Synthesis of Solid Catalysts

408 Pages·2009·117.03 MB·English

SynthesisofSolidCatalysts
Editedby
KrijnP.deJong
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SynthesisofSolidCatalysts
Edited by
Krijn P. de Jong
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2009WILEY-VCHVerlagGmbH&Co.
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ISBN: 978-3-527-32040-0
V
Contents
Preface XIII
ListofContributors XV
Abbreviations XIX
PartI BasicPrinciplesandTools
1 GeneralAspects 3
KrijnP. deJong
1.1 ImportanceofSolidCatalysts 3
1.2 DevelopmentofSolidCatalysts 4
1.3 DevelopmentofSolidCatalystSynthesis 5
1.4 AboutThisBook 10
References 10
2 InterfacialChemistry 13
Alexis Lycourghiotis
2.1 Introduction 13
2.2 InterfacialandBulkDeposition 14
2.3 TheSurfaceoftheOxidicSupports:SurfaceIonization
Models 15
2.3.1 TheChargedSurfaceoftheOxidicSupports 15
2.3.2 HomogeneousSurfaceIonizationModels 16
2.3.3 TheMusicModel 17
2.4 TheSizeandtheStructureoftheInterface 18
2.5 TheArrangementoftheIonsInsidetheInterface
andtheDepositionModes 20
2.5.1 IndifferentIons 20
2.5.2 Transition-MetalIonicSpecies 22
2.6 DeterminingtheModeofInterfacialDepositionandtheSurface
Speciation/StructureoftheDepositedPrecursorSpecies 23
2.6.1 IntroductoryRemarks 23
SynthesisofSolidCatalysts.EditedbyK.P.deJong
2009WILEY-VCHVerlagGmbH&Co.KGaA,Weinheim
ISBN:978-3-527-32040-0
VI Contents
2.6.2 MethodologiesBasedonMacroscopicAdsorptionDataand
PotentiometricTitrationsaswellasonMicroelectrophoretic
MobilityorStreamingPotentialMeasurements 23
2.6.3 SpectroscopicInvestigations 25
2.6.4 Quantum-MechanicalCalculations 26
2.6.5 Electrochemical(Equilibrium)Modeling 26
2.7 ACaseStudy:TheDepositionofCo(H O) 2+AquaComplex
2 6
ontheTitaniaSurface 27
2.7.1 ExperimentalInvestigation 27
2.7.2 Quantum-MechanicalCalculations 28
2.7.3 Electrochemical(Equilibrium)Modeling 29
References 30
3 ElectrostaticAdsorption 33
JohnR. Regalbuto
3.1 Introduction 33
3.2 PurelyElectrostaticAdsorption 37
3.3 ElectrostaticAdsorptionwithMetalRespeciation 38
3.4 ElectrostaticAdsorptionandIonExchange 41
3.5 ElectrostaticAdsorptionandDeposition-Precipitation 45
3.6 ElectrostaticAdsorptionandSurfaceReaction 46
3.7 ElectrostaticsandDissolution,Reaction,andRedeposition 47
3.8 Electrostatics-BasedDesign 48
3.8.1 Well-DispersedSingleMetals 49
3.8.2 SelectiveAdsorptionontoPromoters 51
3.8.3 BimetallicCatalysts 54
3.9 Summary 57
References 57
4 ImpregnationandDrying 59
Eric Marceau,Xavier Carrier,andMichel Che
4.1 Introduction 59
4.2 Impregnation 61
4.2.1 MethodsofImpregnation 61
4.2.2 PhysicalModelsforImpregnation 62
4.3 Drying 64
4.4 TheChemistry 67
4.4.1 ConcentrationsandpH 67
4.4.2 Precursor-SupportInteractions 69
4.4.2.1 Adsorption:FromElectrostaticInteractionstoGrafting 69
4.4.2.2 TheFormationofMixedPhases 70
4.4.3 Ligands 71
