Chemistry of Fossil Fuels and Biofuels

501 Pages·2013·5.835 MB·English

by  Harold Schobert

Chemistry of Fossil Fuels and Biofuels
Focusing on today’s major fuel resources – ethanol, biodiesel, wood, natural gas,
petroleum products, and coal – this book discusses the formation, composition and
properties of the fuels, and the ways in which they are processed for commercial use.
Thebookexaminestheoriginoffuelsthroughnaturalprocessessuchasphotosynthesis
andthegeologicaltransformation ofancientplant material;therelationshipsbetween
their composition, molecular structures, and physical properties; and the various
processes by which they are converted or refined into the fuel products appearing on
today’s market. Fundamental chemical aspects such as catalysis and the behaviour of
reactive intermediates are presented, and global warming and anthropogenic carbon
dioxide emissions are also discussed. The book is suitable for graduate students in
energy engineering, chemical engineering, mechanical engineering, and chemistry,
aswellasforprofessionalscientistsandengineers.
Harold H. Schobert is Professor Emeritus of Fuel Science, The Pennsylvania State
University,andExtra-ordinaryProfessor,CoalResearchGroup,North-WestUniversity.
Arecognizedleadingauthorityonenergytechnology,hehasover30years’experiencein
teachingandresearchonfuelchemistry.
Cambridge Series in Chemical Engineering
SeriesEditor
ArvindVarma,PurdueUniversity
EditorialBoard
ChristopherBowman,UniversityofColorado
EdwardCussler,UniversityofMinnesota
ChaitanKhosla,StanfordUniversity
AthanassiosZ.Panagiotopoulos,PrincetonUniversity
GregoryStephanopolous,MassachusettsInstituteofTechnology
JackieYing,InstituteofBioengineeringandNanotechnology,Singapore
BooksinSeries
BaldeaandDaoutidis,DynamicsandNonlinearControlofIntegratedProcessSystems
Chau,ProcessControl:AFirstCoursewithMATLAB
Cussler,Diffusion:MassTransferinFluidSystems,ThirdEdition
CusslerandMoggridge,ChemicalProductDesign,SecondEdition
Denn,ChemicalEngineering:AnIntroduction
Denn,PolymerMeltProcessing:FoundationsinFluidMechanicsandHeatTransfer
DuncanandReimer,ChemicalEngineeringDesignandAnalysis:AnIntroduction
FanandZhu,PrinciplesofGas-SolidFlows
Fox,ComputationalModelsforTurbulentReactingFlows
Leal,AdvancedTransportPhenomena:FluidMechanicsandConvectiveTransport
MewisandWagner,ColloidalSuspensionRheology
Morbidelli,Gavriilidis,andVarma,CatalystDesign:OptimalDistributionofCatalystinPellets,
Reactors,andMembranes
NobleandTerry,PrinciplesofChemicalSeparationswithEnvironmentalApplications
OrbeyandSandler,ModelingVapor-LiquidEquilibria:CubicEquationsofStateandtheirMixing
Rules
Petyluk,DistillationTheoryanditsApplicationstoOptimalDesignofSeparationUnits
RaoandNott,AnIntroductiontoGranularFlow
Russell,RobinsonandWagner,MassandHeatTransfer:AnalysisofMassContactorsandHeat
Exchangers
Schobert,ChemistryofFossilFuelsandBiofuels
Slattery,AdvancedTransportPhenomena
Varma,Morbidelli,andWu,ParametricSensitivityinChemicalSystems
Chemistry of Fossil Fuels
and Biofuels
HAROLD SCHOBERT
ThePennsylvaniaStateUniversity
and
North-WestUniversity
CAMBRIDGEUNIVERSITYPRESS
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©H.Schobert2013
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andtotheprovisionsofrelevantcollectivelicensingagreements,
noreproductionofanypartmaytakeplacewithout
thewrittenpermissionofCambridgeUniversityPress.
Firstpublished2013
PrintedandboundintheUnitedKingdombytheMPGBooksGroup
AcatalogrecordforthispublicationisavailablefromtheBritishLibrary
LibraryofCongressCataloging-in-PublicationData
Schobert,HaroldH.,1943–
Chemistryoffossilfuelsandbiofuels/HaroldSchobert.
p. cm.– (Cambridgeseriesinchemicalengineering)
ISBN978-0-521-11400-4(Hardback)
1. Fossilfuels–Analysis. 2. Biomassenergy. 3. Energycrops–Composition.
4. Fuelwoodcrops–Composition. I. Title.
TP318.S3682012
553.2–dc23
2012020435
ISBN978-0-521-11400-4Hardback
CambridgeUniversityPresshasnoresponsibilityforthepersistenceor
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“Thebookisawelcomemodernupdatetotheavailableliteratureregardingthegenesis,
characteristics, processing and conversion of fossil and bio-derived fuels. Its compre-
hensive coverage of the chemistry involved with each of these aspects makes it an
importantsourceforupper-levelundergraduates,graduatestudents,andprofessionals
whoneed astrongunderstandingofthefield.Itisaninterestingread foranyonewho
reallywantstounderstandthenatureoffuels.”
RobertG.Jenkins,UniversityofVermont
“Thereisnootherbooklikethisinfieldofenergyscience.Itistheperfectintroduction
to the topic; but Professor Schobert has packed so much in, that it is just as much a
valuablereferenceformoreexperiencedprofessionals.Ittouchesonallaspectsoffuel
formation,transformationanduseaswellasstrategiesformanagingtheendproduct,
carbon dioxide. I will be using it as a text in my own teaching to both senior under-
graduateandgraduatestudents.”
AlanL.Chaffee,MonashUniversity,Australia
“Thisisanexcellentreferenceforthestudentofmodernfuelscienceorthepractitioner
wishing to sharpen their ‘big-picture’ understanding of the field. The book offers a
seasoned balance between technical rigor and readability, providing many helpful
references for the reader interested in further study. I found the text engaging and
enlightening, with the end-of-chapter notes a particularly thought-provoking and
entertainingbonus.”
CharlesJ.Mueller,SandiaNationalLaboratories

