Table Of ContentChemical Looping Partial Oxidation
Gasification, Reforming, and Chemical Syntheses
This is the first comprehensive guide to the principles and techniques of chemical
looping partial oxidation. With authoritative explanations from a pioneer of the chem-
ical loopingprocess, you will:
(cid:129) Gain a holistic overview of metal oxide reaction engineering, with coverage of
ionicdiffusion,nanostructureformation,morphologicalevolution,phaseequilib-
rium, and recyclability properties ofmetaloxides during redox reactions.
(cid:129) Learn about the gasification of solid fuels, the reforming of natural gas, and the
catalyticconversion ofmethane toolefins.
(cid:129) Understandtheimportanceofreactordesignandprocessintegration inenabling
metal oxide oxygen carriers toproduce desiredproducts.
(cid:129) Discoverotherapplicationsofcatalyticmetaloxides,includingtheproductionof
maleic anhydride and solar energy conversions.
®
Aspen Plus simulation software and results accompany the book online. This is an
invaluablereferenceforresearchersandindustryprofessionalsinthefieldsofchemical,
energy, and environmental engineering, and students studying process design and
optimization.
Liang-ShihFan isDistinguished UniversityProfessorand theC. JohnEastonProfes-
sorinEngineering at TheOhioState University. He isaMemberofthe U.S. National
Academy of Engineering, Chinese Academy of Engineering, and Australian Academy
of Technological Sciences andEngineering,and an Academician of Academia Sinica.
Cambridge Series in Chemical Engineering
SeriesEditor
ArvindVarma, Purdue University
EditorialBoard
Christopher Bowman, University ofColorado
Edward Cussler,University of Minnesota
Chaitan Khosla, Stanford University
Athanassios Z. Panagiotopoulos, PrincetonUniversity
GregoryStephanopoulos, Massachusetts Institute ofTechnology
Jackie Ying, Institute ofBioengineering andNanotechnology, Singapore
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CusslerandMoggridge,ChemicalProductDesign,SecondEdition
DePabloandSchieber,MolecularEngineeringThermodynamics
Denn,ChemicalEngineering:AnIntroduction
Denn,PolymerMeltProcessing:FoundationsinFluidMechanicsandHeatTransfer
DuncanandReimer,ChemicalEngineeringDesignandAnalysis:AnIntroduction
FanandZhu,PrinciplesofGas-SolidFlows
Fox,ComputationalModelsforTurbulentReactingFlows
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Chemical Looping Partial
Oxidation
fi
Gasi cation, Reforming, and Chemical Syntheses
LIANG-SHIH FAN
OhioStateUniversity
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www.cambridge.org
Informationonthistitle:www.cambridge.org/9781107194397
DOI:10.1017/9781108157841
©CambridgeUniversityPress2017
Thispublicationisincopyright.Subjecttostatutoryexception
andtotheprovisionsofrelevantcollectivelicensingagreements,
noreproductionofanypartmaytakeplacewithoutthewritten
permissionofCambridgeUniversityPress.
Firstpublished2017
PrintedintheUnitedKingdombyTJInternationalLtd.PadstowCornwall
AcatalogrecordforthispublicationisavailablefromtheBritishLibrary.
LibraryofCongressCataloging-in-PublicationData
Names:Fan,Liang-Shih.
Title:Chemicalloopingpartialoxidation:gasification,reforming,and
chemicalsyntheses/Liang-ShihFan,OhioStateUniversity.
Description:Cambridge:CambridgeUniversityPress,2017.|Includes
bibliographicalreferencesandindex.
Identifiers:LCCN2017014544|ISBN9781107194397(Hardback:alk.paper)
Subjects:LCSH:Synthesisgas.|Biomassenergy.
Classification:LCCTP243.F362017|DDC662/.88–dc23LCrecordavailable
athttps://lccn.loc.gov/2017014544
ISBN978-1-107-19439-7Hardback
Additionalresourcesforthistitleareavailableatwww.cambridge.org/fan
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ofURLsforexternalorthird-partyinternetwebsitesreferredtointhispublication
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accurateorappropriate.
