Table Of Content(cid:2)
AnalyticalCharacterizationMethods
forCrudeOilandRelatedProducts
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Analytical Characterization Methods for
Crude Oil and Related Products
Editedby
AshutoshK.Shukla
PhysicsDepartment
EwingChristianCollege,India
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Thiseditionfirstpublished2018
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Tomyteachers
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vii
Contents
ListofContributors xiii
Preface xvii
1 RheologicalCharacterizationofCrudeOilandRelated
Products 1
FlávioH.Marchesini
1.1 Introduction 1
1.2 SamplePreparationforRheologicalCharacterization 2
(cid:2) 1.2.1 EnsuringtheChemicalStability 2 (cid:2)
1.2.2 ChoosingtheRheometerGeometry 3
1.2.3 ErasingtheThermalMemory 4
1.2.4 PerformingtheCoolingProcess 4
1.3 RheologicalTests 5
1.4 PotentialSourcesofErrors 9
References 10
2 OpticalInterrogationofPetroleumAsphaltenes:Mythsand
Reality 13
IgorN.Evdokimov
2.1 Introduction 13
2.1.1 WhatareAsphaltenes? 13
2.1.2 TheReasonsforIntensiveAsphalteneResearch 14
2.1.3 NoControversyabouttheElementalCompositionof
Asphaltenes 15
2.1.4 ContinuingDebatesontheSizeandtheStructureofAsphaltene
MoleculesandAggregates 15
2.1.5 ConflictingParadigmsbasedonSimilarAnalyticalTechniques:
ApparentSignificanceof“HumanFactors” 18
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2.2 Mythical“CharacteristicSignatures”ofAsphaltenesinOptical
AnalyticalMethods 19
2.2.1 Nonexistent“ResonanceUVAbsorption”ofAsphaltenes 19
2.2.2 Mythical“CharacteristicMonomerPeaks”inFluorescenceEmission
Studies 23
2.3 MisconceptionsaboutthePropertiesofUV/VisAbsorptionSpectra
ofAsphaltenes 29
2.3.1 TheMythabouttheAbsenceofAsphalteneAggregationEffectsin
OpticalAbsorptionStudies 30
2.3.2 TheMythaboutthe“UrbachTail”inOpticalAbsorptionSpectraof
AsphaltenesandCrudeOils 34
2.3.2.1 TaucRange 35
2.3.2.2 UrbachRange 35
2.3.2.3 LowAbsorption(Defects)Range 35
2.3.3 IntheUV/VisSpectralRangeAsphaltenesApparentlyActnotas
Absorbers,butasScatterers 38
2.4 CurrentStateofKnowledgeaboutAsphalteneMonomersand
PrimaryAsphalteneAggregates 42
2.4.1 SomeRequirementsforPreparationofDiluteAsphaltene
Solutions 44
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2.4.2 MultipleStates/PhasesofPrimaryAsphalteneAggregatesRevealed
byOpticalAbsorptionMeasurements 46
2.4.3 MultipleStates/PhasesofPrimaryAsphalteneAggregatesRevealed
byRefractiveIndexMeasurements 47
2.4.3.1 MeanRefractiveIndexatConcentrationsbelowCNAC 50
2.4.3.2 StandardDeviationofRefractiveIndexatConcentrationsbelow
CNAC 50
2.4.4 ConditionsforObservationofAsphalteneMonomersandEvolution
ofPrimaryAsphalteneAggregatesRevealedbyFluorescence
Measurements 53
2.4.4.1 StudiesofSteady-StateFluorescenceEmission 53
2.4.4.2 StudiesofTime-ResolvedFluorescenceEmission 55
2.4.5 EvolutionofPrimaryAsphalteneAggregatesRevealedbyMass
Spectrometry 56
2.4.6 “OpticalInterrogation”RevealsthatPrimaryAsphalteneAggregates
arePorousandEntrap/OccludeMoleculesofMetalloporphyrinsand
otherCompounds 58
2.4.7 ApparentAbsenceof“ConsecutiveAggregation”inAsphaltene
Experiments:RevisedDescriptionoftheObservedNon-monotonic
ConcentrationEffectsinDiluteAsphalteneSolutions 62
References 65
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Contents ix
3 ESRCharacterizationofOrganicFreeRadicalsinCrudeOil
andBy-Products 77
MarileneTuriniPiccinato,CarmenLuisaBarbosaGuedes
andEduardoDiMauro
3.1 Introduction 77
3.2 Organic-FreeRadicalsinCrudeOil 77
3.3 ESRofCrudeOil 78
3.4 By-ProductOilbyESR 85
3.5 ESRandCalculationsontheElectronicStructureofFreeRadicalsin
OilBy-Products 93
References 96
4 High-Field,Pulsed,andDoubleResonanceStudiesofCrude
OilsandtheirDerivatives 101
MaratGafurov,M.Volodin,T.Biktagirov,G.MaminandS.B.Orlinskii
4.1 Introduction 101
