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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


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

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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


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


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


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

PART 1

Principles of catalytic reactionengineering

CHAPTER 1

Catalytic reactor types and their industrialsignificance

Zeynep Ilsen Oumlnsan and Ahmet Kerim AvciDepartment of Chemical Engineering Boğaziccedili University Istanbul Turkey

Abstract

The present chapter is aimed to provide a simplified overview ofthe catalytic reactors used in chemical industry Each reactor typeis described in terms of its key geometric properties operatingcharacteristics advantages and drawbacks among its alternativesand typical areasofuseThesignificanceof the reactors isexplainedin the context of selected industrial examples Industrial reactorsthat do not involve the use of solid catalysts are also discussed

11 Introduction

Todayrsquos chemical markets involve many different products withdiverse physical and chemical properties These products are pro-duced in chemical plants with different architectures and charac-teristics Despite these differences general structure of a chemicalplant can be described by three main groups of unit operationsnamely upstream operations downstream operations and thereaction section as shown in Figure 11 Among these groupsthe reactor is the most critical section that determines the plantprofitability via metrics such as reactant conversion productselectivity and yield high per-pass conversions will reduce theoperating expenses involved in product separation and purifica-tion steps as well as the recycling costs (Figure 11) At this stageselection of the appropriate reactor type and ensuring their effi-cient operation become critical issues to be addressed

In almost all reactors running in the chemical industry thedesired product throughput and quality are provided by cata-lysts the functional materials that allow chemical synthesis tobe carried out at economic scales by increasing the reactionrates Owing to this critical feature more than 98 of the todayrsquosindustrial chemistry is involved with catalysis Since catalystshave direct impact on reactor performance they have to beoperated at their highest possible effectiveness which is deter-mined by the degree of internal and external heat and masstransport resistances defined and explained in detail inChapter 2 At this stage the function of the reactor is to provide

conditions such that the catalyst particles can deliver the bestpossible performance (eg activity selectivity yield) at suffi-cient stability For example for a highly exothermic reactionsystem such as FischerndashTropsch (FT) synthesis heat trans-portremoval rates within the reactor should be very high to pre-vent undesired temperature elevations that can negatively affectproduct distribution and more importantly cause thermallyinduced deactivation of the catalysts Considering the fact thattransport rates are favored by good mixing of the reactive fluidat turbulent conditions the selected reactor type should allow awide operating window in terms of pressure drop which is alimit against the occurrence of well-mixed conditions The pos-sibility of integration and operation of effective external heatexchange systems should also be taken into account in theselected reactor type The final selection is carried out in the con-text of fixed capital investment operating expenses and profit-ability of the technically feasible solutions

Synthesis of commercial chemical products having differentphysical and chemical functional properties involves the existenceof different combinations of catalytic chemistry thermodynamicproperties and heat andmass transport conditions (eg nature ofthe catalyst and fluids) within the reactor volume As a result sev-eral reactor types are being proposed Classification of the reactorscan be carried out based on various criteria such as compatibilitywith the operating mode (batch vs continuous reactors) and thenumber of phases (homogeneous vs heterogeneous reactors)In this chapter reactors are classified according to the positionof the catalyst bed that is whether it is fixed or mobile Inpacked-bed trickle-bed and structured (ie monolith andmicro-channel) reactors catalyst bed is fixed while it is mobile in flui-dized-bed moving-bed and slurry reactors The descriptions ofthese reactor types are summarized in the following sections

12 Reactors with fixed bed of catalysts

121 Packed-bed reactorsIn packed-bed reactors (PBRs) the solid particulate catalystparticles forming the bed are fixed in an enclosed volume The

3

Multiphase Catalytic Reactors Theory Design Manufacturing and Applications First Edition Edited by Zeynep Ilsen Oumlnsan and Ahmet Kerim Avcicopy 2016 John Wiley amp Sons Inc Published 2016 by John Wiley amp Sons Inc

particles are randomly packed so there is not a regular structureand as a result fluid flow takes place through irregular randompaths Reactions take place over the active sites that are buriedwithin the pores of the catalyst particles A simple descriptionof the PBR operation is shown in Figure 12 [1] Owing to theirrelatively simple configuration and operation PBRs are widelyused in the chemical industry They are used in high-throughputcontinuous operations Since the catalyst is considered as a sep-arate solid phase and the fluid types are either gas only or gasndashliquid mixtures PBRs are classified as heterogeneous reactorsIn the case of coexistence of three phases with concurrent down-flow of liquid and gas over the solid packing the reactor is calledas a trickle-bed reactor (see Section 124) The geometry of thecatalyst-containing volume which can be either a tube or a vesseldictates the type of the PBR Descriptions of the so-called tubularand vessel-type PBRs are given later

1211 Tubular PBRsPBRs are known to have inherently weak heat transfer pro-perties due to the presence of voids within the catalyst bed(Figure 12 [1]) that act as resistances against the transport ofheat along the reactor The tubular PBR geometry whichinvolves the location of catalyst-containing tubes in a particularpattern within a shell is preferred over a regular vessel whenhigh rates of heat input or removal are essential for highly

endothermic or exothermic reactions respectively This advan-tage of the tubular configuration however comes at the expenseof higher pressure drop It is also worth noting that the processof catalyst packing and unloading in tubular geometry is moredifficult than that involved in vessels Therefore catalyst lifetimein tubular PBRs should be long enough to minimize the down-times for and costs associated with catalyst changeoverThe shelltube configuration of tubular PBRs depends on the

nature of the catalytic reaction For highly endothermic reac-tions such as catalytic steam reforming the reactor geometryis similar to that of a fired furnace in which the catalyst-packedtubes are heated by the energy released by the combustion of afuel on the shell side Catalytic steam reforming involves theconversion of a hydrocarbon to a hydrogen-rich mixture inthe presence of steam

CmHnOk + m ndash k H2O=mCO

+ m ndash k+ n 2 H2 m gt k ΔH gt 01 1

The process is known as the conventional method of produ-cing hydrogen for meeting the hydrogen demands of the refin-ing and petrochemical industry The most widely used fuel insteam reforming is natural gas which is mostly composed ofmethane

CH4 +H2O=CO+ 3H2 ΔH = 206 kJ mol 1 2

Methane steam reforming is conventionally carried out overNi-based catalysts Owing to the high endothermicity and slowkinetics the process depends strongly on the input of externalenergy at high rates for ensuring commercially viable through-put of hydrogen The critical energy demand of the reaction ismet in a reactor (also called as the reformer) where multipleNi-based catalyst-packed tubes are heated mainly via radiativeheat generated by homogeneous combustion of a fuel typicallynatural gas in a process furnace This configuration sets thebasis for the development and use of various types of commer-cial steam reforming reactors described in Figure 13 [2] whichdiffer in the positions of heat source and the degree of delivery ofthe combustion energy to the so-called reformer tubes A furtherdetailed representation of a tubular reformer is provided inFigure 14 [2] Depending on the capacity of the reactor thenumber of tubes can be increased up to 1000 each having outerdiameter wall thickness and heated length ranges of 10ndash18 cm08ndash20 cm and 10ndash14 m respectively The degree of furnace-to-tube heat transfer affecting the rate of Reaction 12 and hydro-gen production capacity of the reactor is limited by thermalstability of the tube material which is found to decrease signif-icantly with temperature above ca 850 C [3] Therefore specialalloys particularly microalloys composed of 25Cr 35Ni Nb Tiare used to improve the operating window of the reactor [3]The multitubular PBR configuration is preferred when con-

vection is not sufficient for delivering the necessary heat fluxto sustain the operation However in most of the exothermicand endothermic reactions the temperature of the catalystbed can be regulated by convective external heat transfer In

Raw materialinput

Feedprocessing

unit(s)

Upstreamoperations

Recycle stream

To side productprocessing

To sideproductwaste

processingDownstreamoperations

Finishedproduct(s)

Purificationunit(s)

Separationunit(s)

Reactor(s)

Figure 11 Outline of a chemical process

Catalystparticles

Pores

ξ= Rp

Catalyst bedL

Flow

Rtr

z

Figure 12 Schematic presentation of a packed-bed reactor(Source Onsan and Avci [1] Reproduced with permission of Elsevier)

4 Chapter 1

such cases the catalyst-containing tubes are bundled in a shell-and-tube heat exchanger like configuration involving circulationof the heat transfer fluid on the shell side This PBR concept isdescribed in Figure 15 [4] in which alternative methods of cir-culation of the heat transfer fluid around the packed tubes areintroduced Inmildly endothermic or exothermic reactions heattransfer can be realized to provide nearly isothermal conditionsin cross-flow and parallel flow configurations shown inFigure 15a and b [4] respectively In such reactors inside dia-meters and lengths of the tubes are reported to vary between2ndash8 cm and 05ndash15 m respectively [4] For endothermic casesthe heating medium can be a gas or a liquid with the latter

offering better heat transfer rates due to higher convective heattransfer coefficients of liquids Cooling in exothermic reactionsis carried out either by circulation of a heat transfer fluid or byboiling heat transfer In the former case fluids such as moltensalts are force-circulated around the tube bundle The heated liq-uid leaving the reactor is then passed through an external steamgenerator and cooled for the next cycle In the case of boilingheat transfer (Figure 15c [4]) however the cooling fluid thatis fed from the bottom of the reactor rises up due to natural cir-culation induced by the decreasing density profile that is causedby continuous heat absorption from the tubes Partial evapora-tion of the cooling water is also observed Vapor bubbles agitatethe liquid and increase the convective heat transfer coefficientThe resulting vaporndashliquid mixture is then let to settle in a steamdrum where steam is separated and the remaining liquid sentback to the cooling cycle together with some makeup waterEven though this configuration eliminates the need for coolingfluid transportation equipment the tubes may be overheated ifheat generation in the tubes becomes excessive to evaporate cool-ing water on the shell side In such a case the rate of convectiveheat removal will be less than the rate of catalytic heat generationand the tubes are subjected to the risk of burning out

In multitubular PBRs heat management can be improved byincreasing the heat transfer area per catalyst volume which is pos-sible by using tubes with smaller diameters In this case definiteamounts of catalyst will be packed into a higher number of tubeswhich will offer increased external tube surface area for heattransfer Due to the reduced tube cross-sectional area smallertube diameters will also increase the linear flow rate of the reactivemixture and favor well-mixed conditions that increase the heattransport rates However these advantages are naturally limitedby pressure drop as higher flow rates will cause increased fric-tional loss of mechanical energy of the reactive fluid and willrequire increased pumpingcompression costs Neverthelessthe trade-off between heat transfer rates and pressure drop canbe relaxed by the possibility of using different combinations ofsize shape and material of the catalyst pellets [4 5] For examplepellet shapes offering higher void fractions and larger hydraulicdiameters allow lower pressure drop operations It is worth notingthat the rate of catalytic reactions increases with the surface areaof the catalyst bed that necessitates the use of smaller pelletsTherefore pellet size also requires careful optimization

Figure 13 Furnace configurations formultitubular packed-bed reformers(Source Dybkjaer [2] Reproduced withpermission of Elsevier)

Figure 14 Side-fired tubular reformer design by Haldor-Topsoslashe(Source Dybkjaer [2] Reproduced with permission of Elsevier)

Catalytic reactor types and their industrial significance 5

The length and diameter of the tube and the particle size(hydraulic diameter) also affect flow distribution within thepacked tube If the ratio of the tube diameter to that of the particlediameter is above 30 radial variations in velocity can beneglected and plug (piston) flow behavior can be assumedThe ratio of the tube length to particle diameter is also importantif this ratio exceeds 50 axial dispersion and axial heat conduc-tion effects can be ignored These effects bring notable simpli-fications into the modeling of PBRs which are discussed inChapter 3

1212 Vessel-type PBRsThe design and operational requirements explained for tubularPBRs are also valid for PBRs in which the catalyst bed is packedin one vessel as described schematically in Figure 16a [4] Thisreactor configuration is preferred when the reaction is carriedout at adiabatic conditions However as demonstrated inFigure 16b and c [4] bed temperature can be changed by heataddition toremoval from the bed for obtaining a temperature

profile as close as possible to that of the optimum Figure 16b[4] is a representation of addition or removal of heat tofromthe catalyst bed by direct injection of hot or cold feed to thebed This heat management strategy can be used where the heatsof reactions are low Successful implementation of this strategydepends on careful consideration of mixing and redistributionof the injected fluid with that of the reactive mixture and ofthe adiabatic temperature change upon injection which shouldbe within acceptable limits A better regulation of the bed tem-perature is possible by the use of interstage heat exchangersbetween multiple adiabatic beds (Figure 16c [4]) This configu-ration is more suitable for improving conversions or productselectivities in reactions limited by chemical equilibrium Thepossibility of using different heat exchange equipment betweenthe stages helps in handling high reaction enthalpies For endo-thermic reactions interstage heating is usually carried out bymeans of fired heating in which the heat transfer fluid is heatedin a fired furnace and then circulated between the beds to pro-vide heat to the reactive fluid Adiabatic heat generated during

