contributed by experts distinguished in theirrespective fieldsThe total of 15 chapters included in Multiphase Catalytic
Reactors Theory Design Manufacturing and Applications areorganized in six parts Part I is an overview of the principlesof catalytic reaction engineering embracing Chapter 1 whichis a survey of multiphase catalytic reactor types and their indus-trial significance as well as Chapter 2 on the microkinetic anal-ysis of heterogeneous catalytic systems which surveys theformulation of intrinsic rate equations describing chemical rateprocesses and the construction of global rate expressions thatinclude the effects of physical mass and heat transport phenom-ena occurring at the particle scale Chapters 3 through 9 in
xii
Parts II III and IV discuss individual two- and three-phase cat-alytic reactor types and provide design equations and empiricalrelationships that characterize different multiphase reactorsmathematical modeling is an integral part of these chaptersIn Part II two-phase catalytic reactors are grouped as fixed-bed gasndashsolid catalytic reactors (Chapter 3) and fluidized-bedcatalytic reactors (Chapter 4) Part III deals exclusively withthree-phase catalytic reactors and includes Chapter 5 onthree-phase fixed-bed reactors as well as Chapter 6 on three-phase slurry reactors both of which find significant industrialapplications moreover multiphase bioreactors are also includedin Part III as Chapter 7 Part IV is devoted to the discussion ofthe more recent state-of-the-art structured reactors the theoret-ical aspects and examples of structured reactors enabling processintensification in multiphase operation are treated in Chapter 8on monolith reactors and in Chapter 9 on microreactors of dif-ferent configurations including microstructured packed bedsand microchannel reactors Part V of the book is specificallydesigned for surveying the essential tools of catalytic reactormodeling and design and comprises two chapters Chapter 10discusses the recent developments and experimental techniquesinvolved in lab-scale testing of catalytic reactions includingsteady-state and transient flow experiments as well as the micro-kinetic and TAP approaches to kinetic analysis whileChapter 11 surveys the numerical solution techniques that arefrequently used in catalytic reactor analysis and demonstrateswith some case studies The capstone section of the bookPart VI contains four chapters devoted to specific industrialapplications of multiphase catalytic reactors and includes the
recent developments and practices in FischerndashTropsch technol-ogies (Chapter 12) a thorough discussion of reactor modelingsimulation and scale-up approaches involved in the hydrotreat-ing of oil fractions (Chapter 13) a detailed assessment of theperformances of various reactor configurations used for fuelprocessing (Chapter 14) and a comprehensive discussion ofcatalytic deoxygenation of fatty acids in a packed-bed reactoras case study in production of biofuels (Chapter 15)
It is indeed a pleasure to thank all of the contributors whohave made this challenging task achievable The editors are sin-cerely grateful for their willingness to devote their valuable timeand effort to this project for their readiness in sharing theirvision knowledge years of experience and know-how and alsofor their patience in tolerating various expected or unexpectedextensions arising from the busy schedules of different contribu-tors It has definitely been a privilege to work with the authorscoauthors and reviewers involved in this book The editorswould also like to extend their thanks to Wiley-Blackwell fortheir commitment to this project and to Michael Leventhalfor his organization andmanagement of the publication process
On a more personal note the editors would like to take thisopportunity to express their sincere gratitude to the late Profes-sor David L Trimm who has inspired their research in catalysisand catalytic reaction engineering through many years as super-visor mentor colleague and friend
Zeynep Ilsen OumlnsanAhmet Kerim Avci
Istanbul October 2015
Preface xiii
List of contributors
Anton Alvarez-MajmutovInstituto Mexicano del Petroacuteleo Management of Products for theTransformation of Crude Oil Mexico City Mexico
Jorge AncheytaInstituto Mexicano del Petroacuteleo Management of Products for theTransformation of Crude Oil Mexico City Mexico
Ahmet Kerim AvciDepartment of Chemical Engineering Boğaziccedili University Istanbul Turkey
Vivek V BuwaDepartment of Chemical EngineeringIndian Institute of Technology-Delhi New Delhi India
