Table Of ContentHydrocarbonChemistry
Hydrocarbon Chemistry
Volume1
ThirdEdition
GeorgeA.Olah
LokerHydrocarbonResearchInstituteandDepartmentofChemistry
UniversityofSouthernCalifornia,LosAngeles,California
A´rpa´dMolna´r
DepartmentofOrganicChemistry
UniversityofSzeged,Szeged,Hungary
G.K.SuryaPrakash
LokerHydrocarbonResearchInstituteandDepartmentofChemistry
UniversityofSouthernCalifornia,LosAngeles,California
Thiseditionfirstpublished2018
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LibraryofCongressCataloging-in-PublicationData
Names:Olah,GeorgeA.(GeorgeAndrew),1927–2017,author.|Molna´r,A´rpa´d,1942–author.|
Prakash,G.K.Surya,author.
Title:Hydrocarbonchemistry/GeorgeA.Olah,A´rpa´dMolna´r,G.K.SuryaPrakash,Loker
HydrocarbonResearchInstituteandDepartmentofChemistry,UniversityofSouthernCalifornia,
LosAngeles,California,DepartmentofOrganicChemistry,UniversityofSzeged,Szeged,Hungary.
Description:Thirdedition.|Hoboken,NJ:Wiley,[2018]|Includesbibliographicalreferencesand
index.|
Identifiers:LCCN2017022048(print)|LCCN2017023298(ebook)|ISBN9781119390527(pdf)|
ISBN9781119390534(epub)|ISBN9781119390510(hardback)
Subjects:LCSH:Hydrocarbons.|BISAC:SCIENCE/Chemistry/Organic.|SCIENCE/Chemistry/
Industrial&Technical.|TECHNOLOGY&ENGINEERING/Petroleum.
Classification:LCCQD305.H5(ebook)|LCCQD305.H5O432018(print)|DDC547/.01–dc23
LCrecordavailableathttps://lccn.loc.gov/2017022048
Coverimage:©HelenStocker/Gettyimages
CoverdesignbyWiley
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10 9 8 7 6 5 4 3 2 1
v
Contents
PrefacetotheThirdEdition xiii
PrefacetotheSecondEdition xv
PrefacetotheFirstEdition xvii
Introduction xix
IntroductionandGeneralAspects 1
1.1 HydrocarbonsandTheirClasses 1
1.2 Energy–HydrocarbonRelationships 2
1.3 HydrocarbonSources 4
1.3.1 Coal 5
1.3.2 PetroleumOil 7
1.3.3 HeavyOils,TarSand,andBituminousDeposits 8
1.3.4 NaturalandShaleGas 10
1.3.5 OtherNaturalMethaneSources 12
1.3.6 CarbonDioxide 12
1.3.7 Biosources 13
1.3.8 Minerals(Carbonates)andMetalCarbides 14
1.3.9 AbiologicalHydrocarbonSources 15
ExtraterrestrialHydrocarbons 15
1.4 HydrocarbonProductionfromNaturalSources 16
1.4.1 CoalMiningandConversion 17
1.4.2 PetroleumOilRefiningandProcessing 18
1.4.3 NaturalandShaleGasProcessing 20
1.5 HydrocarbonSynthesis 20
1.5.1 Fischer–TropschSynthesisviaSyngas(CO+H )fromCoal
2
orNaturalGas 20
1.5.2 MethaneOligocondensation 22
1.5.3 ConversionthroughMethanol(MobilProcess)orMethyl
Halides 22
1.5.4 CarbonDioxideConversions 23
vi Contents
1.5.5 AdditionalMethaneSources,Production,andConversion
Reactions 25
1.6 NonrenewableandRenewableHydrocarbons 27
1.7 RegenerativeHydrocarbonsfromCO EmissionCapture
2
andRecycling 29
1.8 HydrocarbonFunctionalizationReactions 30
1.8.1 Homolytic(Free-Radical)Reactions 31
1.8.2 Heterolytic(Ionic)Reactions 32
1.8.3 NucleophilicReactions 34
1.8.4 OrganometallicReactions 35
1.9 UseofHydrocarbons,PetroleumOil 35
1.9.1 EnergyGeneration,Storage,andDelivery.Heating 36
1.9.2 TransportationFuels 36
1.9.3 ChemicalProducts,Plastics,andPharmaceuticals 38
References 38
HydrocarbonsfromPetroleumandNaturalGas 49
2.1 Cracking 49
2.1.1 CrackingProcesses 49