Circulationturbine

Steamgenerator

Feedwater

Steam

Feed gas Saturatedsteam

Steam drum

Feedwater

(a) (b) (c)

Figure 15 Heat transfer strategies in multitubular packed-bed reactors (a) Cross-flow (b) parallel flow and (c) boiling-water cooling(Source Eigenberger [4] Reproduced with permission of John Wiley amp Sons Inc)

Interstagegas feed

Feed gas

Interstageheatexchangers

(a) (b) (c)

Figure 16 Various configurations of vessel-type packed-bedreactors (a) Single-bed adiabatic packed-bed reactor(b) adiabatic reactor with interstage gas injection and(c) multiple adiabatic beds with interstage heat exchange(Source Eigenberger [4] Reproduced with permissionof John Wiley amp Sons Inc)

6 Chapter 1

exothermic reactions is removed by contacting the hot bed efflu-ent with interstage heat exchange tubes in which a coolant forexample water is circulated for steam generation purposes

Multiple adiabatic beds with interstage heat exchange config-uration compete with tubular PBR geometry as both configura-tions provide regulation of the bed temperature to improvereactant conversion and product selectivity In this respectthe tubular PBR alternative is better because it offers continuouscontrol over the bed temperature However although tempera-ture regulation is only possible through a stepwise pattern in themultiple adiabatic beds they do offer several practical advan-tages such as the possibility of (i) changing the catalyst bed inindividual stages at different times (ii) distributed stagewisefeeding of a reactant instead of its total feeding at the inletand (iii) drawing a limiting product from an intermediate stagein case of reactions limited by equilibrium [4 5]

Vessel-type PBRs are widely used in chemical industryA descriptive example is ammonia synthesis which is an exo-thermic equilibrium reaction

N2 + 3H2 = 2NH3 ΔH = minus92 4 kJ mol 1 3

The reaction is carried out in a multistage PBR with interstagecooling (Figure 17 [4]) in the 400ndash500 C range and involves theuse of iron-based catalysts In order to favor ammonia produc-tion by shifting the chemical equilibrium to the product sidepressures up to 300 bar are required As adiabatic temperaturerise hinders conversion due to the equilibrium limit the reactivemixture is cooled down between the beds and the recoveredheat is used for steam generation The resulting conditionsdeliver a product mixture including ca 20 NH3 which is sepa-rated by a series of condensers Upon separation unreacted mix-ture of N2 and H2 is combined with fresh makeup feed andrecycled to the first stage of the reactor

Another commercial example involving the use of a vessel-type PBR is autothermal reforming (ATR) of natural gas It isa key step in gas-to-liquid (GTL) processes and is used to pro-duce synthesis gas (CO +H2) for FT synthesis in which a mix-ture of hydrocarbons in the C1ndashC30+ range is synthesized [6] InATR noncatalytic oxidation (Reaction 14) and Ni-catalyzedsteam reforming of natural gas (Reaction 12) are combinedand product distribution is affected by waterndashgas shift(Reaction 15) an important side reaction of steam reforming[3 7]

CH4 + 1 5O2 CO+ 2H2O ΔH = minus519 kJ mol 1 4

CH4 +H2O=CO+ 3H2 ΔH = 206 kJ mol 1 2

CO+H2O=CO2 +H2 ΔH = minus41 kJ mol 1 5

ATR is carried out in an adiabatic PBR as described inFigure 18 [7] Natural gas steam and oxygen (or enrichedair) are cofed to a mixerndashburner unit for ensuring combustionof the homogeneous mixture of reactants taking place in thecombustion chamber Heat produced in the combustion zonewhere temperature can be well above ca 1500 C is thentransferred to the Ni-based catalyst bed on which Reactions12 and 15 take place to produce a mixture of H2 and COat molar ratios close to 2 at temperatures above ca 1000 Cand at pressures up to ca 30 bar [3 7] Success of the reactordepends on keeping the exothermic heat within the vesselthat is operating the reactor adiabatically For this purposethe inner wall of the steel pressure vessel is lined with multiplelayers of refractory insulation A special catalyst pellet shapeincluding numerous holes is used to minimize pressure dropalong the bed and to avoid bypass of gas through the refrac-tory layer

400degC 300 bar 2 NH3

Stage 1Stage 1

Steam

Water

Steam

Water

FeedExit

Stage 2Stage 2

Stage 3Stage 3

20 NH3(N2 H2 CH4)

Circulating gas

Off-gas

NH3 liquid

Fresh gasN2+ 3H2 (+CH4)

Condensationcoolers

Figure 17 Packed-bed reactor with multiple adiabatic bedsfor ammonia synthesis(Source Eigenberger [4] Reproduced with permission ofJohn Wiley amp Sons Inc)


122 Monolith reactorsMonolith reactors are composed of a large number of parallelchannels all of which contain catalyst coated on their innerwalls (Figure 19 [1]) Depending on the porosity of the mono-lith structure active metals can be dispersed directly onto theinner channel walls or the catalyst can be washcoated as a sep-arate layer with a definite thickness In this respect monolithreactors can be classified among PBR types However theircharacteristic properties are notably different from those ofthe PBRs presented in Section 121 Monolith reactors offerstructured well-defined flow paths for the reactive flow whichoccurs through random paths in PBRs In other words the res-idence time of the reactive flow is predictable and the residencetime distribution is narrow in monoliths whereas in a PBR dif-ferent elements of the reactive mixture can pass through the bedat different rates resulting in a wider distribution of residencetimes This is a situation that is crucial for reactions where anintermediate species is the desired product and has to beremoved from the reactor before it is converted into an unde-sired speciesHydraulic diameters of monolithic channels range between

ca 3 times 10minus4 m and 6 times 10minus3 m [8] Combination of such smalldiameter channels leads to surface areas per reactor volume inthe order of ~104 m2m3 (which is ~103 m2m3 for PBRs) andvoid fractions up to ~75 (which is ~40 for PBRs) As shownin Figure 110 [9] these design properties allow monolith reac-tors to operate with pressure drops that are up to three orders ofmagnitude less than those observed in PBRs

Monolith reactors differ from PBRs in terms of transportproperties Owing to the small channel diameters the flowregime is laminar In this case channel shape and diameter dic-tate the values of heat andmass transfer coefficients according tothe definitions of the Nusselt (Nu= hf dh λf ) and Sherwood(Sh = kgdh DAB) numbers respectively Assuming that the flowis fully developed values of Nu and Sh are constant for a givenchannel shape [10] However in the case of PBRs where turbu-lent flow conditions are valid transport coefficients improvewith the degree of turbulence and mixing within the reactorIt is worth noting that transport coefficients in monolith chan-nels can be slightly affected by the flow rate if the surface of thechannel is tortuous The reader is directed to Chapter 8 for adetailed analysis and discussion of monolith reactorsHeat management in monolith reactors via external heating

or cooling is not as effective as in PBRs due to lack of convectiveheat transport in the radial direction At this point the materialof construction of the monolithic structure affects the overallperformance Monolith reactors can be made of metals or cera-mics In case of nonadiabatic reactions metallic monoliths arepreferred due to their higher thermal conductivity which par-tially eliminates the lacking convective contribution Ceramicmonoliths on the other hand have very low thermal conductiv-ities (eg 3 WmK for cordierite [11]) and are suitable for use inadiabatic operationsDespite their notable advantages in terms of residence time

distribution and pressure drop the operating windows of mon-olith reactors are narrower than those of PBRs As the catalyst isintegrated to the monolithic structure replacement of the cata-lyst bed in case of its irreversible deactivation becomes a seriousissue Moreover small channels are subject to the risk of plug-ging either by the dirt and scale that can come together with thefeed stream or by phenomena such as coking that may occurduring reactions involving hydrocarbons conducted at hightemperatures In such as case flow distribution and residencetime in the channels will be disturbed and product distributionwill be adversely affected Prevention of these risks is possible bycareful selection and control of the operating conditions whichin turn put some limitations on the versatility of using monolithreactorsThe capability of offering high surface area-to-volume ratios

together with low pressure drop makes monolith reactors the

Feedstock(+ steam)

Combustionchamber

Catalyst bed

Synthesis gas

Pressureshell

Refractory

Oxygen(or enriched air)

Figure 18 Packed-bed reactor configuration for autothermal reforming ofmethane to synthesis gas(Source Aasberg-Petersen et al [7] Reproduced with permission of Elsevier)

Flow

Pores

L

Figure 19 Schematic presentation of a monolith reactor(Source Onsan and Avci [1] Reproduced with permission of Elsevier)

8 Chapter 1

unique choice for use as three-way catalytic converters in vehi-cles to regulate the emission levels The compact nature of themonolithic catalytic converters allows their integration intothe exhaust gas aftertreatment zone of the vehicles These con-verters involve washcoated layers of precious metal catalysts thatare capable of reducing the NOx CO and unburned hydrocar-bon content of the exhaust gas below the legislative limits Apartfrom vehicular use monolith reactors are also used in NOx

removal from flue gases in power stations because of their capa-bility of providing adiabatic conditions with low pressure dropIt is worth noting that monolith reactors are not limited for useonly in gas-phase reactions and can also be used for handlinggasndashliquid-type reactive mixtures [10]

123 Radial flow reactorsIn addition to monolith reactors pressure drop in fixed-bedoperation can be reduced by employing radial flow reactorsThese units are essentially packed-bed type with gaseous reac-tive flow being in the radial direction that is perpendicular tothe catalyst bed instead of being in the axial direction(Figure 111 [4]) The radial flow pattern is achieved by directingthe flow to the catalyst pellets that are packed between two per-forated cylinders or concentric screens The flow orientation isflexible that is can be either from outside cylinder to inside cyl-inder or vice versa In this design radial flow distance along thecatalyst bed is constant and is independent of the amount of cat-alyst packed This unique featuremakes radial flow reactors suit-able for use in cases where large catalyst volumes are needed inhigh-pressure operations with strict pressure drop limitationsDuring operation however the catalyst bed settles down andcauses a gap for bypassing of the fresh feed through the upper

part of the perforated cylinder This issue can be addressed byrefining the design of the upper closure [4] Radial flow reactorsare used in such applications as the synthesis of ammonia(Figure 112 [12]) and methanol

124 Trickle-bed reactorsTrickle-bed reactors are similar to the PBR geometry describedin Section 1212 with the main difference being the coexistence

1000

100

10

1

01100 1000

Specific surface area AVR in m2m3

Pres

sure

dro

p pe

r le

ngth

in m

bar

m

10 000

Spheres void fraction 40Rings void fraction 45 LD = 1Rings void fraction 60 LD = 1Rings void fraction 80 LD = 1

Corning monoliths OFA 70 ndash 80

15 mm6 mm

2 mm

1 mm05 mm

DaDi= 042

DaDi= 06

DaDi= 084

Da= 12 mm2535 cpsi

5025 cpsiConditions

Air at 20degC 1 barsuperficial velocity 1 ms

10015 cpsi

200125 cpsi

40075 cpsi6004 cpsi

9003 cpsi12003 cpsi

16002 cpsi

Da= 45 mm

Figure 110 Comparison of pressure drop invarious configurations of monoliths andpacking structures(Source Boger et al [9] Reproduced withpermission of American Chemical Society)

Figure 111 Radial flow reactor concept(Source Eigenberger [4] Reproduced with permission of John Wiley ampSons Inc)


of gas and liquid phases in the reactive mixture and puttingtrickle-bed reactors among those classified as three-phase(gasndashliquidndashsolid) reactors In gasndashsolid PBRs described inSection 1212 headspace above the catalyst bed is usually filledwith inert ceramic balls to ensure uniform distribution ofthe gaseous feed over the entire bed Cocurrent feeding of gasand liquid phases however calls for using a more sophisticateddistributor design that is expected to mix the two phasesand then distribute them uniformly across the catalyst bed toensure sufficient wetting of the catalyst pellets and to preventchanneling of the gas and liquid components in the feed Therequirement of sophisticated distributors such as bubble captrays is another factor that differentiates trickle-bed reactorsfrom gasndashsolid PBRs Status of feed mixture distribution tothe catalyst bed dictates the diameter of the reactor which isusually under 5 m Height-to-diameter ratio is usually in therange of 5 and 25 [13] Typical sizes of the catalyst pellets whichcan be cylinder sphere extrudate needle or bead in shaperange between 1 and 5 times 10minus3 m and give bed void fractionsbetween ~035 and 040 [13] Details on the design analysisand operation of trickle-bed reactors are provided in Chapters5 and 13Trickle-bed reactors are mainly used in key petroleum

refining applications such as hydrocracking hydrodesulfuriza-tion and hydroisomerization The process involves thecombination of hydrogenationhydrotreating and cracking of

vacuum gas oil and residues (liquid phase) to produce lighterhydrocarbons such as gasoline in the presence of hydrogen(gas phase) over a catalyst (solid phase) in the 300ndash600 Crange and at pressures up to ~150 atm to ensure high solubilityof the gaseous phase in the liquid Conventional hydrocrakingcatalysts such as Pt on aluminosilicates or zeolites involve twocomponents namely an acidic component for cracking andisomerization reactions and a noble metal component forthe hydrogenation reactions [14] The trickle-bed reactorinvolves the presence of up to six successive catalyst bedsSince hydrocracking reactions are exothermic adiabatic tem-perature rise in each bed is regulated by interstage coolingenabled by the injection of cold hydrogen quenches thegasndashliquid mixture is remixed and redistributed prior to itsentrance to the succeeding bed In hydrodesulfurizationwhich is an important operation in crude oil refining theorganic sulfur components that is sulfides disulfides thiolsand thiophenes existing in crude oil (liquid phase) are con-verted to hydrogen sulfide in the presence of hydrogen (gasphase) over alumina-supported CondashMo or NindashMo catalysts(solid phase) in the 350ndash400 C range The resulting H2S isthen removed by processing over beds of ZnO In hydroisome-rization on the other hand the light alkanes in the C4ndashC6

range are converted to branched-chain isomers in the presenceof hydrogen for producing high-octane component additivesfor being blended into gasoline The process carried out intrickle-bed reactors involves the use of catalysts such asPt supported on chlorinated alumina or on acidic zeolitesIn contrast with hydrocrackers interstage heat exchange isnot used in hydroisomerization reactors which involve milderconditions with temperatures and pressures ranging betweenca 110ndash180 C and 20ndash70 atm respectively As exothermicequilibrium reactions are involved in hydroisomerizationthe catalyst should be able to operate at low temperatures tofavor the desired conversions