Joaquim MS CabralDepartment of Bioengineering and IBB-Institute for Bioengineeringand Biosciences Instituto Superior Teacutecnico Universidade de LisboaLisboa Portugal
Sourav ChatterjeeSchool of Chemistry and Chemical Engineering Queenrsquos University BelfastBelfast UK
Burtron H DavisCenter for Applied Energy Research University of KentuckyLexington KY USA
Pedro FernandesDepartment of Bioengineering and IBB-Institutefor Bioengineering and Biosciences Instituto Superior TeacutecnicoUniversidade de Lisboa Faculdade de EngenhariaUniversidade Lusoacutefona de Humanidadese Tecnologias Lisboa Portugal
Rebecca R FushimiMaterials Science amp Engineering Department Idaho National LaboratoryIdaho Falls ID USA
John T GleavesDepartment of Energy Environmental and Chemical EngineeringWashington University St Louis MO USA
John R GraceDepartment of Chemical and Biological EngineeringThe University of British Columbia VancouverBritish Columbia Canada
Ion IliutaChemical Engineering Department Laval University Queacutebec CityQueacutebec Canada
Gary JacobsCenter for Applied Energy Research University of KentuckyLexington KY USA
Seda KeskinDepartment of Chemical and Biological Engineering Koc UniversityIstanbul Turkey
Teuvo KilpioumlProcess Chemistry Centre Aringbo Akademi University TurkuAringbo Finland
Gunther KolbFraunhofer ICT-IMM Decentralized and Mobile Energy TechnologyDepartment Mainz Germany
Faiumlccedilal LarachiChemical Engineering Department Laval University Queacutebec CityQueacutebec Canada
Carolina LeyvaCentro de Investigacioacuten en Ciencia Aplicada y Tecnologiacutea AvanzadaUnidad Legaria Instituto Politeacutecnico Nacional Mexico City Mexico
Joatildeo P LopesDepartment of Chemical Engineering and BiotechnologyUniversity of Cambridge Cambridge UK
Paumlivi Maumlki-ArvelaProcess Chemistry Centre Aringbo Akademi University TurkuAringbo Finland
Dmitry Yu MurzinProcess Chemistry Centre Aringbo Akademi University TurkuAringbo Finland
Zeynep Ilsen OumlnsanDepartment of Chemical Engineering Boğaziccedili University Istanbul Turkey
Vivek V RanadeChemical Engineering amp Process Development Division National ChemicalLaboratory Pune India
Evgeny RebrovSchool of Engineering University of Warwick Coventry UK
x
Aliacuterio E RodriguesLaboratory of Separation and Reaction EngineeringAssociate Laboratory LSRELCM Department of Chemical EngineeringFaculty of Engineering University of Porto Porto Portugal
Shantanu RoyDepartment of Chemical Engineering Indian Institute of Technology-DelhiNew Delhi India
Tapio SalmiProcess Chemistry Centre Aringbo Akademi UniversityTurkuAringbo Finland
Gregory S YablonskyParks College of Engineering Aviation and TechnologySaint Louis University St Louis MO USA
List of contributors xi
Preface
The single irreplaceable component at the core of a chemicalprocess is the chemical reactor where feed materials are con-verted into desirable products Although the essential variablesby which chemical processes can be controlled are reaction tem-perature pressure feed composition and residence time in thereactor two technological developments of major consequencestarting with 1960s have made possible cost-effective operationunder less severe conditions these are the extensive use of effi-cient catalysts and the introduction of improved or innovativereactor configurations The impact of heterogeneous catalysisis significant in this respect since petroleum refining manufac-turing of chemicals and environmental clean-up which are thethree major areas of the world economy today all requirethe effective use of solid catalysts The challenges involved inthe design of novel solid catalysts and modification of manyexisting ones for higher selectivity and stability have alsoprompted the development of ldquoengineeredrdquo catalysts befittingnovel reactor configurations requiring the use of new supportssuch as monolithic or foam substrates as well as the establish-ment of new techniques for coating surfaces with diverse catalystcomponents in order to ensure longevity particularly in cyclicprocessesIn industrial practice the composition and properties of the