Contents
Preface pagexv
Acknowledgments xvii
Acknowledgmentsforpermissionstouseillustrations xviii
1 Fuelsandtheglobalcarboncycle 1
Notes 8
2 Catalysis,enzymes,andproteins 10
2.1 Catalysis 10
2.2 Proteins 11
2.3 Enzymes 13
Notes 17
3 Photosynthesisandtheformationofpolysaccharides 19
3.1 Watersplittinginphotosynthesis 20
3.2 Carbondioxidefixation 24
3.3 Glucose,cellulose,andstarch 27
Notes 32
4 Ethanol 35
4.1 Fermentationchemistry 35
4.2 Commercialproductionofethanolviafermentation 38
4.3 Ethanolasamotorvehiclefuel 42
4.4 Issuesaffectingpossiblelarge-scaleproductionoffuelethanol 47
4.5 Cellulosicethanol 48
Notes 49
5 Plantoilsandbiodiesel 53
5.1 Biosynthesisofplantoils 53
5.2 Directuseofvegetableoilsasdieselfuel 57
5.3 Transesterificationofplantoils 59
5.4 Biodiesel 62
Notes 66
viii Contents
6 Compositionandreactionsofwood 69
6.1 Woodcombustion 78
6.2 Woodpyrolysis 79
6.2.1 Charcoal 79
6.2.2 Methanol 81
6.3 Woodgasification 82
6.4 Woodsaccharificationandfermentation 83
Notes 84
7 Reactiveintermediates 87
7.1 Bondformationanddissociation 87
7.2 Radicals 89
7.2.1 Initiationreactions 89
7.2.2 Propagationreactions 91
7.2.3 Terminationreactions 94
7.3 Radicalreactionswithoxygen 95
7.4 Carbocations 97
7.5 Hydrogenredistribution 100
Notes 101
8 Formationoffossilfuels 103
8.1 Diagenesis:fromorganicmattertokerogen 104
8.2 Catagenesis:fromkerogentofossilfuels 109
8.3 Catagenesisofalgalandliptinitickerogens 111
8.4 Catagenesisofhumickerogen 117
8.5 Summary 127
Notes 128
9 Structure–propertyrelationshipsamonghydrocarbons 132
9.1 Intermolecularinteractions 132
9.2 Volatility 134
9.3 Meltingandfreezing 142
9.4 DensityandAPIgravity 145
9.5 Viscosity 148
9.6 Watersolubility 151
9.7 Heatofcombustion 152
9.8 Thespecialeffectsofaromaticity 156
Notes 158
10 Composition,properties,andprocessingofnaturalgas 161
10.1 Gasprocessing 164
10.1.1 Dehydration 164
10.1.2 Gassweetening 166
Contents ix
10.1.3 SeparationofC þhydrocarbons 168
2
10.2 Naturalgasasapremiumfuel 170
Notes 171
11 Composition,classification,andpropertiesofpetroleum 174
11.1 Composition 174
11.1.1 Alkanes 174
11.1.2 Cycloalkanes 175
11.1.3 Aromatics 177
11.1.4 Heteroatomiccompounds 179
11.1.5 Inorganiccomponents 180
11.2 Classificationandpropertiesofpetroleums 181
11.2.1 APIgravity 181
11.2.2 Carbonpreferenceindex 181
11.2.3 Age–depthrelationships 182
11.2.4 Compositionrelationships 183
11.3 Asphalts,oilsands,andotherunconventionaloils 187
Notes 189
12 Petroleumdistillation 192
12.1 Desalting 193
12.2 Principlesofdistillation 194
12.3 Refinerydistillationoperations 198
12.3.1 Atmospheric-pressuredistillation 198
12.3.2 Vacuumdistillation 199
12.4 Introductiontopetroleumdistillationproducts 200
12.4.1 Gasoline 200
12.4.2 Naphtha 201
12.4.3 Kerosene 201
12.4.4 Dieselfuel 202
12.4.5 Fueloils 202
12.4.6 Lubricatingoils 203
12.4.7 Waxes 203
12.4.8 Asphalt 204
Notes 204
13 Heterogeneouscatalysis 206
13.1 Catalyticmaterials 207
13.1.1 Theactivespecies 207
13.1.2 Thesupport 207
13.1.3 Thepromoter 209
13.1.4 Preparation 209
13.2 Adsorptiononcatalystsurfaces 210
13.3 Mechanismsofcatalyticreactions 216