4.2 EPR:BasicPrinciplesandMagneticInteractions 103
4.3 EPRPulseSequences 109
4.4 ApplicationExamples 112
4.4.1 W-Band,RelaxationStudiesofVO2+andFRinAsphaltenes
(cid:2) Fractions 112 (cid:2)
4.4.2 ENDORofVO2+inCrudeOilSamples 116
4.5 Conclusion 121
Acknowledgments 121
References 121
5 NMRSpectroscopicAnalysisinCharacterizationofCrudeOil
andRelatedProducts 125
SiavashIravani
5.1 Introduction 125
5.2 1HNMRand13CNMRSpectroscopyAnalysisMethods 126
5.3 NMRTechniques 127
5.4 ApplicationofNMRAnalysisinCharacterizationofCrudeOiland
RelatedProducts 129
5.5 AsphalteneCharacterizationusingNMRTechniques 134
5.6 Conclusions 137
References 137
6 NMRSpectroscopyinBitumenCharacterization 141
CatarinaVaranda,InêsPortugal,JorgeRibeiro,CarlosM.Silva
andArturM.S.Silva
6.1 Introduction 141
6.2 1Hand13CNMRSpectroscopy 143
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6.3 Phosphorus-31NMRSpectroscopy 152
6.4 NMRImagingandSolid-StateNMR 154
6.4.1 Solid-StateNMR 154
6.4.2 NMRImaging 155
6.5 Conclusion 156
References 157
7 ApplicationsofLowFieldMagneticResonanceinViscous
CrudeOil/WaterPropertyDetermination 163
JonathanL.BryanandApostolosKantzas
7.1 Introduction 163
7.2 BackgroundforNMRMeasurements 165
7.2.1 InterpretationofNMRRelaxationRates 167
7.2.2 InterpretationofNMRAmplitudes 171
7.3 FluidContentinOil/WaterSystems 175
7.4 OilViscosityfromNMR 181
7.4.1 ViscosityPredictionsinHighViscosityBitumen 187
7.4.2 ViscosityPredictionsinOilfieldEmulsions 189
7.5 FluidSaturationsandViscosityinPorousMedia 192
7.5.1 PredictionofSaturationsandViscosityfromT relaxation
2
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7.5.2 PredictionofSaturationsfromT –T RelaxationDistributions 200
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7.6 NMRinOil-SolventSystems 206
7.6.1 PredictionsofSolventContentinOil–LiquidSolventSystems 207
7.6.2 PredictionsofNon-EquilibriumViscosityinOil–VaporSolvent
Systems 213
7.7 SummaryofNMRandFluidPropertyMeasurements 215
Acknowledgments 216
References 217
8 ApplicationofNear-InfraredSpectroscopytothe
CharacterizationofPetroleum 221
PatriciaAraujoPantoja,JuanLópez-Gejo,ClaudioAugustoOllerdo
NascimentoandGaloAntonioCarrilloLeRoux
8.1 Introduction 221
8.2 SampleHandlingandPreparation 222
8.3 Near-InfraredSpectroscopy 223
8.3.1 Near-InfraredinRefineries 227
8.4 Chemometrics 228
8.4.1 Pretreatment 228
8.4.1.1 Smoothing 228
8.4.1.2 MultiplicativeScatterCorrection 228
8.4.1.3 MeanCentering 229
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8.4.1.4 Derivation 230
8.4.2 CalibrationModel 230
8.4.2.1 PrincipalComponentAnalysis(PCA) 231
8.4.2.2 PartialLeastSquaresRegression 232
8.4.2.3 ArtificialNeuralNetworks 234
8.4.3 Validation 234
8.4.4 OtherMethods 235
8.5 CommercialNIREquipmentandIndustrialApplications 236
8.5.1 IndustrialApplications 236
8.5.1.1 PipelineProductAnalysisandIdentification 238
8.5.1.2 CrudeDistillationOptimization 238
8.5.1.3 ProductBlending 238
8.5.1.4 EthanolFermentation 238
8.5.1.5 ConjugatedDiolefinsinPygas 238
8.5.1.6 RegulatoryFuelScreening 238
8.6 Conclusions 239
References 239
9 RamanandInfraredSpectroscopyofCrudeOilandits
Constituents 245
(cid:2) JohannesKieferandStellaCorsetti (cid:2)
9.1 Introduction 245
9.2 FundamentalsofRamanandInfraredSpectroscopy 246
9.3 InfraredSpectroscopy 249
9.4 RamanSpectroscopy 251
9.5 EvaluationofVibrationalSpectra 257
9.6 Applications 261
9.7 Conclusion 266
References 267
Index 271
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Description:Basic theory, applications, and recent trends in analytical techniques used in crude oil and related products analysis This book covers the application of different spectroscopic methods to characterize crude oil and related products. Its topics are presented in a pedagogical manner so that those ne