complex feed mixtures that are processed for producing a rangeof valuable chemicals generally necessitate the use of heteroge-neous catalytic reactors Numerous chemical and physical rateprocesses take place in a heterogeneous reactor at differentlength and time scales and frequently in different phasesThe prerequisite for the successful design and operation of cat-alytic reactors is a thorough microkinetic analysis starting fromintrinsic kinetic models of the steady-state chemical activity andleading to global rate expressions obtained by overlaying theeffects of physical rate phenomena occurring at the particlescale Kinetic models of increasing complexity may be requireddepending on the variety of components and number of reac-tions involved The second critical stage in reactor modelingand design is a macrokinetic analysis including the detaileddescription of physical transport phenomena at the reactor scaleand utilizing the global rate expressions of the microkineticanalysis The final catalytic reactor model which integrates theseessential stages can successfully predict the performance anddynamics of plant-scale industrial reactors as well as simulatingtheir start-up shutdown and cyclic operation Taking intoaccount engineered catalysts and new reactor configurations
the modeling and scaling up of reactions conducted at thebench-scale to pilot plant and industrial-scale reactor levels haveto be modified in order to include simultaneous multiscaleapproaches along with the conventional sequential modesMultiphase Catalytic Reactors Theory Design Manufactur-
ing and Applications is a comprehensive up-to-date compila-tion on multiphase catalytic reactors which will serve as anexcellent reference book for graduate students researchersand specialists both in academia and in industry The contentof the book is planned to cover topics starting from the firstprinciples involved in macrokinetic analysis of two- andthree-phase catalytic reactors to their particular industrial appli-cations The main objective is to provide definitive accounts onacademic aspects of multiphase catalytic reactor modeling anddesign along with detailed descriptions of some of the mostrecent industrial applications employing multiphase catalyticreactors in such a way as to balance the academic and industrialcomponents as much as possible Accordingly seven chaptersare included in Parts II III and IV to review the relevantmathematical models and model equations utilized in the fun-damental analysis and macroscopic design of specific reactortypes together with some useful approximations for theirdesign and scale-up from a practical standpoint while the fourchapters in Part VI describe specific industrial applications andcontain pointers that tie in with the modeling and designapproaches presented for the particular multiphase catalyticreactor types discussed in Parts II III and IV Furthermorethe chapters included in Parts I and V of the book containdetailed reviews of the basic principles and essential tools ofcatalytic reaction engineering that are crucial for the successfuldesign and operation of catalytic reactors All chapters ofthe book are contributed by experts distinguished in theirrespective fieldsThe total of 15 chapters included in Multiphase Catalytic
Reactors Theory Design Manufacturing and Applications areorganized in six parts Part I is an overview of the principlesof catalytic reaction engineering embracing Chapter 1 whichis a survey of multiphase catalytic reactor types and their indus-trial significance as well as Chapter 2 on the microkinetic anal-ysis of heterogeneous catalytic systems which surveys theformulation of intrinsic rate equations describing chemical rateprocesses and the construction of global rate expressions thatinclude the effects of physical mass and heat transport phenom-ena occurring at the particle scale Chapters 3 through 9 in
xii
Parts II III and IV discuss individual two- and three-phase cat-alytic reactor types and provide design equations and empiricalrelationships that characterize different multiphase reactorsmathematical modeling is an integral part of these chaptersIn Part II two-phase catalytic reactors are grouped as fixed-bed gasndashsolid catalytic reactors (Chapter 3) and fluidized-bedcatalytic reactors (Chapter 4) Part III deals exclusively withthree-phase catalytic reactors and includes Chapter 5 onthree-phase fixed-bed reactors as well as Chapter 6 on three-phase slurry reactors both of which find significant industrialapplications moreover multiphase bioreactors are also includedin Part III as Chapter 7 Part IV is devoted to the discussion ofthe more recent state-of-the-art structured reactors the theoret-ical aspects and examples of structured reactors enabling processintensification in multiphase operation are treated in Chapter 8on monolith reactors and in Chapter 9 on microreactors of dif-ferent configurations including microstructured packed bedsand microchannel reactors Part V of the book is specificallydesigned for surveying the essential tools of catalytic reactormodeling and design and comprises two chapters Chapter 10discusses the recent developments and experimental techniquesinvolved in lab-scale testing of catalytic reactions includingsteady-state and transient flow experiments as well as the micro-kinetic and TAP approaches to kinetic analysis whileChapter 11 surveys the numerical solution techniques that arefrequently used in catalytic reactor analysis and demonstrateswith some case studies The capstone section of the bookPart VI contains four chapters devoted to specific industrialapplications of multiphase catalytic reactors and includes the