125 Short contact time reactorsPressure drop in fixed beds can be reduced by minimizing theamount of catalyst used which leads to the existence of shortcontact times In addition to reduction of pressure drop thesereactors are ideal for carrying out reactions whose extent andproduct distribution depend strongly on the contact time(eg direct partial oxidation of hydrocarbons to synthesisgas) A typical concept of such a reactor called the disk reactoris shown in Figure 113 [4] The reactor involves a thin layer ofcatalyst in the form of wire gauzes or pellets whose height anddiameter are in the orders of centimeters and meters respec-tively Quenching at the downstream of the catalyst bed helpsin halting further conversion of the products into otherunwanted speciesIn addition to the disk reactor short contact times can also be

achieved in monolith reactors (Section 122) and in microchan-nel reactors (Section 125) the latter involving fluid mechanical

Main inlet

Manhole andcatalyst

loading holes

Shellof internals

Outlet

Cold bypass

Lower exchangers

Transfer tube

Perforatedcenter tube

Innerannular space

Outerannular space

Pressure shell

Innerbasket lid

Outerbasket lid

Ouench

No 1 bed

No 2 bed

Figure 112 Radial flow ammonia synthesis converter by Haldor-Topsoslashe(Source Couper et al [12] Reproduced with permission of Elsevier)

10 Chapter 1

properties and architectures similar to those of monolithswhere the existence of thin layers of washcoated porouscatalysts together with high fraction of void space allows fastfluid flow almost without compromise from pressure drop(Figure 114 [1]) These factors lead to the occurrence of contacttimes in the order of milliseconds whereas it is in the order ofseconds in PBRs Like in the case of monoliths the existence of astructured flow pattern in microchannel units leads to precisecontrol of residence times that promotes selective productionsEven though such similarities exist between monolith andmicrochannel reactors they differ in certain aspects Micro-channel units have channel diameters in the submillimeterrange whereas larger diameter channels up to 6 times 10minus3 m areused in monoliths Owing to the constant Nu and Sh numbersper cross-sectional channel shape higher heat and mass trans-port coefficients can be obtained in microchannels as a result ofthe smaller hydraulic diameters which also lead to higher surfacearea-to-volume ratios (ie up to ~5 times 104 m2m3) than those ofmonoliths These factors favor precise regulation of reactiontemperature an important benefit for strongly exothermic reac-tions Due to their special manufacturing techniques involvingmicromachining and bonding of the plates (Figure 114 [1])various nonlinear patterns (eg wavy shapes) along the channellength which induce static mixing and improve heat transportcan be implemented in microchannels [15] On the other handin monoliths channels are limited to have straight axial pat-terns Finally the range of materials of construction is versatile(eg various metals and ceramics polymers silicon) in micro-channels whereas monoliths can be made of ceramics andmetals only

In addition to their advantages stated earlier compact dimen-sions of the microchannel reactors allow inherently safe produc-tions as the risks associated with reactions (eg thermalrunaway) are not significant due to the small quantities in the

order of microliters processed in each channel Even thoughsmall throughput is a disadvantage of short contact time reac-tors the capacity of the microchannel reactors can be rapidlyincreased through the so-called numbering-up approach whichis much simpler than the traditional scaling-up approach Theresulting capacities are expected to be suitable for small-scalethroughput industries such as pharmaceuticals and fine chem-ical productions Applications of microchannel reactors in theseindustries are provided by Hessel et al [16] Nevertheless pro-duction capacities of the microchannel units and other shortcontact time reactors are far from being able to compete withthose of the continuously operating commercial reactorsinvolved in the petroleum and petrochemical industries Thereader is directed to Chapters 9 and 14 for more detailed infor-mation about the microchannel reactors

13 Reactors with moving bed of catalysts

131 Fluidized-bed reactorsFluidized-bed reactors (FBRs) are continuously operating unitsof the gasndashsolid type involving a catalyst bed which is fluidizedwhen the volumetric flow rate of the gaseous feed stream exceedsa limiting value called the minimum fluidization flow rate Theresulting degree of mixing between the gas and solid phases inthe FBR brings several operational advantages over a gasndashsolidPBR (Section 121) FBRs offer uniform temperature distribu-tion due to intensive mixing which minimizes the chance ofhot spot formation in exothermic reactions Heat management

(c)

(b)

Catalystwashcoat

Microchannel

Microchannel

Wall

Line of symmetry xL

y

Ls

δs

δsH2

H2

HS

yw

Pores

Lines of symmetry

Bonding

Bonding

(a)

Figure 114 Schematic presentation of a microchannel reactor (a) Machinedplates with microchannels (b) microchannel reactor block obtained afterbonding the plates and (c) characteristic section of the multichannel reactor(Source Onsan and Avci [1] Reproduced with permission of Elsevier)

Catalyst

Quench

Figure 113 Disk reactor concept(Source Eigenberger [4] Reproduced with permission of John Wiley ampSons Inc)


in FBRs is conventionally carried out by the heat transfer sur-faces that are immersed into the reactor vessel In this respectfluidization favors heat transfer coefficients and subsequentfast heat exchange between the bed and immersed heat transfersurfaces Mobility of the catalyst phase widens the operatingwindow for allowable pressure drop Therefore pellet sizessmaller than those involved in PBRs can be used in FBRs andhigher reaction rates can be obtained due to increased catalyticsurface area per unit bed volume Even though higher heats ofreactions evolve with increased rates the possibility of fast heatexchange helps in effective regulation of the bed temperatureFBRs also allow constant catalytic activity either by online addi-tion of fresh catalyst or by its continuous regeneration in a sep-arate zone like in the case of the fluidized catalytic cracking(FCC) operation described later Modeling and design aspectsof FBRs are explained in detail in Chapter 4The advantages listed previously for FBRs however have to be

considered together with several operational limitations Fluidi-zation of the catalyst pellets at high velocities can cause unavoid-able acceleration of the erosion of both reactor vessel and heatexchange surfaces and their undesirable breakdown into smallerparticle sizes eventually calls for the need of cost-intensive cata-lyst separationgas purification equipment In contrast withbreakdown the pellets can also merge into each other and theresulting increase in particle weights can cause defluidizationwhich can seriously disturb the reactor operationMoreover res-idence time distribution is not narrow in FBRs due to the chaoticmovement of reactive fluid inside the vessel Another operationaldrawback of FBRs is linked with their high sensitivity against thepresence of sulfur in the gaseous feed mixture Once they enterthe reactor sulfur-containingmolecules can immediately poisonthe entire bed due to intense mixing of the phases and the highlyexposed surface area of small catalyst particles and can eventuallycause a suddendrop in pressure This serious drawback howeveris less serious in gasndashsolid PBRs as sulfur poisoning moves like awave front In otherwords at the beginning of the operation onlythe section of the packed bednear the inletwill be poisoned whilepellets at the downstream will remain active until the ones at theupstream are saturated with sulfurApart from the operational drawbacks stated earlier capital

and operating expenses involved in an FBR exceed those of aPBR of equivalent capacity due to requirements of larger vesselvolume for handling fluidization and of installing gas purifica-tion and solid circulation components Chaotic nature of theoperation also calls for a tedious preliminary study of the proc-ess of interest at the pilot scale that should be followed by a laborand cost-intensive scaling-up stage all of which eventuallyincrease the capital cost of the commercial FBR unitAlthough not as widely used as a gasndashsolid PBR FBR remains

as the only choice for processes such as FCC and high-temperature FischerndashTropsch (HTFT) synthesis both of whichhave key roles in the petroleum processing and petrochemicalindustries FCC is a critical step in petroleum refining andinvolves catalytic breakdown of heavy gas oil molecules into

commercially valuable products such as gasoline diesel and ole-fins The FBR reactor shown in Figure 115 [17] is composed ofa riser and a regenerator between which the catalyst is circulatedcontinuously at rates that can exceed 100 tonsmin Endother-mic cracking reactions that take place in the riser at tempera-tures of 500ndash550 C unavoidably deposit coke on the surfaceof the zeolite-based catalyst pellets [17] Spent catalysts are con-tinuously transported to the regenerator in which coke is burnedoff with hot air at ca 730 C for the restoration of the catalyticactivity The cycle is completed when the regenerated catalystsare conveyed back to the riser unit Heat needed to drive theendothermic cracking reactions is supplied by the hot catalyststhat come from the regenerator HTFT synthesis on the otherhand involves catalytic conversion of synthesis gas into a hydro-carbon mixture rich in olefins and gasoline The process is car-ried out at 340 C and 20 atm over iron-based catalysts As FTsynthesis is strongly exothermic and the product distributionis a strong function of temperature the catalyst bed should bemaintained at isothermal conditions This requirement is metby the circulating fluidized-bed (CFB) reactor known as theSasol Synthol reactor shown in Figure 116a [12] in which heatreleased during reactions is absorbed by the cooling coilsimmersed into the reactor vessel to produce steam [18 19]These reactors can operate with capacities up to 8 times 103 bar-relsday (33 times 105 tonsyear) CFB reactors are then replacedby turbulent FBRs known as Sasol Advanced Synthol reactors(Figure 116b [19]) due to their smaller size lower capitalexpense requirements and maintenance costs and their abilityto operate at higher conversions and capacities up to 2 times 104

Product

a

fb

c

d

Flue gas

e

Feed oil

Air

Figure 115 Riser cracking process by UOP (a) Reactor (b) stripper(c) riser (d) slide valve (e) air grid and (f ) regenerator(Source Werther [17] Reproduced with permission of John Wiley ampSons Inc)

12 Chapter 1

barrelsday (85 times 105 tonsyear) with lower pressure drop [1819] The use of FBRs in HTFT is extensively discussed inChapter 12

132 Slurry reactorsSlurry reactors involve the coexistence and intense mixing ofgas liquid and solid phases in the same volume The possibilityto run slurry reactors in the batch semibatch or continuousmodes differentiates these reactors from others in terms of oper-ational flexibility In slurry reactors the roles of the three phasescan be different that is liquid can be a reactant a product or aninert that serves as a contacting medium for gas and solids Sim-ilarly dissolved gas can either be a reactant or an inert for indu-cing mixing of liquid and solids via bubbling The solid phaseusually corresponds to the finely dispersed catalyst particles withdiameters lower than 5 times 10minus3 m [20]