2.1.2 MechanismofCracking 52
2.1.3 ComparisonofCrackingOperations 58
2.2 Reforming 62
2.2.1 ThermalReforming 64
2.2.2 CatalyticReforming 64
Hydroforming 64
Metal-CatalyzedReforming 65
2.3 DehydrogenationwithOlefinProduction 71
2.3.1 ThermalDehydrogenation 71
2.3.2 CatalyticDehydrogenationtoAlkenes 73
HeterogeneousCatalysts 73
HomogeneousCatalysts 78
2.3.3 OxidativeDehydrogenation 80
2.3.4 PracticalApplications 85
C –C Alkenes 85
2 3
C Alkenes 86
4
Buta-1,3-dieneandIsoprene 87
HigherOlefins 88
Styrene 88
2.4 UpgradingofNatural-GasLiquids 89
2.5 AromaticsProduction 89
2.5.1 CatalyticDehydrogenationandDehydrocyclization 90
2.5.2 PracticalApplications 100
References 102
Contents vii
SynthesisfromC Sources 125
3.1 AspectsofC Chemistry 126
1
3.2 ChemicalReductiontoMethanolandOxygenates;
RecyclingofCO 127
2
3.2.1 CatalyticReductionandBireforming 129
HeterogeneousHydrogenation 129
HomogeneousHydrogenation 137
3.2.2 OtherReductions 143
IonicReduction 143
ElectrochemicalandElectrocatalyticReduction 143
Photoreduction 146
EnzymaticReduction 148
3.3 Fischer–TropschChemistry 149
3.3.1 Catalysts 151
3.3.2 Mechanism 153
3.3.3 RelatedProcesses 159
3.3.4 PracticalApplications 165
3.4 MethanolSynthesis 166
3.5 OligocondensationofMethane 173
3.5.1 CatalyticOxidativeCondensation 173
3.5.2 High-TemperatureSelf-Condensation 180
3.5.3 NonoxidativeActivationofMethane 181
3.5.4 DehydroaromatizationofMethane 183
3.6 HydrocarbonsfromMethaneDerivatives 186
3.6.1 HydrocarbonsfromMethanol 186
3.6.1.1 MethanolConversiontoHydrocarbons 186
3.6.1.2 MethanoltoHydrocarbonTechnologies 196
MethanoltoGasoline 196
MethanoltoOlefin 197
MethanoltoPropylene 198
3.6.2 HydrocarbonsfromMethylHalides 198
3.6.3 HydrocarbonsfromSulfuratedMethanes 200
References 200
Isomerization 237
4.1 Acid-CatalyzedandBifunctionalIsomerization 238
4.1.1 Alkanes 238
Mechanism 243
4.1.2 Arylalkanes 250
Side-ChainIsomerization 250
PositionalIsomerization 250
4.1.3 AlkenesandDienes 256
4.2 Base-CatalyzedIsomerization 262
viii Contents
4.2.1 Alkenes 262
4.2.2 TheReversibleAcetylene–AlleneTransformation 265
4.3 Metal-CatalyzedIsomerization 266
4.3.1 Alkanes 266
4.3.2 Alkenes 270
4.3.3 DienesandEnynes 276
4.4 PericyclicRearrangements 277
4.5 PracticalApplications 284
4.5.1 IsomerizationofC –C Hydrocarbons 284
4 6
Alkanes 284
Alkenes 285
4.5.2 IsomerizationofXylenes 286
References 287
Alkylations 305
5.1 Acid-CatalyzedAlkylation 305
5.1.1 AlkylationofAlkaneswithAlkenes 305
5.1.2 AlkylationofAlkanesunderSuperacidicConditions 314
Alkylolysis(AlkylativeCleavage) 317
5.1.3 AlkylationofAlkenesandAlkynes 318
AlkylationofAlkeneswithOrganicHalides 318
AlkylationofAlkynes 320
AlkylationwithCarbonylCompounds:ThePrinsReaction 320
5.1.4 AlkylationofAromatics 322
5.1.4.1 AlkylationInducedbyFriedel–CraftsCatalysts 324
Catalysts 324
AlkylationwithAlkylHalides 326
AlkylationwithAlkenes 331
AlkylationwithAlkanes 335
AlkylationwithOtherReagents 338
5.1.4.2 TheuseofSolidAcidCatalystsinAlkylations 340
5.1.4.3 TransalkylationandDealkylation 347
5.2 Base-CatalyzedAlkylation 350
5.3 AlkylationthroughOrganometallics 352
5.4 MiscellaneousAlkylations 356
5.4.1 Side-ChainAlkylation 356