recent developments and practices in FischerndashTropsch technol-ogies (Chapter 12) a thorough discussion of reactor modelingsimulation and scale-up approaches involved in the hydrotreat-ing of oil fractions (Chapter 13) a detailed assessment of theperformances of various reactor configurations used for fuelprocessing (Chapter 14) and a comprehensive discussion ofcatalytic deoxygenation of fatty acids in a packed-bed reactoras case study in production of biofuels (Chapter 15)
It is indeed a pleasure to thank all of the contributors whohave made this challenging task achievable The editors are sin-cerely grateful for their willingness to devote their valuable timeand effort to this project for their readiness in sharing theirvision knowledge years of experience and know-how and alsofor their patience in tolerating various expected or unexpectedextensions arising from the busy schedules of different contribu-tors It has definitely been a privilege to work with the authorscoauthors and reviewers involved in this book The editorswould also like to extend their thanks to Wiley-Blackwell fortheir commitment to this project and to Michael Leventhalfor his organization andmanagement of the publication process
On a more personal note the editors would like to take thisopportunity to express their sincere gratitude to the late Profes-sor David L Trimm who has inspired their research in catalysisand catalytic reaction engineering through many years as super-visor mentor colleague and friend
Zeynep Ilsen OumlnsanAhmet Kerim Avci
Istanbul October 2015
Preface xiii
Aliacuterio E RodriguesLaboratory of Separation and Reaction EngineeringAssociate Laboratory LSRELCM Department of Chemical EngineeringFaculty of Engineering University of Porto Porto Portugal
Shantanu RoyDepartment of Chemical Engineering Indian Institute of Technology-DelhiNew Delhi India
Tapio SalmiProcess Chemistry Centre Aringbo Akademi UniversityTurkuAringbo Finland
Gregory S YablonskyParks College of Engineering Aviation and TechnologySaint Louis University St Louis MO USA
List of contributors xi
Preface
The single irreplaceable component at the core of a chemicalprocess is the chemical reactor where feed materials are con-verted into desirable products Although the essential variablesby which chemical processes can be controlled are reaction tem-perature pressure feed composition and residence time in thereactor two technological developments of major consequencestarting with 1960s have made possible cost-effective operationunder less severe conditions these are the extensive use of effi-cient catalysts and the introduction of improved or innovativereactor configurations The impact of heterogeneous catalysisis significant in this respect since petroleum refining manufac-turing of chemicals and environmental clean-up which are thethree major areas of the world economy today all requirethe effective use of solid catalysts The challenges involved inthe design of novel solid catalysts and modification of manyexisting ones for higher selectivity and stability have alsoprompted the development of ldquoengineeredrdquo catalysts befittingnovel reactor configurations requiring the use of new supportssuch as monolithic or foam substrates as well as the establish-ment of new techniques for coating surfaces with diverse catalystcomponents in order to ensure longevity particularly in cyclicprocessesIn industrial practice the composition and properties of the
complex feed mixtures that are processed for producing a rangeof valuable chemicals generally necessitate the use of heteroge-neous catalytic reactors Numerous chemical and physical rateprocesses take place in a heterogeneous reactor at differentlength and time scales and frequently in different phasesThe prerequisite for the successful design and operation of cat-alytic reactors is a thorough microkinetic analysis starting fromintrinsic kinetic models of the steady-state chemical activity andleading to global rate expressions obtained by overlaying theeffects of physical rate phenomena occurring at the particlescale Kinetic models of increasing complexity may be requireddepending on the variety of components and number of reac-tions involved The second critical stage in reactor modelingand design is a macrokinetic analysis including the detaileddescription of physical transport phenomena at the reactor scaleand utilizing the global rate expressions of the microkineticanalysis The final catalytic reactor model which integrates theseessential stages can successfully predict the performance anddynamics of plant-scale industrial reactors as well as simulatingtheir start-up shutdown and cyclic operation Taking intoaccount engineered catalysts and new reactor configurations