Slurry reactors are typically used for highly exothermic reac-tions Heat removal from the reaction mixture is provided bycooling coils immersed into the reactor vessel Intense mixingwhich is enabled either by gas bubbling or by a mechanical agi-tator increases the heat transfer coefficient between the reactionmixture and coils and improves the rate of heat removal Highheat capacity and heat transfer coefficients of the slurries areother factors that further promote heat transport and tempera-ture control Excellent heat management capabilities of slurryreactors make them promising candidates for several processeswith the most popular one being the low-temperature FischerndashTropsch (LTFT) synthesis that involves conversion of syngasinto a hydrocarbon mixture heavier than that synthesized inHTFT LTFT is carried out in the ~190ndash250 C range and at

pressures between 20 and 40 atm over Co-based catalysts[6 18] As Co is more active than the Fe catalyst of HTFT[21] exothermic heat generation is higher and the demandfor fast heat removal becomes more critical The reaction startsin the gasndashsolid mode where the synthesis gas with a molar H2CO ratio of ~2 contacts the Co-based catalyst pellets In thecourse of reaction the liquid phase called wax is produced firstin the pores of the pellets and then in the entire reactor Theseconditions can be handled in a slurry bubble column reactor(SBCR) a special version of the slurry reactor described inFigure 117 [21] The same process can also be carried out ina multitubular PBR involving trickle flow However the slurrybubble column offers several advantages such as lower pressuredrop (ca 1 atm in SBCR vs 4 atm in PBR) higher intrinsic cat-alytic activity due to the possibility of using small particle sizesthat minimize intraparticle diffusion limitations higher masstransfer coefficients due to well mixing longer runs due to pos-sibility of online additionremoval of the catalyst better temper-ature control improving reactant conversion and productselectivity and lower capital expenditure requirements [21]Nevertheless the drawbacks brought by the mobility of the cat-alyst phase that is the need for catalystndashwax separation and therisk of immediate catalyst poisoning should not be underesti-mated in SBCR operation Apart from LTFT synthesis slurryreactors are used in other applications such as oxidation andhydroformylation of olefins methanation and polymerizationreactions and ethynylation of aldehydes [20] Further informa-tion regarding the modeling and design of the slurry reactors ispresented in Chapter 6 The reader is also directed to Chapter 12for a detailed discussion about the use of slurry reactors in LTFT

Tail gas

Cyclones

Catalyst-settlinghopper

Slide valves

Fresh feed andrecycle

Feed preheater

(a) (b)

Gas and catalystmixture

Riser

Reactor

Gooseneck

Cooler groups

CatalystStandpipe

Cooling-oiloutlet

Cooling-oilinlet

Steam

ProductsGases

Cyclones

Fluidized

Boiler feedwater

Gasdistributor

Total feed

Figure 116 High-temperature FischerndashTropsch synthesis reactors (a) Sasol Synthol circulating fluidized-bed reactor(Source Couper et al [12] Reproduced with permission of Elsevier) (b) Sasol Advanced Synthol turbulent fluidized-bed reactor(Source Steynberg et al [19] Reproduced with permission of Elsevier)


133 Moving-bed reactorsMoving-bed reactors are preferred when there is a need for con-tinuous catalyst regeneration In this operation fresh catalyst isfed from the top of the reactor and it moves in the downflowdirection by gravitational forces Spent catalyst leaving the reac-tor at the bottom is usually replaced in the continuous modeWhile the catalyst movement is downward reactive mixtureflow can be cocurrent or countercurrent to that of the cata-lyst flowMoving-bed reactors do not involve intense mixing of the cat-

alyst bed with the reaction mixture In this respect heat manage-ment within the bed is not as efficient as that involved in FBRs orin slurry reactors High heat capacity of the circulating catalystpellets dictates the heat transport in the moving-bed reactors Asdescribed in Chapter 13 these reactors are used in catalytichydrotreating of heavy oils in which the moving bed ensuressteady conditions for the catalyst and therefore minimizes theneed for periodic shutdowns

14 Reactors without a catalyst bed

The reactor types introduced in Sections 12 and 13 depend onthe existence of a catalyst bed either fixed or moving for theoperation However there are multiphase reactions such asthe gasndashliquid type which do not involve the use of a solid cat-alyst Gas cleaningpurification applications such as removal of

CO2 or H2S from gas streams via mono-diethanolamine ordi-triethylene glycol solutions and removal of nitrogenoxides by water liquid-phase processes of oxidation nitrationalkylation hydrogenation or manufacturing of products suchas sulfuric acid nitric acid and adipic acid and biochemicalprocesses such as fermentation and oxidation of wastewaterare examples of industrial applications of gasndashliquid reactions[22] Depending on factors such as residence time distributionof the phases throughput demand of the process and heattransfer requirements gas and liquid phases can be contactedin various configurations that is gas can be distributed intothe bulk liquid in the form of bubbles (bubble columns platecolumns) liquid can be sprayed to the bulk gas in the form ofdroplets (spray columns) or both phases can be contacted asthin films over an inert packing or on the reactor wall (packedcolumns wetted wall columns) The common direction for liq-uid flow is from the top to the bottom of the reactor and gas flowis usually in the opposite direction Column-type reactors pre-sented here involve a vessel and the particular componentsrequired to introduce or contact the phases (eg spargers forgas bubbling spraying equipments for showering down the liq-uid packing materials for contacting gas and liquid films liquiddistributors for ensuring uniform wetting of the packings sieveplates for directing the liquid flow and for providing cross-contact with the rising gas) In general reactor performance isaffected by the gas solubility which is expected to be high forimproved rates Operating temperature should be low whilepressure should be high for increasing gas solubility in the reac-tor Depending on the heat of reaction heat transfer equipmentcan be integrated to the reactor structure for regulating the tem-perature in the desired limitsIn some gasndashliquid reactions a mechanical agitator can be

integrated into the reactor for improving mixing and masstransfer between the phases In this case the reactor is calledas a stirred-tank reactor (Figure 118 [12]) The agitator is com-posed of an impeller that is mounted on a mechanically rotatedshaft Rotation and desired level of fluid mixing are provided bya variable speed electric motor that is placed on the reactor ves-sel Gasndashliquid stirred-tank reactors are also equipped by spar-gers for dispersing the gas bubbles into the liquid and by bafflesto minimize swirl and vortex formations In general four baffleseach of which is one-tenth of the vessel diameter are placed intothe inner perimeter of the vessel Aspect ratio which is definedas the ratio of the liquid height in the tank to the tank diameteris usually set up to be ~3 for increasing the residence timeof the gas and improving the extent of reaction betweenphases In such configurations mixing is provided by multipleimpellers mounted on the same shaft with distances up to onetank diameter [23]In stirred-tank reactors the possibility of regulating the agi-

tation speed and the selection of various impeller types and dia-meters allow control over the degree of mixing of differentfluids which is quantified by the impeller Reynolds number(Re = D2Sρμ D impeller diameter S speed of agitation ρ fluid

Steam

Slurry bed

Gaseous products

Boiler feedwater

Wax

Gas distributor

Syngas feed

Figure 117 Slurry bubble column reactor for low-temperatureFischerndashTropsch synthesis(Source Espinoza et al [21] Reproduced with permission of Elsevier)

14 Chapter 1

Multiphase Catalytic Reactors


Edited by



















10 9 8 7 6 5 4 3 2 1

Contents


Preface xii



11 Introduction 3




15 Summary 16

References 16








effectiveness 41




26 Summary 50

Nomenclature 50

Greek letters 51

References 51










37 Conclusions 73

Nomenclature 74

Greek letters 75

References 75




processes 81

v




upflow 85




flow regimes 91



Nomenclature 93

Greek letters 93

References 93



51 Introduction 97











Nomenclature 126

Greek letters 127

Subscripts 128

Superscripts 128

Abbreviations 128

References 128


61 Introduction 132







Acknowledgments 152

Nomenclature 152

Greek letters 153

Subscripts 153

References 153

vi Contents


71 Introduction 156


operation 157



75 Aeration 166

76 Mixing 166


78 Scale-up 167



Nomenclature 168

Greek letters 169

Subscripts 169

References 169









85 Conclusions 207

Nomenclature 207

Greek letters 208

Superscripts 208

Subscripts 208

References 209


91 Introduction 213




Nomenclature 226

Greek letters 227

Subscripts 227

References 228









107 Conclusions 248

References 249




Contents vii






115 Summary 265

Nomenclature 266

Greek letters 267


References 267





123 1950ndash1985 period 274


125 The future 288

References 291







hydrotreaters 316


unit 324

Nomenclature 326

Greek letters 327

Subscripts 327

Non-SI units 327

References 327










reactors 353



viii Contents

Nomenclature 359

References 359




153 Assumptions 366










Acknowledgments 375

Nomenclature 375

Greek letters 375

References 376

Index 377

Contents ix


























x






Preface






xii







Preface xiii

PART 1


CHAPTER 1



Abstract


11 Introduction







3









CH4 +H2O=CO+ 3H2 ΔH = 206 kJ mol 1 2



Raw materialinput

Feedprocessing

unit(s)

Upstreamoperations

Recycle stream


To sideproductwaste


Finishedproduct(s)

Purificationunit(s)

Separationunit(s)

Reactor(s)


Catalystparticles

Pores

ξ= Rp

Catalyst bedL

Flow

Rtr

z


4 Chapter 1










Circulationturbine

Steamgenerator

Feedwater

Steam


Steam drum

Feedwater

(a) (b) (c)


Interstagegas feed

Feed gas


(a) (b) (c)


6 Chapter 1








CH4 +H2O=CO+ 3H2 ΔH = 206 kJ mol 1 2




Stage 1Stage 1

Steam

Water

Steam

Water

FeedExit

Stage 2Stage 2

Stage 3Stage 3

20 NH3(N2 H2 CH4)

Circulating gas

Off-gas

NH3 liquid


Condensationcoolers









Feedstock(+ steam)

Combustionchamber

Catalyst bed

Synthesis gas

Pressureshell

Refractory



Flow

Pores

L


8 Chapter 1






1000

100

10

1

01100 1000


Pres

sure

dro

p pe

r le

ngth

in m

bar

m

10 000



15 mm6 mm

2 mm

1 mm05 mm

DaDi= 042

DaDi= 06

DaDi= 084

Da= 12 mm2535 cpsi

5025 cpsiConditions


10015 cpsi

200125 cpsi

40075 cpsi6004 cpsi

9003 cpsi12003 cpsi

16002 cpsi

Da= 45 mm










Main inlet

Manhole andcatalyst

loading holes

Shellof internals

Outlet

Cold bypass

Lower exchangers

Transfer tube


Innerannular space

Outerannular space

Pressure shell

Innerbasket lid

Outerbasket lid

Ouench

No 1 bed

No 2 bed


10 Chapter 1






(c)

(b)

Catalystwashcoat

Microchannel

Microchannel

Wall

Line of symmetry xL

y

Ls

δs

δsH2

H2

HS

yw

Pores

Lines of symmetry

Bonding

Bonding

(a)


Catalyst

Quench








Product

a

fb

c

d

Flue gas

e

Feed oil

Air


12 Chapter 1





Tail gas

Cyclones


Slide valves


Feed preheater

(a) (b)


Riser

Reactor

Gooseneck

Cooler groups

CatalystStandpipe

Cooling-oiloutlet

Cooling-oilinlet

Steam

ProductsGases

Cyclones

Fluidized

Boiler feedwater

Gasdistributor

Total feed










Steam

Slurry bed

Gaseous products

Boiler feedwater

Wax

Gas distributor

Syngas feed


14 Chapter 1


Edited by



















10 9 8 7 6 5 4 3 2 1

Contents


Preface xii



11 Introduction 3




15 Summary 16

References 16








effectiveness 41




26 Summary 50

Nomenclature 50

Greek letters 51

References 51










37 Conclusions 73

Nomenclature 74

Greek letters 75

References 75




processes 81

v




upflow 85




flow regimes 91



Nomenclature 93

Greek letters 93

References 93



51 Introduction 97











Nomenclature 126

Greek letters 127

Subscripts 128

Superscripts 128

Abbreviations 128

References 128


61 Introduction 132







Acknowledgments 152

Nomenclature 152

Greek letters 153

Subscripts 153

References 153

vi Contents


71 Introduction 156


operation 157



75 Aeration 166

76 Mixing 166


78 Scale-up 167



Nomenclature 168

Greek letters 169

Subscripts 169

References 169









85 Conclusions 207

Nomenclature 207

Greek letters 208

Superscripts 208

Subscripts 208

References 209


91 Introduction 213




Nomenclature 226

Greek letters 227

Subscripts 227

References 228









107 Conclusions 248

References 249




Contents vii






115 Summary 265

Nomenclature 266

Greek letters 267


References 267





123 1950ndash1985 period 274


125 The future 288

References 291







hydrotreaters 316


unit 324

Nomenclature 326

Greek letters 327

Subscripts 327

Non-SI units 327

References 327










reactors 353



viii Contents

Nomenclature 359

References 359




153 Assumptions 366










Acknowledgments 375

Nomenclature 375

Greek letters 375

References 376

Index 377

Contents ix


























x






Preface






xii







Preface xiii

PART 1


CHAPTER 1



Abstract


11 Introduction







3









CH4 +H2O=CO+ 3H2 ΔH = 206 kJ mol 1 2



Raw materialinput

Feedprocessing

unit(s)

Upstreamoperations

Recycle stream


To sideproductwaste


Finishedproduct(s)

Purificationunit(s)

Separationunit(s)

Reactor(s)


Catalystparticles

Pores

ξ= Rp

Catalyst bedL

Flow

Rtr

z


4 Chapter 1










Circulationturbine

Steamgenerator

Feedwater

Steam


Steam drum

Feedwater

(a) (b) (c)


Interstagegas feed

Feed gas


(a) (b) (c)