4.4.4 Counterions 73
4.5 ImpregnationandDryingofanMoO /Al O Catalyst 74
x 2 3
4.5.1 MolybdenumSpeciationandItsConsequences 74
Contents VII
4.5.2 DegreesofFreedom:DryingParametersandLigandsinSolution 76
4.6 Conclusions 77
References 78
5 Sol-GelProcessing 83
MironV.Landau
5.1 Introduction 83
5.2 PhysicochemicalBasisandPrinciplesofSol-GelProcessing 85
5.2.1 Activation 86
5.2.2 Polycondensation 87
5.2.3 Gelation/Aging/Washing 89
5.2.4 GelDrying/Desolvation 90
5.2.5 StabilizationofXero-andAerogels 90
5.3 ApplicationofSol-GelProcessingforthePreparation
ofSolidCatalysts 91
5.3.1 BulkCatalyticPhaseMaterials:Xero-andAerogels 91
5.3.1.1 MonometallicCatalyticMaterials 91
5.3.1.2 MultimetallicCompositeCatalyticPhases 94
5.3.2 CatalyticMaterialsandModifiersEntrappedinPorousMatrices 97
5.3.2.1 AtomsorMolecularSubstancesEntrappedbyCocondensation
attheColloidizationStep 98
5.3.2.2 MolecularSubstancesAdsorbedorEntrapped
attheGelationStep 103
5.4 Summary 106
References 106
6 DepositionPrecipitation 111
KrijnP. deJong
6.1 Introduction 111
6.2 TheoryandPractice 112
6.3 MechanisticStudies 115
6.3.1 Kinetics 115
6.3.2 MolecularDetails 118
6.4 CaseStudies 120
6.4.1 pHIncrease 120
6.4.2 ReductionDepositionPrecipitation 124
6.4.3 LigandRemoval 128
6.4.4 MiscellaneousMethods 129
6.5 Summary,Conclusions,andOutlook 131
Acknowledgments 131
References 132
7 Coprecipitation 135
Martin Lok
7.1 Introduction 135
VIII Contents
7.2 BasicPrinciplesofPrecipitationandNucleation 136
7.3 RawMaterials 139
7.4 PrecipitationConditions 141
7.5 ProcessOperation 141
7.6 Examples 145
7.6.1 HighMetalNickel/AluminaCatalysts 145
7.6.2 Single-StepSulfur-PromotedNickel/AluminaCatalyst 146
7.6.3 Copper/ZincMethanolCatalysts 147
7.6.4 Iron-BasedFischer–TropschCatalysts 148
7.6.5 UnsupportedMetalSulfideCatalystsforHydrotreating 148
7.7 NewDevelopmentsinProcessMonitoring 148
Acknowledgments 149
References 149
8 ClustersandImmobilization 153
SophieHermans
8.1 Introduction 153
8.2 TheSurfaceofCommonSupports 154
8.3 ClustersinCatalysis 157
8.4 ReactionwithUnmodifiedSurface 160
8.5 ‘‘Ship-in-a-Bottle’’Synthesis 163
8.6 Tethering 167
8.7 ConcludingRemarks 168
References 169
9 ShapingofSolidCatalysts 173
Bettina Kraushaar-CzarnetzkiandSteffen PeterMu¨ller
9.1 ObjectivesofCatalystShaping 173
9.2 Fixed-BedReactors – ParticleBeds 177
9.2.1 Pelleting 177
9.2.2 Granulation 179
9.2.3 Extrusion 181
9.2.4 TailoringofthePore-SizeDistribution 184
9.2.5 Fixed-BedEgg-ShellCatalysts 186
9.3 Fixed-BedReactors – Monoliths 187
9.3.1 Honeycombs 187
9.3.1.1 CeramicHoneycombs 188
9.3.1.2 MetallicHoneycombs 190
9.3.2 Open-CellFoams 192
9.3.3 CoatingofMonoliths 194
9.4 CatalystsforMoving-BedReactors 195
9.5 CatalystsforFluidizedBeds 196
References 198
Contents IX
10 SpaceandTime-ResolvedSpectroscopyofCatalystBodies 201