the modeling and scaling up of reactions conducted at thebench-scale to pilot plant and industrial-scale reactor levels haveto be modified in order to include simultaneous multiscaleapproaches along with the conventional sequential modesMultiphase Catalytic Reactors Theory Design Manufactur-
ing and Applications is a comprehensive up-to-date compila-tion on multiphase catalytic reactors which will serve as anexcellent reference book for graduate students researchersand specialists both in academia and in industry The contentof the book is planned to cover topics starting from the firstprinciples involved in macrokinetic analysis of two- andthree-phase catalytic reactors to their particular industrial appli-cations The main objective is to provide definitive accounts onacademic aspects of multiphase catalytic reactor modeling anddesign along with detailed descriptions of some of the mostrecent industrial applications employing multiphase catalyticreactors in such a way as to balance the academic and industrialcomponents as much as possible Accordingly seven chaptersare included in Parts II III and IV to review the relevantmathematical models and model equations utilized in the fun-damental analysis and macroscopic design of specific reactortypes together with some useful approximations for theirdesign and scale-up from a practical standpoint while the fourchapters in Part VI describe specific industrial applications andcontain pointers that tie in with the modeling and designapproaches presented for the particular multiphase catalyticreactor types discussed in Parts II III and IV Furthermorethe chapters included in Parts I and V of the book containdetailed reviews of the basic principles and essential tools ofcatalytic reaction engineering that are crucial for the successfuldesign and operation of catalytic reactors All chapters ofthe book are contributed by experts distinguished in theirrespective fieldsThe total of 15 chapters included in Multiphase Catalytic
Reactors Theory Design Manufacturing and Applications areorganized in six parts Part I is an overview of the principlesof catalytic reaction engineering embracing Chapter 1 whichis a survey of multiphase catalytic reactor types and their indus-trial significance as well as Chapter 2 on the microkinetic anal-ysis of heterogeneous catalytic systems which surveys theformulation of intrinsic rate equations describing chemical rateprocesses and the construction of global rate expressions thatinclude the effects of physical mass and heat transport phenom-ena occurring at the particle scale Chapters 3 through 9 in
xii
Parts II III and IV discuss individual two- and three-phase cat-alytic reactor types and provide design equations and empiricalrelationships that characterize different multiphase reactorsmathematical modeling is an integral part of these chaptersIn Part II two-phase catalytic reactors are grouped as fixed-bed gasndashsolid catalytic reactors (Chapter 3) and fluidized-bedcatalytic reactors (Chapter 4) Part III deals exclusively withthree-phase catalytic reactors and includes Chapter 5 onthree-phase fixed-bed reactors as well as Chapter 6 on three-phase slurry reactors both of which find significant industrialapplications moreover multiphase bioreactors are also includedin Part III as Chapter 7 Part IV is devoted to the discussion ofthe more recent state-of-the-art structured reactors the theoret-ical aspects and examples of structured reactors enabling processintensification in multiphase operation are treated in Chapter 8on monolith reactors and in Chapter 9 on microreactors of dif-ferent configurations including microstructured packed bedsand microchannel reactors Part V of the book is specificallydesigned for surveying the essential tools of catalytic reactormodeling and design and comprises two chapters Chapter 10discusses the recent developments and experimental techniquesinvolved in lab-scale testing of catalytic reactions includingsteady-state and transient flow experiments as well as the micro-kinetic and TAP approaches to kinetic analysis whileChapter 11 surveys the numerical solution techniques that arefrequently used in catalytic reactor analysis and demonstrateswith some case studies The capstone section of the bookPart VI contains four chapters devoted to specific industrialapplications of multiphase catalytic reactors and includes the