5.4.2 RelatedReactions 358
5.5 PracticalApplications 360
5.5.1 Isoalkane–AlkeneAlkylation 360
5.5.2 Ethylbenzene 364
5.5.3 Cumene 365
5.5.4 Xylenes 366
Contents ix
5.5.5 para-Ethyltoluene 367
5.5.6 DetergentAlkylates 368
References 369
AdditionReactions 389
6.1 Hydration 389
6.1.1 AlkenesandDienes 389
6.1.2 Alkynes 392
6.1.3 PracticalApplications 395
ProductionofAlcoholsbyHydrationofAlkenes 395
ProductionofOctane-EnhancingOxygenates 396
Acetaldehyde 397
6.2 HXAddition 398
6.2.1 Hydrohalogenation 398
Alkenes 398
Dienes 403
Alkynes 404
6.2.2 HypohalousAcidsandHypohalites 407
6.2.3 HydrogenCyanide 409
6.2.4 PracticalApplications 411
EthylChloride 411
HydrochlorinationofButa-1,3-diene 411
VinylChloride 411
EthyleneChlorohydrin 412
PropyleneChlorohydrin 412
Adiponitrile 412
Acrylonitrile 413
6.3 HalogenAddition 413
6.3.1 Alkenes 413
6.3.2 Dienes 419
6.3.3 Alkynes 422
6.3.4 PracticalApplications 422
VinylChloride 422
ChlorinationofButa-1,3-diene 424
6.4 AdditiontoFormC–NBonds 424
6.4.1 Alkenes 425
6.4.2 Dienes 428
6.4.3 Alkynes 429
6.4.4 Aziridination 432
6.5 AdditiontoFormC–O,C–S,andC–PBonds 433
6.5.1 Hydroalkoxylation 433
6.5.2 Hydrothiolation 435
x Contents
6.5.3 Hydroaryloxylation 436
6.5.4 Acyloxylation 437
6.5.5 Hydrophosphination 438
6.6 Hydrometalation 439
6.6.1 Hydroboration 439
Alkenes 440
Dienes 446
Alkynes 448
6.6.2 Hydroalumination 449
6.6.3 Hydrosilylation 450
Alkenes 452
Dienes 456
Alkynes 457
6.6.4 Hydrozirconation 459
6.6.5 HydrometalationwithOtherMetals 461
6.7 Halometalation 462
6.8 Solvometalation 465
6.9 Carbometalation 466
6.10 Cycloaddition 471
References 477
CarbonylationandCarboxylation 509
7.1 Carbonylation 509
7.1.1 Carbonylation(Hydroformylation)ofAlkenes 510
HydroformylationinBiphasicSolventSystems 515
TheUseofHeterogeneousCatalysts 516
HydroformylationofHigherAlkenes 518
HydroformylationofInternalAlkenes 519
AsymmetricHydroformylation 520
7.1.2 DienesandAlkynes 522
7.1.3 ThePauson–KhandCyclization 523
7.1.4 CarbonylationofAlkanesandAromatics 525
7.1.5 SynthesisofAlcohols 526
7.1.6 IndustrialSynthesisofAldehydesbytheOxoReaction 527
7.1.7 CarbonylativeSonogashiraCoupling 529
7.1.8 Aminomethylation 530
7.2 Carboxylation 533
7.2.1 TheKoch–HaafReaction 533
7.2.2 Acid-CatalyzedCarboxylations 534
SaturatedHydrocarbons 534
AromaticHydrocarbons 536
7.2.3 CarboxylationMediatedbyMetalCatalysts 537
7.2.3.1 Carboxylationofsp3,sp2,andspC–HBonds 537
Contents xi
7.2.3.2 HydrocarboxylationofUnsaturatedHydrocarbons 539
HydrocarboxylationandHydroesterification 539
Aminocarboxylation 545
7.2.4 PracticalApplications 547
NeocarboxylicAcids 547
HydrocarboxymethylationofLong-ChainAlkenes 547
PropionicAcid 547
AcrylicAcidandAcrylates 548
References 548
Acylation 569
8.1 AcylationofAromatics 569
8.1.1 GeneralCharacteristics 569
8.1.2 CatalystsandReactionConditions 571
NewSolubleCatalysts 573
SolidCatalysts 575
8.1.3 Formylation 577
TheGattermann–KochReaction 577
TheGattermannReaction 579
OtherFormylations 580
8.1.4 TheHouben–HoeschReaction 581
8.2 AcylationofAliphaticCompounds 581
8.2.1 AcylationofAlkanes 581
8.2.2 AcylationofAlkenes 582
8.2.3 AcylationofAlkynes 585
References 586
