Deactivation of heavy oil hydroprocessing catalysts: fundamentals and modeling

339 Pages·2016·10.498 MB·English

by  Ancheyta Juárez, Jorge

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DEACTIVATION
OF HEAVY OIL
HYDROPROCESSING
CATALYSTS
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DEACTIVATION
OF HEAVY OIL
HYDROPROCESSING
CATALYSTS
Fundamentals and Modeling
JORGEANCHEYTA
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LibraryofCongressCataloging-in-PublicationData:
Names:AncheytaJuárez,Jorge,author.
Title:Deactivationofheavyoilhydroprocessingcatalysts:fundamentalsand
modeling/JorgeAncheyta.
Description:Hoboken,NewJersey:JohnWiley&Sons,2016.|Includes
bibliographicalreferencesandindex.
Identifiers:LCCN2016019443|ISBN9781118769843(cloth)|ISBN9781118769812
(epub)
Subjects:LCSH:Petroleum–Refining.|Catalystpoisoning.
Classification:LCCTP690.8.A532016|DDC622/.33827–dc23LCrecordavailableat
https://lccn.loc.gov/2016019443
CoverimagecourtesyofGettyImages/avdeev007
Typesetin10/12pt,TimesLTStdbySPiGlobal,Chennai,India.
PrintedintheUnitedStatesofAmerica
10987654321
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TABLE OF CONTENTS
AbouttheAuthor xi
(cid:2) Preface xiii (cid:2)
Nomenclature xvii
1 PropertiesofHeavyOils 1
1.1 Introduction, 1
1.2 RefiningofPetroleum, 3
1.2.1 Desalting, 4
1.2.2 AtmosphericorPrimaryDistillation, 4
1.2.3 VacuumorSecondaryDistillation, 5
1.2.4 SolventExtractionandDewaxing, 5
1.2.5 Deasphalting, 6
1.2.6 GasandLiquidSweetening, 6
1.2.7 SourWaterTreatment, 7
1.2.8 CatalyticReforming, 7
1.2.9 Isomerization, 7
1.2.10Alkylation, 8
1.2.11Polymerization, 8
1.2.12CatalyticHydrotreating, 8
1.2.13FluidCatalyticCracking, 9
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vi TABLEOFCONTENTS
1.2.14Gasification, 9
1.2.15Coking, 10
1.2.16Visbreaking, 11
1.2.17ResidueFluidCatalyticCracking(RFCC), 12
1.2.18HydrovisbreakingProcess, 12
1.2.19Fixed-BedHydroprocessing, 13
1.2.20Moving-BedHydroprocessing, 13
1.2.21Ebullated-BedHydroprocessing, 14
1.2.22Slurry-BedHydroprocessing, 14
1.3 PropertiesofHeavyPetroleum, 14
1.3.1 PhysicalandChemicalProperties, 14
1.3.2 Asphaltenes, 15
1.3.3 TendencytoCokeFormation, 18
1.3.4 ViscosityofCrudeOilsandBlends, 19
1.3.5 StabilityandCompatibility, 25
1.4 AssayofPetroleum, 28
References, 29
2 PropertiesofCatalystsforHeavyOilHydroprocessing 31
2.1 Introduction, 31
2.2 HydroprocessingCatalyst, 34
(cid:2) 2.2.1 CatalystSupport, 34 (cid:2)
2.2.2 ChemicalComposition, 36
2.2.3 ShapeandSize, 37
2.2.4 PoreSizeDistribution, 39
2.2.5 MechanicalProperties, 40
2.2.6 ActiveMetals, 41
2.3 CharacterizationofCatalysts, 43
2.3.1 Activity, 43
2.3.2 TexturalProperties, 44
2.3.3 SurfaceProperties, 45
2.4 GeneralAspectsforDevelopingCatalystsforHydroprocessingofHeavy
Crude, 49
2.4.1 PreparationofSupports, 49
2.4.2 PreparationofCatalysts, 52
2.4.3 CharacterizationofCatalysts, 53
2.5 CatalystforMayaCrudeOilHydroprocessing, 54
2.5.1 CompositionofMayaCrudeOil, 55
2.5.2 CatalystLoadingandPretreatment, 56
2.5.3 FeedstocksandCharacterizationTechniques, 56
2.5.4 ActiveSitesandCatalyticActivity, 58