recent developments and practices in FischerndashTropsch technol-ogies (Chapter 12) a thorough discussion of reactor modelingsimulation and scale-up approaches involved in the hydrotreat-ing of oil fractions (Chapter 13) a detailed assessment of theperformances of various reactor configurations used for fuelprocessing (Chapter 14) and a comprehensive discussion ofcatalytic deoxygenation of fatty acids in a packed-bed reactoras case study in production of biofuels (Chapter 15)
It is indeed a pleasure to thank all of the contributors whohave made this challenging task achievable The editors are sin-cerely grateful for their willingness to devote their valuable timeand effort to this project for their readiness in sharing theirvision knowledge years of experience and know-how and alsofor their patience in tolerating various expected or unexpectedextensions arising from the busy schedules of different contribu-tors It has definitely been a privilege to work with the authorscoauthors and reviewers involved in this book The editorswould also like to extend their thanks to Wiley-Blackwell fortheir commitment to this project and to Michael Leventhalfor his organization andmanagement of the publication process
On a more personal note the editors would like to take thisopportunity to express their sincere gratitude to the late Profes-sor David L Trimm who has inspired their research in catalysisand catalytic reaction engineering through many years as super-visor mentor colleague and friend
Zeynep Ilsen OumlnsanAhmet Kerim Avci
Istanbul October 2015
Preface xiii
Preface
The single irreplaceable component at the core of a chemicalprocess is the chemical reactor where feed materials are con-verted into desirable products Although the essential variablesby which chemical processes can be controlled are reaction tem-perature pressure feed composition and residence time in thereactor two technological developments of major consequencestarting with 1960s have made possible cost-effective operationunder less severe conditions these are the extensive use of effi-cient catalysts and the introduction of improved or innovativereactor configurations The impact of heterogeneous catalysisis significant in this respect since petroleum refining manufac-turing of chemicals and environmental clean-up which are thethree major areas of the world economy today all requirethe effective use of solid catalysts The challenges involved inthe design of novel solid catalysts and modification of manyexisting ones for higher selectivity and stability have alsoprompted the development of ldquoengineeredrdquo catalysts befittingnovel reactor configurations requiring the use of new supportssuch as monolithic or foam substrates as well as the establish-ment of new techniques for coating surfaces with diverse catalystcomponents in order to ensure longevity particularly in cyclicprocessesIn industrial practice the composition and properties of the
complex feed mixtures that are processed for producing a rangeof valuable chemicals generally necessitate the use of heteroge-neous catalytic reactors Numerous chemical and physical rateprocesses take place in a heterogeneous reactor at differentlength and time scales and frequently in different phasesThe prerequisite for the successful design and operation of cat-alytic reactors is a thorough microkinetic analysis starting fromintrinsic kinetic models of the steady-state chemical activity andleading to global rate expressions obtained by overlaying theeffects of physical rate phenomena occurring at the particlescale Kinetic models of increasing complexity may be requireddepending on the variety of components and number of reac-tions involved The second critical stage in reactor modelingand design is a macrokinetic analysis including the detaileddescription of physical transport phenomena at the reactor scaleand utilizing the global rate expressions of the microkineticanalysis The final catalytic reactor model which integrates theseessential stages can successfully predict the performance anddynamics of plant-scale industrial reactors as well as simulatingtheir start-up shutdown and cyclic operation Taking intoaccount engineered catalysts and new reactor configurations