6 Chapter 1








CH4 +H2O=CO+ 3H2 ΔH = 206 kJ mol 1 2




Stage 1Stage 1

Steam

Water

Steam

Water

FeedExit

Stage 2Stage 2

Stage 3Stage 3

20 NH3(N2 H2 CH4)

Circulating gas

Off-gas

NH3 liquid


Condensationcoolers









Feedstock(+ steam)

Combustionchamber

Catalyst bed

Synthesis gas

Pressureshell

Refractory



Flow

Pores

L


8 Chapter 1






1000

100

10

1

01100 1000


Pres

sure

dro

p pe

r le

ngth

in m

bar

m

10 000



15 mm6 mm

2 mm

1 mm05 mm

DaDi= 042

DaDi= 06

DaDi= 084

Da= 12 mm2535 cpsi

5025 cpsiConditions


10015 cpsi

200125 cpsi

40075 cpsi6004 cpsi

9003 cpsi12003 cpsi

16002 cpsi

Da= 45 mm










Main inlet

Manhole andcatalyst

loading holes

Shellof internals

Outlet

Cold bypass

Lower exchangers

Transfer tube


Innerannular space

Outerannular space

Pressure shell

Innerbasket lid

Outerbasket lid

Ouench

No 1 bed

No 2 bed


10 Chapter 1






(c)

(b)

Catalystwashcoat

Microchannel

Microchannel

Wall

Line of symmetry xL

y

Ls

δs

δsH2

H2

HS

yw

Pores

Lines of symmetry

Bonding

Bonding

(a)


Catalyst

Quench








Product

a

fb

c

d

Flue gas

e

Feed oil

Air


12 Chapter 1





Tail gas

Cyclones


Slide valves


Feed preheater

(a) (b)


Riser

Reactor

Gooseneck

Cooler groups

CatalystStandpipe

Cooling-oiloutlet

Cooling-oilinlet

Steam

ProductsGases

Cyclones

Fluidized

Boiler feedwater

Gasdistributor

Total feed










Steam

Slurry bed

Gaseous products

Boiler feedwater

Wax

Gas distributor

Syngas feed


14 Chapter 1















10 9 8 7 6 5 4 3 2 1

Contents


Preface xii



11 Introduction 3




15 Summary 16

References 16








effectiveness 41




26 Summary 50

Nomenclature 50

Greek letters 51

References 51










37 Conclusions 73

Nomenclature 74

Greek letters 75

References 75




processes 81

v




upflow 85




flow regimes 91



Nomenclature 93

Greek letters 93

References 93



51 Introduction 97











Nomenclature 126

Greek letters 127

Subscripts 128

Superscripts 128

Abbreviations 128

References 128


61 Introduction 132







Acknowledgments 152

Nomenclature 152

Greek letters 153

Subscripts 153

References 153

vi Contents


71 Introduction 156


operation 157



75 Aeration 166

76 Mixing 166


78 Scale-up 167



Nomenclature 168

Greek letters 169

Subscripts 169

References 169









85 Conclusions 207

Nomenclature 207

Greek letters 208

Superscripts 208

Subscripts 208

References 209


91 Introduction 213




Nomenclature 226

Greek letters 227

Subscripts 227

References 228









107 Conclusions 248

References 249




Contents vii






115 Summary 265

Nomenclature 266

Greek letters 267


References 267





123 1950ndash1985 period 274


125 The future 288

References 291







hydrotreaters 316


unit 324

Nomenclature 326

Greek letters 327

Subscripts 327

Non-SI units 327

References 327










reactors 353



viii Contents

Nomenclature 359

References 359




153 Assumptions 366










Acknowledgments 375

Nomenclature 375

Greek letters 375

References 376

Index 377

Contents ix


























x






Preface






xii







Preface xiii

PART 1


CHAPTER 1



Abstract


11 Introduction







3









CH4 +H2O=CO+ 3H2 ΔH = 206 kJ mol 1 2



Raw materialinput

Feedprocessing

unit(s)

Upstreamoperations

Recycle stream


To sideproductwaste


Finishedproduct(s)

Purificationunit(s)

Separationunit(s)

Reactor(s)


Catalystparticles

Pores

ξ= Rp

Catalyst bedL

Flow

Rtr

z


4 Chapter 1










Circulationturbine

Steamgenerator

Feedwater

Steam


Steam drum

Feedwater

(a) (b) (c)


Interstagegas feed

Feed gas


(a) (b) (c)


6 Chapter 1








CH4 +H2O=CO+ 3H2 ΔH = 206 kJ mol 1 2




Stage 1Stage 1

Steam

Water

Steam

Water

FeedExit

Stage 2Stage 2

Stage 3Stage 3

20 NH3(N2 H2 CH4)

Circulating gas

Off-gas

NH3 liquid


Condensationcoolers









Feedstock(+ steam)

Combustionchamber

Catalyst bed

Synthesis gas

Pressureshell

Refractory



Flow

Pores

L


8 Chapter 1






1000

100

10

1

01100 1000


Pres

sure

dro

p pe

r le

ngth

in m

bar

m

10 000



15 mm6 mm

2 mm

1 mm05 mm

DaDi= 042

DaDi= 06

DaDi= 084

Da= 12 mm2535 cpsi

5025 cpsiConditions


10015 cpsi

200125 cpsi

40075 cpsi6004 cpsi

9003 cpsi12003 cpsi

16002 cpsi

Da= 45 mm










Main inlet

Manhole andcatalyst

loading holes

Shellof internals

Outlet

Cold bypass

Lower exchangers

Transfer tube


Innerannular space

Outerannular space

Pressure shell

Innerbasket lid

Outerbasket lid

Ouench

No 1 bed

No 2 bed


10 Chapter 1






(c)

(b)

Catalystwashcoat

Microchannel

Microchannel

Wall

Line of symmetry xL

y

Ls

δs

δsH2

H2

HS

yw

Pores

Lines of symmetry

Bonding

Bonding

(a)


Catalyst

Quench








Product

a

fb

c

d

Flue gas

e

Feed oil

Air


12 Chapter 1





Tail gas

Cyclones


Slide valves


Feed preheater

(a) (b)


Riser

Reactor

Gooseneck

Cooler groups

CatalystStandpipe

Cooling-oiloutlet

Cooling-oilinlet

Steam

ProductsGases

Cyclones

Fluidized

Boiler feedwater

Gasdistributor

Total feed










Steam

Slurry bed

Gaseous products

Boiler feedwater

Wax

Gas distributor

Syngas feed


14 Chapter 1

Contents


Preface xii



11 Introduction 3




15 Summary 16

References 16








effectiveness 41




26 Summary 50

Nomenclature 50

Greek letters 51

References 51










37 Conclusions 73

Nomenclature 74

Greek letters 75

References 75




processes 81

v




upflow 85




flow regimes 91



Nomenclature 93

Greek letters 93

References 93



51 Introduction 97











Nomenclature 126

Greek letters 127

Subscripts 128

Superscripts 128

Abbreviations 128

References 128


61 Introduction 132







Acknowledgments 152

Nomenclature 152

Greek letters 153

Subscripts 153

References 153

vi Contents


71 Introduction 156


operation 157



75 Aeration 166

76 Mixing 166


78 Scale-up 167



Nomenclature 168

Greek letters 169

Subscripts 169

References 169









85 Conclusions 207

Nomenclature 207

Greek letters 208

Superscripts 208

Subscripts 208

References 209


91 Introduction 213




Nomenclature 226

Greek letters 227

Subscripts 227

References 228









107 Conclusions 248

References 249




Contents vii






115 Summary 265

Nomenclature 266

Greek letters 267


References 267





123 1950ndash1985 period 274


125 The future 288

References 291







hydrotreaters 316


unit 324

Nomenclature 326

Greek letters 327

Subscripts 327

Non-SI units 327

References 327










reactors 353



viii Contents

Nomenclature 359

References 359




153 Assumptions 366










Acknowledgments 375

Nomenclature 375

Greek letters 375

References 376

Index 377

Contents ix


























x






Preface






xii







Preface xiii

PART 1


CHAPTER 1



Abstract


11 Introduction







3









CH4 +H2O=CO+ 3H2 ΔH = 206 kJ mol 1 2



Raw materialinput

Feedprocessing

unit(s)

Upstreamoperations

Recycle stream


To sideproductwaste


Finishedproduct(s)

Purificationunit(s)

Separationunit(s)

Reactor(s)


Catalystparticles

Pores

ξ= Rp

Catalyst bedL

Flow

Rtr

z


4 Chapter 1










Circulationturbine

Steamgenerator

Feedwater

Steam


Steam drum

Feedwater

(a) (b) (c)


Interstagegas feed

Feed gas


(a) (b) (c)


6 Chapter 1








CH4 +H2O=CO+ 3H2 ΔH = 206 kJ mol 1 2




Stage 1Stage 1

Steam

Water

Steam

Water

FeedExit

Stage 2Stage 2

Stage 3Stage 3

20 NH3(N2 H2 CH4)

Circulating gas

Off-gas

NH3 liquid


Condensationcoolers









Feedstock(+ steam)

Combustionchamber

Catalyst bed

Synthesis gas

Pressureshell

Refractory



Flow

Pores

L


8 Chapter 1






1000

100

10

1

01100 1000


Pres

sure

dro

p pe

r le

ngth

in m

bar

m

10 000



15 mm6 mm

2 mm

1 mm05 mm

DaDi= 042

DaDi= 06

DaDi= 084

Da= 12 mm2535 cpsi

5025 cpsiConditions


10015 cpsi

200125 cpsi

40075 cpsi6004 cpsi

9003 cpsi12003 cpsi

16002 cpsi

Da= 45 mm










Main inlet

Manhole andcatalyst

loading holes

Shellof internals

Outlet

Cold bypass

Lower exchangers

Transfer tube


Innerannular space

Outerannular space

Pressure shell

Innerbasket lid

Outerbasket lid

Ouench

No 1 bed

No 2 bed


10 Chapter 1






(c)

(b)

Catalystwashcoat

Microchannel

Microchannel

Wall

Line of symmetry xL

y

Ls

δs

δsH2

H2

HS

yw

Pores

Lines of symmetry

Bonding

Bonding

(a)


Catalyst

Quench








Product

a

fb

c

d

Flue gas

e

Feed oil

Air


12 Chapter 1





Tail gas

Cyclones


Slide valves


Feed preheater

(a) (b)


Riser

Reactor

Gooseneck

Cooler groups

CatalystStandpipe

Cooling-oiloutlet

Cooling-oilinlet

Steam

ProductsGases

Cyclones

Fluidized

Boiler feedwater

Gasdistributor

Total feed










Steam

Slurry bed

Gaseous products

Boiler feedwater

Wax

Gas distributor

Syngas feed


14 Chapter 1




upflow 85




flow regimes 91



Nomenclature 93

Greek letters 93

References 93



51 Introduction 97











Nomenclature 126

Greek letters 127

Subscripts 128

Superscripts 128

Abbreviations 128

References 128


61 Introduction 132







Acknowledgments 152

Nomenclature 152

Greek letters 153

Subscripts 153

References 153

vi Contents


71 Introduction 156


operation 157



75 Aeration 166

76 Mixing 166


78 Scale-up 167



Nomenclature 168

Greek letters 169

Subscripts 169

References 169









85 Conclusions 207

Nomenclature 207

Greek letters 208

Superscripts 208

Subscripts 208

References 209


91 Introduction 213




Nomenclature 226

Greek letters 227

Subscripts 227

References 228









107 Conclusions 248

References 249




Contents vii






115 Summary 265

Nomenclature 266

Greek letters 267


References 267





123 1950ndash1985 period 274


125 The future 288

References 291







hydrotreaters 316


unit 324

Nomenclature 326

Greek letters 327

Subscripts 327

Non-SI units 327

References 327










reactors 353



viii Contents

Nomenclature 359

References 359




153 Assumptions 366










Acknowledgments 375

Nomenclature 375

Greek letters 375

References 376

Index 377

Contents ix


























x






Preface






xii







Preface xiii

PART 1


CHAPTER 1



Abstract


11 Introduction







3









CH4 +H2O=CO+ 3H2 ΔH = 206 kJ mol 1 2



Raw materialinput

Feedprocessing

unit(s)

Upstreamoperations

Recycle stream


To sideproductwaste


Finishedproduct(s)

Purificationunit(s)

Separationunit(s)

Reactor(s)


Catalystparticles

Pores

ξ= Rp

Catalyst bedL

Flow

Rtr

z


4 Chapter 1










Circulationturbine

Steamgenerator

Feedwater

Steam


Steam drum

Feedwater

(a) (b) (c)


Interstagegas feed

Feed gas


(a) (b) (c)


6 Chapter 1








CH4 +H2O=CO+ 3H2 ΔH = 206 kJ mol 1 2




Stage 1Stage 1

Steam

Water

Steam

Water

FeedExit

Stage 2Stage 2

Stage 3Stage 3

20 NH3(N2 H2 CH4)

Circulating gas

Off-gas

NH3 liquid


Condensationcoolers









Feedstock(+ steam)