BertM.Weckhuysen
10.1 Introduction 201
10.2 Space-andTime-ResolvedMethodsAppliedtoCatalystBodies 201
10.2.1 InvasiveMethods 202
10.2.2 NoninvasiveMethods 205
10.3 CaseStudies 209
10.3.1 Keggin-TypeCo-MoComplexesinCatalystBodies 209
10.3.2 SpeciationofCoComplexesinCatalystBodies 212
10.4 FutureProspects 215
Acknowledgments 215
References 216
11 High-ThroughputExperimentation 217
Uwe RodemerckandDavid Linke
11.1 Introduction 217
11.2 SynthesisStrategies 219
11.2.1 CombinatorialStrategies 220
11.2.2 MethodstoReduceExperiments 220
11.3 CatalystLibrariesforPrimaryScreening 223
11.3.1 Wafer-BasedPreparation 223
11.3.2 SinglePellets 224
11.3.3 SingleBeads 225
11.4 CatalystLibrariesforSecondaryScreening 225
11.4.1 ImpregnationTechniques 226
11.4.2 Precipitation 226
11.4.3 HydrothermalSynthesis 230
11.4.4 Sol-GelChemistry 231
11.4.5 Drying,Calcination,andShaping 231
11.5 CatalystLibrariesforSpecialReactorTypes 234
11.6 AnIndustrialPointofView 234
11.7 Conclusions 235
References 236
PartII CaseStudies
12 ConceptsforPreparationofZeolite-BasedCatalysts 243
Metin BulutandPierreA. Jacobs
12.1 IntroductionandScope 243
12.2 ZeoliteEffectsinCatalysis 245
12.2.1 BrønstedAcidityinMetallosilicateZeolites 245
12.2.2 ZeoliteProtonicSuperacidity 246
12.2.3 BrønstedAcidityinSubstitutedFour-Coordinated
Aluminophosphates 247
12.2.4 ZeoliteShapeSelectivity 250
X Contents
12.2.5 ConcentrationEffectsbySpecificAdsorption 253
12.2.6 SiteIsolationortheRoleofZeolitesasSolidSolvents 254
12.3 Zeolitization 254
12.3.1 OverallStepsinZeoliteCrystallization 255
12.3.2 ClassicModelforZeoliteGrowth 257
12.3.3 TheAggregationModel 259
12.3.4 ZeolitizationParameters 260
12.3.5 NanocrystallineZeolites 264
12.3.6 ZeoliteSynthesisviatheDryGelRoute 265
12.3.7 AlPO -n-BasedMolecularSieveZeolites 266
4
12.3.8 IonothermalSynthesisMethod 267
12.3.9 ZeoliteswithPoresBeyondthe12-MR 267
12.3.10 UpscalingofZeoliteSynthesis 268
References 268
FurtherReading 276
13 OrderedMesoporousMaterials 277
YingWanandDongyuanZhao
13.1 Introduction 277
13.2 MesoporousSilica 277
13.2.1 MCM-41 279
13.2.2 SBA-15 280
13.2.3 MCM-48 281
13.2.4 Pore-SizeControl 282
13.3 OrganicGroupFunctionalizedMesoporousSilicates 284
13.3.1 OrganicGroupsAnchoredtoMesoporousSilicates 284
13.3.2 PeriodicMesoporousOrganosilicas 285
13.3.3 AdsorptionandCatalysis 285
13.4 Metal-SubstitutedMesoporousSilicaMolecularSieves 287
13.5 Carbon 289
13.5.1 TheHard-TemplatingApproach 289
13.5.2 TheSupramolecular-TemplatingApproach 290
13.6 NonsiliceousOxides 293
13.6.1 TheSupramolecular-TemplatingApproach 293
13.6.2 TheHard-TemplatingApproach 294
13.7 Nonoxides 294
13.7.1 SiC-BasedMaterials 294
13.7.2 MetalSulfides 296
13.8 SummaryandRemarks 296
Acknowledgments 297
References 297
14 HydrotreatingCatalysts 301
Sonja Eijsbouts
14.1 Introduction 301