the modeling and scaling up of reactions conducted at thebench-scale to pilot plant and industrial-scale reactor levels haveto be modified in order to include simultaneous multiscaleapproaches along with the conventional sequential modesMultiphase Catalytic Reactors Theory Design Manufactur-
ing and Applications is a comprehensive up-to-date compila-tion on multiphase catalytic reactors which will serve as anexcellent reference book for graduate students researchersand specialists both in academia and in industry The contentof the book is planned to cover topics starting from the firstprinciples involved in macrokinetic analysis of two- andthree-phase catalytic reactors to their particular industrial appli-cations The main objective is to provide definitive accounts onacademic aspects of multiphase catalytic reactor modeling anddesign along with detailed descriptions of some of the mostrecent industrial applications employing multiphase catalyticreactors in such a way as to balance the academic and industrialcomponents as much as possible Accordingly seven chaptersare included in Parts II III and IV to review the relevantmathematical models and model equations utilized in the fun-damental analysis and macroscopic design of specific reactortypes together with some useful approximations for theirdesign and scale-up from a practical standpoint while the fourchapters in Part VI describe specific industrial applications andcontain pointers that tie in with the modeling and designapproaches presented for the particular multiphase catalyticreactor types discussed in Parts II III and IV Furthermorethe chapters included in Parts I and V of the book containdetailed reviews of the basic principles and essential tools ofcatalytic reaction engineering that are crucial for the successfuldesign and operation of catalytic reactors All chapters ofthe book are contributed by experts distinguished in theirrespective fieldsThe total of 15 chapters included in Multiphase Catalytic
Reactors Theory Design Manufacturing and Applications areorganized in six parts Part I is an overview of the principlesof catalytic reaction engineering embracing Chapter 1 whichis a survey of multiphase catalytic reactor types and their indus-trial significance as well as Chapter 2 on the microkinetic anal-ysis of heterogeneous catalytic systems which surveys theformulation of intrinsic rate equations describing chemical rateprocesses and the construction of global rate expressions thatinclude the effects of physical mass and heat transport phenom-ena occurring at the particle scale Chapters 3 through 9 in
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Parts II III and IV discuss individual two- and three-phase cat-alytic reactor types and provide design equations and empiricalrelationships that characterize different multiphase reactorsmathematical modeling is an integral part of these chaptersIn Part II two-phase catalytic reactors are grouped as fixed-bed gasndashsolid catalytic reactors (Chapter 3) and fluidized-bedcatalytic reactors (Chapter 4) Part III deals exclusively withthree-phase catalytic reactors and includes Chapter 5 onthree-phase fixed-bed reactors as well as Chapter 6 on three-phase slurry reactors both of which find significant industrialapplications moreover multiphase bioreactors are also includedin Part III as Chapter 7 Part IV is devoted to the discussion ofthe more recent state-of-the-art structured reactors the theoret-ical aspects and examples of structured reactors enabling processintensification in multiphase operation are treated in Chapter 8on monolith reactors and in Chapter 9 on microreactors of dif-ferent configurations including microstructured packed bedsand microchannel reactors Part V of the book is specificallydesigned for surveying the essential tools of catalytic reactormodeling and design and comprises two chapters Chapter 10discusses the recent developments and experimental techniquesinvolved in lab-scale testing of catalytic reactions includingsteady-state and transient flow experiments as well as the micro-kinetic and TAP approaches to kinetic analysis whileChapter 11 surveys the numerical solution techniques that arefrequently used in catalytic reactor analysis and demonstrateswith some case studies The capstone section of the bookPart VI contains four chapters devoted to specific industrialapplications of multiphase catalytic reactors and includes the
recent developments and practices in FischerndashTropsch technol-ogies (Chapter 12) a thorough discussion of reactor modelingsimulation and scale-up approaches involved in the hydrotreat-ing of oil fractions (Chapter 13) a detailed assessment of theperformances of various reactor configurations used for fuelprocessing (Chapter 14) and a comprehensive discussion ofcatalytic deoxygenation of fatty acids in a packed-bed reactoras case study in production of biofuels (Chapter 15)