Dedicated to
Fan club members
For their past and continuing devotion
to the demonstration of the Syngas Chemical Looping Pilot Operation
at the National Carbon Capture Center in Alabama
Contents
In Cooperationwith ProfessorFan’s Research Group Members page xiv
Preface xv
Nomenclature xix
Abbreviations xxiii
1 Overview 1
1.1 Introduction 1
1.2 EnergyScenarios and CO Capture Methods 3
2
1.2.1 EnergyScenarios 3
1.2.2 CO Capture Methods 4
2
1.3 MetalOxideReaction Engineering 5
1.3.1 MetalOxideApplications andProperties 5
1.3.2 Source and Cost ofMetalOxides 7
1.3.3 Ionic DiffusionMechanism in Metal Oxide 9
1.3.4 Ionic Diffusionin Microscale:Nanostructure Formation 15
1.3.5 Iron Oxide Reduction Mechanism 18
1.3.6 Transition MetalOxidesfor Chemical Looping Applications 19
1.4 Chemical Looping Classification 22
1.5 Chemical Looping Partial Oxidation Historical andRecent
Developments 24
1.6 Ohio State Chemical Looping Technology Platform 29
1.6.1 Chemical Looping Full OxidationTechnology –Category 1 31
1.6.2 Chemical Looping Partial Oxidation Technology – Category 2 38
1.7 Concluding Remarks 48
References 49
2 Metal Oxide Oxygen Carriers 55
2.1 Introduction 55
2.2 Thermodynamic Principles and Reactivity 57
2.2.1 Modified Ellingham Diagram 57
2.2.2 Single Metal Oxides 60
2.2.3 Complex and MixedMetalOxideBasedMaterials 66
2.2.4 Recyclabilityand Strength 68
2.2.5 Effect of Elevated Pressures 70
ix
x Contents
2.3 Morphology and Ionic Diffusion 83
2.3.1 Core–Shell StructureFormation 85
2.3.2 Morphology Evolutionand Nanostructure Formation 86
2.3.3 Impact ofIonic Diffusion on Morphology 97
2.4 Ionic Diffusion Behavior Modeling 101
2.4.1 Density Functional Theory(DFT) Calculations 102
2.4.2 Ionic DiffusionGrainModel 115
2.5 PhaseDiagrams for Oxygen Carriers 123
2.5.1 Single MetalOxygenCarriers 125
2.5.2 Binary MetalOxygen Carriers 129
2.6 Oxygen Carrier Attrition 136
2.6.1 Types ofAttrition Tests 137
2.6.2 Attrition Studieson DifferentOxygen Carriers 143
2.7 EnhancementTechniques for Oxygen Carrier Performance 155
2.7.1 Other Physical Property Enhancement Techniques 156
2.7.2 Other Chemical Property EnhancementTechniques 156
2.8 Concluding Remarks 160
References 161
3 Oxidative Coupling ofMethane 172
3.1 Introduction 172
3.2 Oxidative Couplingof Methane 174
3.2.1 Oxidative Coupling ofMethane Reactions 176
3.2.2 Co-feed Ethylene Formation Mechanism 178
3.2.3 Co-feed Carbon Oxide Formation Mechanism 180
3.2.4 Roleof OxygenSpecies 182
3.3 Co-feed MetalOxideCatalysts 184
3.4 Redox Catalytic Metal Oxides 187
3.5 Substituted and ComplexMetalOxide Catalysts 191
3.5.1 Halogen-Based Metal Catalysts 192
3.5.2 Solid Electrolyte Metal Catalysts 192
3.5.3 Soft Oxidant Based Metal Catalysts 194
3.6 Reaction Engineering 195
3.6.1 Co-feed Elementary Kinetic Model 195
3.6.2 Co-feed Global Kinetic Models 199
3.6.3 Co-feed Fixed Bed Reactor Behavior 204
3.6.4 Redox ReactionKinetics 207
3.6.5 Co-feed Reactor Design 209
3.6.6 Redox Reactor Design 212
3.7 Process Engineering 214
3.7.1 Process DesignPerspective 214
3.7.2 Redox Heat Integration 215
3.7.3 Product Processing 219
Contents xi
3.8 Concluding Remarks 221
References 223
4 Syngas Generation 236
4.1 Introduction 236
4.2 Conventional Syngas Generation Processes 237
4.2.1 CoalGasification 237
4.2.2 Natural Gas ReformingTechnologies 243
4.2.3 Biomass Gasification 249
4.3 SyngasGeneration Metal Oxides inChemical Looping 250
4.3.1 Selection ofOxygen Carrier 251
4.4 Chemical Looping UsingFluidized Bed Reducers 253
4.4.1 Steam MethaneReforming–Chemical Looping Combustion
(SMR–CLC) Systems 254
4.4.2 CLG/CLR with a Fluidized Bed Reducer 256
4.5 SyngasGeneration with Moving Bed Reducer 269
4.5.1 Iron Oxide Based OxygenCarriers 269
4.5.2 CLR in Fixed Bed Reactors 271
4.5.3 Reactor Designof CLG/CLR System With MovingBed Reducer 274
4.5.4 ExperimentalStudies onMoving Bed Reducers for CLG/CLR
Applications 281
4.6 Chemical Looping CO Neutral andNegative Processes 287
2
4.6.1 CO as Feedstockand Conversion inProcess Systems 287
2
4.6.2 Reducer Modularization and Product YieldEnhancement 293
4.7 Concluding Remarks 299
References 300
5 Catalytic Metal Oxides and Applications 307
5.1 Introduction 307
5.2 DuPont’sProcess for Production ofTetrahydrofuran (THF) 309
5.2.1 THF Synthesis Processes 310
5.2.2 DuPont’sMethod for THF Production 310
5.2.3 Catalytic MetalOxideVPO 311
5.2.4 Lab-Scale Tests 314
5.2.5 Bench-ScaleTests 315
5.2.6 Pilot UnitTests 316
5.2.7 Commercial-Scale Tests 318
5.3 Syngasand Hydrogen Generation with Solar Energy 320
5.3.1 Concentrating Solar Thermal Receiver Design 322
5.3.2 Solar ThermochemicalProcess 324
5.3.3 Solar Thermal Water Splitting Process 328
5.4 SelectivePartial Oxidation ofCH toHCHO 336
4
5.4.1 SiO Supported V O and MoO as Catalytic Metal Oxides 336
2 2 5 3