Combustionchamber

Catalyst bed

Synthesis gas

Pressureshell

Refractory



Flow

Pores

L


8 Chapter 1






1000

100

10

1

01100 1000


Pres

sure

dro

p pe

r le

ngth

in m

bar

m

10 000



15 mm6 mm

2 mm

1 mm05 mm

DaDi= 042

DaDi= 06

DaDi= 084

Da= 12 mm2535 cpsi

5025 cpsiConditions


10015 cpsi

200125 cpsi

40075 cpsi6004 cpsi

9003 cpsi12003 cpsi

16002 cpsi

Da= 45 mm










Main inlet

Manhole andcatalyst

loading holes

Shellof internals

Outlet

Cold bypass

Lower exchangers

Transfer tube


Innerannular space

Outerannular space

Pressure shell

Innerbasket lid

Outerbasket lid

Ouench

No 1 bed

No 2 bed


10 Chapter 1






(c)

(b)

Catalystwashcoat

Microchannel

Microchannel

Wall

Line of symmetry xL

y

Ls

δs

δsH2

H2

HS

yw

Pores

Lines of symmetry

Bonding

Bonding

(a)


Catalyst

Quench








Product

a

fb

c

d

Flue gas

e

Feed oil

Air


12 Chapter 1





Tail gas

Cyclones


Slide valves


Feed preheater

(a) (b)


Riser

Reactor

Gooseneck

Cooler groups

CatalystStandpipe

Cooling-oiloutlet

Cooling-oilinlet

Steam

ProductsGases

Cyclones

Fluidized

Boiler feedwater

Gasdistributor

Total feed










Steam

Slurry bed

Gaseous products

Boiler feedwater

Wax

Gas distributor

Syngas feed


14 Chapter 1


71 Introduction 156


operation 157



75 Aeration 166

76 Mixing 166


78 Scale-up 167



Nomenclature 168

Greek letters 169

Subscripts 169

References 169









85 Conclusions 207

Nomenclature 207

Greek letters 208

Superscripts 208

Subscripts 208

References 209


91 Introduction 213




Nomenclature 226

Greek letters 227

Subscripts 227

References 228









107 Conclusions 248

References 249




Contents vii






115 Summary 265

Nomenclature 266

Greek letters 267


References 267





123 1950ndash1985 period 274


125 The future 288

References 291







hydrotreaters 316


unit 324

Nomenclature 326

Greek letters 327

Subscripts 327

Non-SI units 327

References 327










reactors 353



viii Contents

Nomenclature 359

References 359




153 Assumptions 366










Acknowledgments 375

Nomenclature 375

Greek letters 375

References 376

Index 377

Contents ix


























x






Preface






xii







Preface xiii

PART 1


CHAPTER 1



Abstract


11 Introduction







3









CH4 +H2O=CO+ 3H2 ΔH = 206 kJ mol 1 2



Raw materialinput

Feedprocessing

unit(s)

Upstreamoperations

Recycle stream


To sideproductwaste


Finishedproduct(s)

Purificationunit(s)

Separationunit(s)

Reactor(s)


Catalystparticles

Pores

ξ= Rp

Catalyst bedL

Flow

Rtr

z


4 Chapter 1










Circulationturbine

Steamgenerator

Feedwater

Steam


Steam drum

Feedwater

(a) (b) (c)


Interstagegas feed

Feed gas


(a) (b) (c)


6 Chapter 1








CH4 +H2O=CO+ 3H2 ΔH = 206 kJ mol 1 2




Stage 1Stage 1

Steam

Water

Steam

Water

FeedExit

Stage 2Stage 2

Stage 3Stage 3

20 NH3(N2 H2 CH4)

Circulating gas

Off-gas

NH3 liquid


Condensationcoolers









Feedstock(+ steam)

Combustionchamber

Catalyst bed

Synthesis gas

Pressureshell

Refractory



Flow

Pores

L


8 Chapter 1






1000

100

10

1

01100 1000


Pres

sure

dro

p pe

r le

ngth

in m

bar

m

10 000



15 mm6 mm

2 mm

1 mm05 mm

DaDi= 042

DaDi= 06

DaDi= 084

Da= 12 mm2535 cpsi

5025 cpsiConditions


10015 cpsi

200125 cpsi

40075 cpsi6004 cpsi

9003 cpsi12003 cpsi

16002 cpsi

Da= 45 mm










Main inlet

Manhole andcatalyst

loading holes

Shellof internals

Outlet

Cold bypass

Lower exchangers

Transfer tube


Innerannular space

Outerannular space

Pressure shell

Innerbasket lid

Outerbasket lid

Ouench

No 1 bed

No 2 bed


10 Chapter 1






(c)

(b)

Catalystwashcoat

Microchannel

Microchannel

Wall

Line of symmetry xL

y

Ls

δs

δsH2

H2

HS

yw

Pores

Lines of symmetry

Bonding

Bonding

(a)


Catalyst

Quench








Product

a

fb

c

d

Flue gas

e

Feed oil

Air


12 Chapter 1





Tail gas

Cyclones


Slide valves


Feed preheater

(a) (b)


Riser

Reactor

Gooseneck

Cooler groups

CatalystStandpipe

Cooling-oiloutlet

Cooling-oilinlet

Steam

ProductsGases

Cyclones

Fluidized

Boiler feedwater

Gasdistributor

Total feed










Steam

Slurry bed

Gaseous products

Boiler feedwater

Wax

Gas distributor

Syngas feed


14 Chapter 1






115 Summary 265

Nomenclature 266

Greek letters 267


References 267





123 1950ndash1985 period 274


125 The future 288

References 291







hydrotreaters 316


unit 324

Nomenclature 326

Greek letters 327

Subscripts 327

Non-SI units 327

References 327










reactors 353



viii Contents

Nomenclature 359

References 359




153 Assumptions 366










Acknowledgments 375

Nomenclature 375

Greek letters 375

References 376

Index 377

Contents ix


























x






Preface






xii







Preface xiii

PART 1


CHAPTER 1



Abstract


11 Introduction







3









CH4 +H2O=CO+ 3H2 ΔH = 206 kJ mol 1 2



Raw materialinput

Feedprocessing

unit(s)

Upstreamoperations

Recycle stream


To sideproductwaste


Finishedproduct(s)

Purificationunit(s)

Separationunit(s)

Reactor(s)


Catalystparticles

Pores

ξ= Rp

Catalyst bedL

Flow

Rtr

z


4 Chapter 1










Circulationturbine

Steamgenerator

Feedwater

Steam


Steam drum

Feedwater

(a) (b) (c)


Interstagegas feed

Feed gas


(a) (b) (c)


6 Chapter 1








CH4 +H2O=CO+ 3H2 ΔH = 206 kJ mol 1 2




Stage 1Stage 1

Steam

Water

Steam

Water

FeedExit

Stage 2Stage 2

Stage 3Stage 3

20 NH3(N2 H2 CH4)

Circulating gas

Off-gas

NH3 liquid


Condensationcoolers









Feedstock(+ steam)

Combustionchamber

Catalyst bed

Synthesis gas

Pressureshell

Refractory



Flow

Pores

L


8 Chapter 1






1000

100

10

1

01100 1000


Pres

sure

dro

p pe

r le

ngth

in m

bar

m

10 000



15 mm6 mm

2 mm

1 mm05 mm

DaDi= 042

DaDi= 06

DaDi= 084

Da= 12 mm2535 cpsi

5025 cpsiConditions


10015 cpsi

200125 cpsi

40075 cpsi6004 cpsi

9003 cpsi12003 cpsi

16002 cpsi

Da= 45 mm










Main inlet

Manhole andcatalyst

loading holes

Shellof internals

Outlet

Cold bypass

Lower exchangers

Transfer tube


Innerannular space

Outerannular space

Pressure shell

Innerbasket lid

Outerbasket lid

Ouench

No 1 bed

No 2 bed


10 Chapter 1






(c)

(b)

Catalystwashcoat

Microchannel

Microchannel

Wall

Line of symmetry xL

y

Ls

δs

δsH2

H2

HS

yw

Pores

Lines of symmetry

Bonding

Bonding

(a)


Catalyst

Quench








Product

a

fb

c

d

Flue gas

e

Feed oil

Air


12 Chapter 1





Tail gas

Cyclones


Slide valves


Feed preheater

(a) (b)


Riser

Reactor

Gooseneck

Cooler groups

CatalystStandpipe

Cooling-oiloutlet

Cooling-oilinlet

Steam

ProductsGases

Cyclones

Fluidized

Boiler feedwater

Gasdistributor

Total feed










Steam

Slurry bed

Gaseous products

Boiler feedwater

Wax

Gas distributor

Syngas feed


14 Chapter 1

Nomenclature 359

References 359




153 Assumptions 366










Acknowledgments 375

Nomenclature 375

Greek letters 375

References 376

Index 377

Contents ix


























x






Preface






xii







Preface xiii

PART 1


CHAPTER 1



Abstract


11 Introduction







3









CH4 +H2O=CO+ 3H2 ΔH = 206 kJ mol 1 2



Raw materialinput

Feedprocessing

unit(s)

Upstreamoperations

Recycle stream


To sideproductwaste


Finishedproduct(s)

Purificationunit(s)

Separationunit(s)

Reactor(s)


Catalystparticles

Pores

ξ= Rp

Catalyst bedL

Flow

Rtr

z


4 Chapter 1










Circulationturbine

Steamgenerator

Feedwater

Steam


Steam drum

Feedwater

(a) (b) (c)


Interstagegas feed

Feed gas


(a) (b) (c)


6 Chapter 1








CH4 +H2O=CO+ 3H2 ΔH = 206 kJ mol 1 2




Stage 1Stage 1

Steam

Water

Steam

Water

FeedExit

Stage 2Stage 2

Stage 3Stage 3

20 NH3(N2 H2 CH4)

Circulating gas

Off-gas

NH3 liquid


Condensationcoolers









Feedstock(+ steam)

Combustionchamber

Catalyst bed

Synthesis gas

Pressureshell

Refractory



Flow

Pores

L


8 Chapter 1






1000

100

10

1

01100 1000


Pres

sure

dro

p pe

r le

ngth

in m

bar

m

10 000



15 mm6 mm

2 mm

1 mm05 mm

DaDi= 042

DaDi= 06

DaDi= 084

Da= 12 mm2535 cpsi

5025 cpsiConditions


10015 cpsi

200125 cpsi

40075 cpsi6004 cpsi

9003 cpsi12003 cpsi

16002 cpsi

Da= 45 mm










Main inlet

Manhole andcatalyst

loading holes

Shellof internals

Outlet

Cold bypass

Lower exchangers

Transfer tube


Innerannular space

Outerannular space

Pressure shell

Innerbasket lid

Outerbasket lid

Ouench

No 1 bed

No 2 bed


10 Chapter 1






(c)

(b)

Catalystwashcoat

Microchannel

Microchannel

Wall

Line of symmetry xL

y

Ls

δs

δsH2

H2

HS

yw

Pores

Lines of symmetry

Bonding

Bonding

(a)


Catalyst

Quench








Product

a

fb

c

d

Flue gas

e

Feed oil

Air


12 Chapter 1





Tail gas

Cyclones


Slide valves


Feed preheater

(a) (b)


Riser

Reactor

Gooseneck

Cooler groups

CatalystStandpipe

Cooling-oiloutlet

Cooling-oilinlet

Steam

ProductsGases

Cyclones

Fluidized

Boiler feedwater

Gasdistributor

Total feed










Steam

Slurry bed

Gaseous products

Boiler feedwater

Wax

Gas distributor

Syngas feed


14 Chapter 1


























x






Preface






xii







Preface xiii

PART 1


CHAPTER 1



Abstract


11 Introduction







3









CH4 +H2O=CO+ 3H2 ΔH = 206 kJ mol 1 2



Raw materialinput

Feedprocessing

unit(s)

Upstreamoperations

Recycle stream


To sideproductwaste


Finishedproduct(s)

Purificationunit(s)

Separationunit(s)

Reactor(s)


Catalystparticles

Pores

ξ= Rp

Catalyst bedL

Flow

Rtr

z


4 Chapter 1










Circulationturbine

Steamgenerator

Feedwater

Steam


Steam drum

Feedwater

(a) (b) (c)


Interstagegas feed

Feed gas


(a) (b) (c)


6 Chapter 1








CH4 +H2O=CO+ 3H2 ΔH = 206 kJ mol 1 2




Stage 1Stage 1

Steam

Water

Steam

Water

FeedExit

Stage 2Stage 2

Stage 3Stage 3

20 NH3(N2 H2 CH4)

Circulating gas

Off-gas

NH3 liquid


Condensationcoolers









Feedstock(+ steam)