It is indeed a pleasure to thank all of the contributors whohave made this challenging task achievable The editors are sin-cerely grateful for their willingness to devote their valuable timeand effort to this project for their readiness in sharing theirvision knowledge years of experience and know-how and alsofor their patience in tolerating various expected or unexpectedextensions arising from the busy schedules of different contribu-tors It has definitely been a privilege to work with the authorscoauthors and reviewers involved in this book The editorswould also like to extend their thanks to Wiley-Blackwell fortheir commitment to this project and to Michael Leventhalfor his organization andmanagement of the publication process
On a more personal note the editors would like to take thisopportunity to express their sincere gratitude to the late Profes-sor David L Trimm who has inspired their research in catalysisand catalytic reaction engineering through many years as super-visor mentor colleague and friend
Zeynep Ilsen OumlnsanAhmet Kerim Avci
Istanbul October 2015
Preface xiii
Parts II III and IV discuss individual two- and three-phase cat-alytic reactor types and provide design equations and empiricalrelationships that characterize different multiphase reactorsmathematical modeling is an integral part of these chaptersIn Part II two-phase catalytic reactors are grouped as fixed-bed gasndashsolid catalytic reactors (Chapter 3) and fluidized-bedcatalytic reactors (Chapter 4) Part III deals exclusively withthree-phase catalytic reactors and includes Chapter 5 onthree-phase fixed-bed reactors as well as Chapter 6 on three-phase slurry reactors both of which find significant industrialapplications moreover multiphase bioreactors are also includedin Part III as Chapter 7 Part IV is devoted to the discussion ofthe more recent state-of-the-art structured reactors the theoret-ical aspects and examples of structured reactors enabling processintensification in multiphase operation are treated in Chapter 8on monolith reactors and in Chapter 9 on microreactors of dif-ferent configurations including microstructured packed bedsand microchannel reactors Part V of the book is specificallydesigned for surveying the essential tools of catalytic reactormodeling and design and comprises two chapters Chapter 10discusses the recent developments and experimental techniquesinvolved in lab-scale testing of catalytic reactions includingsteady-state and transient flow experiments as well as the micro-kinetic and TAP approaches to kinetic analysis whileChapter 11 surveys the numerical solution techniques that arefrequently used in catalytic reactor analysis and demonstrateswith some case studies The capstone section of the bookPart VI contains four chapters devoted to specific industrialapplications of multiphase catalytic reactors and includes the
recent developments and practices in FischerndashTropsch technol-ogies (Chapter 12) a thorough discussion of reactor modelingsimulation and scale-up approaches involved in the hydrotreat-ing of oil fractions (Chapter 13) a detailed assessment of theperformances of various reactor configurations used for fuelprocessing (Chapter 14) and a comprehensive discussion ofcatalytic deoxygenation of fatty acids in a packed-bed reactoras case study in production of biofuels (Chapter 15)
It is indeed a pleasure to thank all of the contributors whohave made this challenging task achievable The editors are sin-cerely grateful for their willingness to devote their valuable timeand effort to this project for their readiness in sharing theirvision knowledge years of experience and know-how and alsofor their patience in tolerating various expected or unexpectedextensions arising from the busy schedules of different contribu-tors It has definitely been a privilege to work with the authorscoauthors and reviewers involved in this book The editorswould also like to extend their thanks to Wiley-Blackwell fortheir commitment to this project and to Michael Leventhalfor his organization andmanagement of the publication process
On a more personal note the editors would like to take thisopportunity to express their sincere gratitude to the late Profes-sor David L Trimm who has inspired their research in catalysisand catalytic reaction engineering through many years as super-visor mentor colleague and friend
Zeynep Ilsen OumlnsanAhmet Kerim Avci
Istanbul October 2015
Preface xiii