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TABLEOFCONTENTS vii
2.5.5 ExperimentswithNaphthaDilutedFeedstock, 59
2.5.6 ExperimentswithDieselDilutedFeedstock, 63
2.5.7 ExperimentswithPureMayaCrudeOil, 66
2.5.8 CharacterizationofSpentCatalysts, 68
2.5.9 FinalComments, 77
2.6 ConcludingRemarks, 78
References, 79
3 DeactivationofHydroprocessingCatalysts 89
3.1 Introduction, 89
3.2 HydroprocessingofHeavyOils, 90
3.2.1 GeneralAspects, 90
3.2.2 ReactorsforHydroprocessing, 92
3.2.3 ProcessVariables, 102
3.2.4 EffectofReactionConditionsonCatalystDeactivation, 105
3.3 MechanismsofCatalystDeactivation, 106
3.4 AsphaltenesandTheirEffectonCatalystDeactivation, 114
3.4.1 ThermalReaction, 114
3.4.2 CatalyticReaction, 117
References, 122
(cid:2) 4 CharacterizationofSpentHydroprocessingCatalyst 127 (cid:2)
4.1 Introduction, 127
4.2 CharacterizationTechniques, 128
4.2.1 TemperatureProgrammedOxidation(TPO), 128
4.2.2 NuclearMagneticResonance, 129
4.2.3 RamanSpectrometry, 131
4.2.4 SEM-EDXAnalysis, 131
4.2.5 ThermogravimetricAnalysis(TGA), 134
4.3 EarlyDeactivationofDifferentSupportedCoMoCatalysts, 138
4.3.1 ExperimentalProcedure, 138
4.3.2 ResultsandDiscussion, 142
4.3.3 Conclusions, 150
4.4 CarbonandMetalDepositionDuringtheHydroprocessingofMayaCrude
Oil, 150
4.4.1 Preparation,Evaluation,andCharacterizationofCatalyst, 150
4.4.2 CatalystCharacterization, 151
4.4.3 ResultsandDiscussion, 152
4.4.4 Conclusions, 164
4.5 CharacterizationStudyofNiMo/SiO –Al O SpentHydroprocessing
2 2 3
CatalystsforHeavyOils, 164
4.5.1 SamplesofSpentCatalysts, 164
4.5.2 CatalystCharacterization, 165
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viii TABLEOFCONTENTS
4.5.3 ResultsandDiscussion, 166
4.5.4 Conclusions, 172
4.6 CharacterizationofSpentCatalystsAlongaBench-ScaleReactor, 173
4.6.1 ExperimentalProcedure, 173
4.6.2 Results, 175
4.6.3 Discussion, 187
4.6.4 Conclusions, 191
4.7 HydrodesulfurizationActivityofUsedHydrotreatingCatalysts, 192
4.7.1 ExperimentalProcedure, 192
4.7.2 ResultsandDiscussion, 194
4.7.3 Conclusions, 203
References, 203
5 ModelingCatalystDeactivation 207
5.1 Introduction, 207
5.2 EffectofReactorConfigurationontheCycleLengthofHeavyOil
Fixed-BedHydroprocessing, 216
5.2.1 ExperimentalProcedure, 216
5.2.2 ModelingApproach, 218
5.2.3 ResultsandDiscussion, 224
5.2.4 Conclusions, 232
(cid:2) 5.3 EffectofDifferentHeavyFeedstocksontheDeactivationofaCommercial (cid:2)
Catalyst, 232
5.3.1 ExperimentalProcedure, 232
5.3.2 ResultsandDiscussion, 234
5.3.3 Conclusions, 240
5.4 ModelingtheDeactivationbyMetalDepositionofHeavyOil
HydrotreatingCatalyst, 240
5.4.1 TheModel, 240
5.4.2 ExperimentalProcedure, 245
5.4.3 ResultsandDiscussion, 245
5.4.4 Conclusions, 251
5.5 KineticModelforHydrocrackingofHeavyOilinaCSTRInvolving
Short-TermCatalystDeactivation, 252
5.5.1 ExperimentalProcedure, 252
5.5.2 ResultsandDiscussion, 253
5.5.3 Conclusions, 259
5.6 ModelingtheKineticsofParallelThermalandCatalyticHydrotreatingof
HeavyOil, 260
5.6.1 TheModel, 260
5.6.2 ExperimentalProcedure, 264
5.6.3 ResultsandDiscussion, 265
5.6.4 Conclusions, 271
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