Combustionchamber

Catalyst bed

Synthesis gas

Pressureshell

Refractory



Flow

Pores

L


8 Chapter 1






1000

100

10

1

01100 1000


Pres

sure

dro

p pe

r le

ngth

in m

bar

m

10 000



15 mm6 mm

2 mm

1 mm05 mm

DaDi= 042

DaDi= 06

DaDi= 084

Da= 12 mm2535 cpsi

5025 cpsiConditions


10015 cpsi

200125 cpsi

40075 cpsi6004 cpsi

9003 cpsi12003 cpsi

16002 cpsi

Da= 45 mm










Main inlet

Manhole andcatalyst

loading holes

Shellof internals

Outlet

Cold bypass

Lower exchangers

Transfer tube


Innerannular space

Outerannular space

Pressure shell

Innerbasket lid

Outerbasket lid

Ouench

No 1 bed

No 2 bed


10 Chapter 1






(c)

(b)

Catalystwashcoat

Microchannel

Microchannel

Wall

Line of symmetry xL

y

Ls

δs

δsH2

H2

HS

yw

Pores

Lines of symmetry

Bonding

Bonding

(a)


Catalyst

Quench








Product

a

fb

c

d

Flue gas

e

Feed oil

Air


12 Chapter 1





Tail gas

Cyclones


Slide valves


Feed preheater

(a) (b)


Riser

Reactor

Gooseneck

Cooler groups

CatalystStandpipe

Cooling-oiloutlet

Cooling-oilinlet

Steam

ProductsGases

Cyclones

Fluidized

Boiler feedwater

Gasdistributor

Total feed










Steam

Slurry bed

Gaseous products

Boiler feedwater

Wax

Gas distributor

Syngas feed


14 Chapter 1






Preface






xii







Preface xiii

PART 1


CHAPTER 1



Abstract


11 Introduction







3









CH4 +H2O=CO+ 3H2 ΔH = 206 kJ mol 1 2



Raw materialinput

Feedprocessing

unit(s)

Upstreamoperations

Recycle stream


To sideproductwaste


Finishedproduct(s)

Purificationunit(s)

Separationunit(s)

Reactor(s)


Catalystparticles

Pores

ξ= Rp

Catalyst bedL

Flow

Rtr

z


4 Chapter 1










Circulationturbine

Steamgenerator

Feedwater

Steam


Steam drum

Feedwater

(a) (b) (c)


Interstagegas feed

Feed gas


(a) (b) (c)


6 Chapter 1








CH4 +H2O=CO+ 3H2 ΔH = 206 kJ mol 1 2




Stage 1Stage 1

Steam

Water

Steam

Water

FeedExit

Stage 2Stage 2

Stage 3Stage 3

20 NH3(N2 H2 CH4)

Circulating gas

Off-gas

NH3 liquid


Condensationcoolers









Feedstock(+ steam)

Combustionchamber

Catalyst bed

Synthesis gas

Pressureshell

Refractory



Flow

Pores

L


8 Chapter 1






1000

100

10

1

01100 1000


Pres

sure

dro

p pe

r le

ngth

in m

bar

m

10 000



15 mm6 mm

2 mm

1 mm05 mm

DaDi= 042

DaDi= 06

DaDi= 084

Da= 12 mm2535 cpsi

5025 cpsiConditions


10015 cpsi

200125 cpsi

40075 cpsi6004 cpsi

9003 cpsi12003 cpsi

16002 cpsi

Da= 45 mm










Main inlet

Manhole andcatalyst

loading holes

Shellof internals

Outlet

Cold bypass

Lower exchangers

Transfer tube


Innerannular space

Outerannular space

Pressure shell

Innerbasket lid

Outerbasket lid

Ouench

No 1 bed

No 2 bed


10 Chapter 1






(c)

(b)

Catalystwashcoat

Microchannel

Microchannel

Wall

Line of symmetry xL

y

Ls

δs

δsH2

H2

HS

yw

Pores

Lines of symmetry

Bonding

Bonding

(a)


Catalyst

Quench








Product

a

fb

c

d

Flue gas

e

Feed oil

Air


12 Chapter 1





Tail gas

Cyclones


Slide valves


Feed preheater

(a) (b)


Riser

Reactor

Gooseneck

Cooler groups

CatalystStandpipe

Cooling-oiloutlet

Cooling-oilinlet

Steam

ProductsGases

Cyclones

Fluidized

Boiler feedwater

Gasdistributor

Total feed










Steam

Slurry bed

Gaseous products

Boiler feedwater

Wax

Gas distributor

Syngas feed


14 Chapter 1







Preface xiii

PART 1


CHAPTER 1



Abstract


11 Introduction







3









CH4 +H2O=CO+ 3H2 ΔH = 206 kJ mol 1 2



Raw materialinput

Feedprocessing

unit(s)

Upstreamoperations

Recycle stream


To sideproductwaste


Finishedproduct(s)

Purificationunit(s)

Separationunit(s)

Reactor(s)


Catalystparticles

Pores

ξ= Rp

Catalyst bedL

Flow

Rtr

z


4 Chapter 1










Circulationturbine

Steamgenerator

Feedwater

Steam


Steam drum

Feedwater

(a) (b) (c)


Interstagegas feed

Feed gas


(a) (b) (c)


6 Chapter 1








CH4 +H2O=CO+ 3H2 ΔH = 206 kJ mol 1 2




Stage 1Stage 1

Steam

Water

Steam

Water

FeedExit

Stage 2Stage 2

Stage 3Stage 3

20 NH3(N2 H2 CH4)

Circulating gas

Off-gas

NH3 liquid


Condensationcoolers









Feedstock(+ steam)

Combustionchamber

Catalyst bed

Synthesis gas

Pressureshell

Refractory



Flow

Pores

L


8 Chapter 1






1000

100

10

1

01100 1000


Pres

sure

dro

p pe

r le

ngth

in m

bar

m

10 000



15 mm6 mm

2 mm

1 mm05 mm

DaDi= 042

DaDi= 06

DaDi= 084

Da= 12 mm2535 cpsi

5025 cpsiConditions


10015 cpsi

200125 cpsi

40075 cpsi6004 cpsi

9003 cpsi12003 cpsi

16002 cpsi

Da= 45 mm










Main inlet

Manhole andcatalyst

loading holes

Shellof internals

Outlet

Cold bypass

Lower exchangers

Transfer tube


Innerannular space

Outerannular space

Pressure shell

Innerbasket lid

Outerbasket lid

Ouench

No 1 bed

No 2 bed


10 Chapter 1






(c)

(b)

Catalystwashcoat

Microchannel

Microchannel

Wall

Line of symmetry xL

y

Ls

δs

δsH2

H2

HS

yw

Pores

Lines of symmetry

Bonding

Bonding

(a)


Catalyst

Quench








Product

a

fb

c

d

Flue gas

e

Feed oil

Air


12 Chapter 1





Tail gas

Cyclones


Slide valves


Feed preheater

(a) (b)


Riser

Reactor

Gooseneck

Cooler groups

CatalystStandpipe

Cooling-oiloutlet

Cooling-oilinlet

Steam

ProductsGases

Cyclones

Fluidized

Boiler feedwater

Gasdistributor

Total feed










Steam

Slurry bed

Gaseous products

Boiler feedwater

Wax

Gas distributor

Syngas feed


14 Chapter 1

PART 1


CHAPTER 1



Abstract


11 Introduction







3









CH4 +H2O=CO+ 3H2 ΔH = 206 kJ mol 1 2



Raw materialinput

Feedprocessing

unit(s)

Upstreamoperations

Recycle stream


To sideproductwaste


Finishedproduct(s)

Purificationunit(s)

Separationunit(s)

Reactor(s)


Catalystparticles

Pores

ξ= Rp

Catalyst bedL

Flow

Rtr

z


4 Chapter 1










Circulationturbine

Steamgenerator

Feedwater

Steam


Steam drum

Feedwater

(a) (b) (c)


Interstagegas feed

Feed gas


(a) (b) (c)


6 Chapter 1








CH4 +H2O=CO+ 3H2 ΔH = 206 kJ mol 1 2




Stage 1Stage 1

Steam

Water

Steam

Water

FeedExit

Stage 2Stage 2

Stage 3Stage 3

20 NH3(N2 H2 CH4)

Circulating gas

Off-gas

NH3 liquid


Condensationcoolers









Feedstock(+ steam)

Combustionchamber

Catalyst bed

Synthesis gas

Pressureshell

Refractory



Flow

Pores

L


8 Chapter 1






1000

100

10

1

01100 1000


Pres

sure

dro

p pe

r le

ngth

in m

bar

m

10 000



15 mm6 mm

2 mm

1 mm05 mm

DaDi= 042

DaDi= 06

DaDi= 084

Da= 12 mm2535 cpsi

5025 cpsiConditions


10015 cpsi

200125 cpsi

40075 cpsi6004 cpsi

9003 cpsi12003 cpsi

16002 cpsi

Da= 45 mm










Main inlet

Manhole andcatalyst

loading holes

Shellof internals

Outlet

Cold bypass

Lower exchangers

Transfer tube


Innerannular space

Outerannular space

Pressure shell

Innerbasket lid

Outerbasket lid

Ouench

No 1 bed

No 2 bed


10 Chapter 1






(c)

(b)

Catalystwashcoat

Microchannel

Microchannel

Wall

Line of symmetry xL

y

Ls

δs

δsH2

H2

HS

yw

Pores

Lines of symmetry

Bonding

Bonding

(a)


Catalyst

Quench








Product

a

fb

c

d

Flue gas

e

Feed oil

Air


12 Chapter 1





Tail gas

Cyclones


Slide valves


Feed preheater

(a) (b)


Riser

Reactor

Gooseneck

Cooler groups

CatalystStandpipe

Cooling-oiloutlet

Cooling-oilinlet

Steam

ProductsGases

Cyclones

Fluidized

Boiler feedwater

Gasdistributor

Total feed










Steam

Slurry bed

Gaseous products

Boiler feedwater

Wax

Gas distributor

Syngas feed


14 Chapter 1

CHAPTER 1



Abstract


11 Introduction







3









CH4 +H2O=CO+ 3H2 ΔH = 206 kJ mol 1 2



Raw materialinput

Feedprocessing

unit(s)

Upstreamoperations

Recycle stream


To sideproductwaste


Finishedproduct(s)

Purificationunit(s)

Separationunit(s)

Reactor(s)


Catalystparticles

Pores

ξ= Rp

Catalyst bedL

Flow

Rtr

z


4 Chapter 1










Circulationturbine

Steamgenerator

Feedwater

Steam


Steam drum

Feedwater

(a) (b) (c)


Interstagegas feed

Feed gas


(a) (b) (c)


6 Chapter 1








CH4 +H2O=CO+ 3H2 ΔH = 206 kJ mol 1 2




Stage 1Stage 1

Steam

Water

Steam

Water

FeedExit

Stage 2Stage 2

Stage 3Stage 3

20 NH3(N2 H2 CH4)

Circulating gas

Off-gas

NH3 liquid


Condensationcoolers









Feedstock(+ steam)

Combustionchamber

Catalyst bed

Synthesis gas

Pressureshell

Refractory



Flow

Pores

L


8 Chapter 1






1000

100

10

1

01100 1000


Pres

sure

dro

p pe

r le

ngth

in m

bar

m

10 000



15 mm6 mm

2 mm

1 mm05 mm

DaDi= 042

DaDi= 06

DaDi= 084

Da= 12 mm2535 cpsi

5025 cpsiConditions


10015 cpsi

200125 cpsi

40075 cpsi6004 cpsi

9003 cpsi12003 cpsi

16002 cpsi

Da= 45 mm










Main inlet

Manhole andcatalyst

loading holes

Shellof internals

Outlet

Cold bypass

Lower exchangers

Transfer tube


Innerannular space

Outerannular space

Pressure shell

Innerbasket lid

Outerbasket lid

Ouench

No 1 bed

No 2 bed


10 Chapter 1






(c)

(b)

Catalystwashcoat

Microchannel

Microchannel

Wall

Line of symmetry xL

y

Ls

δs

δsH2

H2

HS

yw

Pores

Lines of symmetry

Bonding

Bonding

(a)


Catalyst

Quench








Product

a

fb

c

d

Flue gas

e

Feed oil

Air


12 Chapter 1





Tail gas

Cyclones


Slide valves


Feed preheater

(a) (b)


Riser

Reactor

Gooseneck

Cooler groups

CatalystStandpipe

Cooling-oiloutlet

Cooling-oilinlet

Steam

ProductsGases

Cyclones

Fluidized

Boiler feedwater

Gasdistributor

Total feed










Steam

Slurry bed

Gaseous products

Boiler feedwater

Wax

Gas distributor

Syngas feed


14 Chapter 1








CH4 +H2O=CO+ 3H2 ΔH = 206 kJ mol 1 2



Raw materialinput

Feedprocessing

unit(s)

Upstreamoperations

Recycle stream


To sideproductwaste


Finishedproduct(s)

Purificationunit(s)

Separationunit(s)

Reactor(s)


Catalystparticles

Pores

ξ= Rp

Catalyst bedL

Flow

Rtr

z


4 Chapter 1










Circulationturbine

Steamgenerator

Feedwater

Steam


Steam drum

Feedwater

(a) (b) (c)


Interstagegas feed

Feed gas


(a) (b) (c)


6 Chapter 1








CH4 +H2O=CO+ 3H2 ΔH = 206 kJ mol 1 2




Stage 1Stage 1

Steam

Water

Steam

Water

FeedExit

Stage 2Stage 2

Stage 3Stage 3

20 NH3(N2 H2 CH4)

Circulating gas

Off-gas

NH3 liquid


Condensationcoolers









Feedstock(+ steam)

Combustionchamber

Catalyst bed

Synthesis gas

Pressureshell

Refractory



Flow

Pores

L


8 Chapter 1






1000

100

10

1

01100 1000


Pres

sure

dro

p pe

r le

ngth

in m

bar

m

10 000



15 mm6 mm

2 mm

1 mm05 mm

DaDi= 042

DaDi= 06

DaDi= 084

Da= 12 mm2535 cpsi

5025 cpsiConditions


10015 cpsi

200125 cpsi

40075 cpsi6004 cpsi

9003 cpsi12003 cpsi

16002 cpsi

Da= 45 mm










Main inlet

Manhole andcatalyst

loading holes

Shellof internals

Outlet

Cold bypass

Lower exchangers

Transfer tube


Innerannular space

Outerannular space

Pressure shell

Innerbasket lid

Outerbasket lid

Ouench

No 1 bed

No 2 bed


10 Chapter 1






(c)

(b)

Catalystwashcoat

Microchannel

Microchannel

Wall

Line of symmetry xL

y

Ls

δs

δsH2

H2

HS

yw

Pores

Lines of symmetry

Bonding

Bonding

(a)


Catalyst

Quench








Product

a

fb

c

d

Flue gas

e

Feed oil

Air


12 Chapter 1





Tail gas

Cyclones


Slide valves


Feed preheater

(a) (b)


Riser

Reactor

Gooseneck

Cooler groups

CatalystStandpipe

Cooling-oiloutlet

Cooling-oilinlet

Steam

ProductsGases

Cyclones

Fluidized

Boiler feedwater

Gasdistributor

Total feed










Steam

Slurry bed

Gaseous products

Boiler feedwater

Wax

Gas distributor

Syngas feed


14 Chapter 1










Circulationturbine

Steamgenerator

Feedwater

Steam


Steam drum

Feedwater

(a) (b) (c)


Interstagegas feed

Feed gas


(a) (b) (c)


6 Chapter 1








CH4 +H2O=CO+ 3H2 ΔH = 206 kJ mol 1 2




Stage 1Stage 1

Steam

Water

Steam

Water

FeedExit

Stage 2Stage 2

Stage 3Stage 3

20 NH3(N2 H2 CH4)

Circulating gas

Off-gas

NH3 liquid


Condensationcoolers









Feedstock(+ steam)

Combustionchamber

Catalyst bed

Synthesis gas

Pressureshell

Refractory



Flow

Pores

L


8 Chapter 1






1000

100

10

1

01100 1000


Pres

sure

dro

p pe

r le

ngth

in m

bar

m

10 000



15 mm6 mm

2 mm

1 mm05 mm

DaDi= 042

DaDi= 06

DaDi= 084

Da= 12 mm2535 cpsi

5025 cpsiConditions


10015 cpsi

200125 cpsi

40075 cpsi6004 cpsi

9003 cpsi12003 cpsi

16002 cpsi

Da= 45 mm










Main inlet

Manhole andcatalyst

loading holes

Shellof internals

Outlet

Cold bypass

Lower exchangers

Transfer tube


Innerannular space

Outerannular space

Pressure shell

Innerbasket lid

Outerbasket lid

Ouench

No 1 bed

No 2 bed


10 Chapter 1






(c)

(b)

Catalystwashcoat

Microchannel

Microchannel

Wall

Line of symmetry xL

y

Ls

δs

δsH2

H2

HS

yw

Pores

Lines of symmetry

Bonding

Bonding

(a)


Catalyst

Quench








Product

a

fb

c

d

Flue gas

e

Feed oil

Air


12 Chapter 1





Tail gas

Cyclones


Slide valves


Feed preheater

(a) (b)


Riser

Reactor

Gooseneck

Cooler groups

CatalystStandpipe

Cooling-oiloutlet

Cooling-oilinlet

Steam

ProductsGases

Cyclones

Fluidized

Boiler feedwater

Gasdistributor

Total feed










Steam

Slurry bed

Gaseous products

Boiler feedwater

Wax

Gas distributor

Syngas feed


14 Chapter 1








CH4 +H2O=CO+ 3H2 ΔH = 206 kJ mol 1 2




Stage 1Stage 1

Steam

Water

Steam

Water

FeedExit

Stage 2Stage 2

Stage 3Stage 3

20 NH3(N2 H2 CH4)

Circulating gas

Off-gas

NH3 liquid


Condensationcoolers









Feedstock(+ steam)

Combustionchamber

Catalyst bed

Synthesis gas

Pressureshell

Refractory



Flow

Pores

L


8 Chapter 1






1000

100

10

1

01100 1000


Pres

sure

dro

p pe

r le

ngth

in m

bar

m

10 000



15 mm6 mm

2 mm

1 mm05 mm

DaDi= 042

DaDi= 06

DaDi= 084

Da= 12 mm2535 cpsi

5025 cpsiConditions


10015 cpsi

200125 cpsi

40075 cpsi6004 cpsi

9003 cpsi12003 cpsi

16002 cpsi

Da= 45 mm










Main inlet

Manhole andcatalyst

loading holes

Shellof internals

Outlet

Cold bypass

Lower exchangers

Transfer tube


Innerannular space

Outerannular space

Pressure shell

Innerbasket lid

Outerbasket lid

Ouench

No 1 bed

No 2 bed


10 Chapter 1






(c)

(b)

Catalystwashcoat

Microchannel

Microchannel

Wall

Line of symmetry xL

y

Ls

δs

δsH2

H2

HS

yw

Pores

Lines of symmetry

Bonding

Bonding

(a)


Catalyst

Quench








Product

a

fb

c

d

Flue gas

e

Feed oil

Air


12 Chapter 1





Tail gas

Cyclones


Slide valves


Feed preheater

(a) (b)


Riser

Reactor

Gooseneck

Cooler groups

CatalystStandpipe

Cooling-oiloutlet

Cooling-oilinlet

Steam

ProductsGases

Cyclones

Fluidized

Boiler feedwater

Gasdistributor

Total feed










Steam

Slurry bed

Gaseous products

Boiler feedwater

Wax

Gas distributor

Syngas feed


14 Chapter 1







Feedstock(+ steam)

Combustionchamber

Catalyst bed

Synthesis gas

Pressureshell

Refractory



Flow

Pores

L


8 Chapter 1






1000

100

10

1

01100 1000


Pres

sure

dro

p pe

r le

ngth

in m

bar

m

10 000



15 mm6 mm

2 mm

1 mm05 mm

DaDi= 042

DaDi= 06

DaDi= 084

Da= 12 mm2535 cpsi

5025 cpsiConditions


10015 cpsi

200125 cpsi

40075 cpsi6004 cpsi

9003 cpsi12003 cpsi

16002 cpsi

Da= 45 mm










Main inlet

Manhole andcatalyst

loading holes

Shellof internals

Outlet

Cold bypass

Lower exchangers

Transfer tube


Innerannular space

Outerannular space

Pressure shell

Innerbasket lid

Outerbasket lid

Ouench

No 1 bed

No 2 bed


10 Chapter 1






(c)

(b)

Catalystwashcoat

Microchannel

Microchannel

Wall

Line of symmetry xL

y

Ls

δs

δsH2

H2

HS

yw

Pores

Lines of symmetry

Bonding

Bonding

(a)


Catalyst

Quench








Product

a

fb

c

d

Flue gas

e

Feed oil

Air


12 Chapter 1





Tail gas

Cyclones


Slide valves


Feed preheater

(a) (b)


Riser

Reactor

Gooseneck

Cooler groups

CatalystStandpipe

Cooling-oiloutlet

Cooling-oilinlet

Steam

ProductsGases

Cyclones

Fluidized

Boiler feedwater

Gasdistributor

Total feed










Steam

Slurry bed

Gaseous products

Boiler feedwater

Wax

Gas distributor

Syngas feed


14 Chapter 1






1000

100

10

1

01100 1000


Pres

sure

dro

p pe

r le

ngth

in m

bar

m

10 000



15 mm6 mm

2 mm

1 mm05 mm

DaDi= 042

DaDi= 06

DaDi= 084

Da= 12 mm2535 cpsi

5025 cpsiConditions


10015 cpsi

200125 cpsi

40075 cpsi6004 cpsi

9003 cpsi12003 cpsi

16002 cpsi

Da= 45 mm










Main inlet

Manhole andcatalyst

loading holes

Shellof internals

Outlet

Cold bypass

Lower exchangers

Transfer tube


Innerannular space

Outerannular space

Pressure shell

Innerbasket lid

Outerbasket lid

Ouench

No 1 bed

No 2 bed


10 Chapter 1






(c)

(b)

Catalystwashcoat

Microchannel

Microchannel

Wall

Line of symmetry xL

y

Ls

δs

δsH2

H2

HS

yw

Pores

Lines of symmetry

Bonding

Bonding

(a)


Catalyst

Quench








Product

a

fb

c

d

Flue gas

e

Feed oil

Air


12 Chapter 1





Tail gas

Cyclones


Slide valves


Feed preheater

(a) (b)


Riser

Reactor

Gooseneck

Cooler groups

CatalystStandpipe

Cooling-oiloutlet

Cooling-oilinlet

Steam

ProductsGases

Cyclones

Fluidized

Boiler feedwater

Gasdistributor

Total feed










Steam

Slurry bed

Gaseous products

Boiler feedwater

Wax

Gas distributor

Syngas feed


14 Chapter 1







Main inlet

Manhole andcatalyst

loading holes

Shellof internals

Outlet

Cold bypass

Lower exchangers

Transfer tube


Innerannular space

Outerannular space

Pressure shell

Innerbasket lid

Outerbasket lid

Ouench

No 1 bed

No 2 bed


10 Chapter 1






(c)

(b)

Catalystwashcoat

Microchannel

Microchannel

Wall

Line of symmetry xL

y

Ls

δs

δsH2

H2

HS

yw

Pores

Lines of symmetry

Bonding

Bonding

(a)


Catalyst

Quench








Product

a

fb

c

d

Flue gas

e

Feed oil

Air


12 Chapter 1





Tail gas

Cyclones


Slide valves


Feed preheater

(a) (b)


Riser

Reactor

Gooseneck

Cooler groups

CatalystStandpipe

Cooling-oiloutlet

Cooling-oilinlet

Steam

ProductsGases

Cyclones

Fluidized

Boiler feedwater

Gasdistributor

Total feed










Steam

Slurry bed

Gaseous products

Boiler feedwater

Wax

Gas distributor

Syngas feed


14 Chapter 1






(c)

(b)

Catalystwashcoat

Microchannel

Microchannel

Wall

Line of symmetry xL

y

Ls

δs

δsH2

H2

HS

yw

Pores

Lines of symmetry

Bonding

Bonding

(a)


Catalyst

Quench








Product

a

fb

c

d

Flue gas

e

Feed oil

Air


12 Chapter 1





Tail gas

Cyclones


Slide valves


Feed preheater

(a) (b)


Riser

Reactor

Gooseneck

Cooler groups

CatalystStandpipe

Cooling-oiloutlet

Cooling-oilinlet

Steam

ProductsGases

Cyclones

Fluidized

Boiler feedwater

Gasdistributor

Total feed










Steam

Slurry bed

Gaseous products

Boiler feedwater

Wax

Gas distributor

Syngas feed


14 Chapter 1






Product

a

fb

c

d

Flue gas

e

Feed oil

Air


12 Chapter 1





Tail gas

Cyclones


Slide valves


Feed preheater

(a) (b)


Riser

Reactor

Gooseneck

Cooler groups

CatalystStandpipe

Cooling-oiloutlet

Cooling-oilinlet

Steam

ProductsGases

Cyclones

Fluidized

Boiler feedwater

Gasdistributor

Total feed










Steam

Slurry bed

Gaseous products

Boiler feedwater

Wax

Gas distributor

Syngas feed


14 Chapter 1





Tail gas

Cyclones


Slide valves


Feed preheater

(a) (b)


Riser

Reactor

Gooseneck

Cooler groups

CatalystStandpipe

Cooling-oiloutlet

Cooling-oilinlet

Steam

ProductsGases

Cyclones

Fluidized

Boiler feedwater

Gasdistributor

Total feed










Steam

Slurry bed

Gaseous products

Boiler feedwater

Wax

Gas distributor

Syngas feed


14 Chapter 1








Steam

Slurry bed

Gaseous products

Boiler feedwater

Wax

Gas distributor

Syngas feed


14 Chapter 1

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