Table Of Content(cid:2)
Nano-andBiocatalystsforBiodieselProduction
(cid:2) (cid:2)
(cid:2)
(cid:2)
Nano- and Biocatalysts for Biodiesel Production
Edited by
Avinash P. Ingle
BiotechnologyCentre
DepartmentofAgriculturalBotany
Dr.PanjabraoDeshmukhKrishiVidyapeeth
Akola,Maharashtra
(cid:2) India (cid:2)
(cid:2)
(cid:2)
Thiseditionfirstpublished2021
©2021byJohnWiley&SonsLtd.Allrightsreserved.
Allrightsreserved.Nopartofthispublicationmaybereproduced,storedinaretrievalsystem,or
transmitted,inanyformorbyanymeans,electronic,mechanical,photocopying,recordingorotherwise,
exceptaspermittedbylaw.Adviceonhowtoobtainpermissiontoreusematerialfromthistitleisavailable
athttp://www.wiley.com/go/permissions.
TherightofAvinashP.Ingletobeidentifiedastheauthoroftheeditorialmaterialinthisworkhasbeen
assertedinaccordancewithlaw.
RegisteredOffices
JohnWiley&Sons,Inc.,111RiverStreet,Hoboken,NJ07030,USA
JohnWiley&SonsLtd,TheAtrium,SouthernGate,Chichester,WestSussex,PO198SQ,UK
EditorialOffice
TheAtrium,SouthernGate,Chichester,WestSussex,PO198SQ,UK
Fordetailsofourglobaleditorialoffices,customerservices,andmoreinformationaboutWileyproducts
visitusatwww.wiley.com.
Wileyalsopublishesitsbooksinavarietyofelectronicformatsandbyprint-on-demand.Somecontentthat
appearsinstandardprintversionsofthisbookmaynotbeavailableinotherformats.
LimitofLiability/Disclaimerof Warranty
Inviewofongoingresearch,equipmentmodifications,changesingovernmentalregulations,andthe
constantflowofinformationrelatingtotheuseofexperimentalreagents,equipment,anddevices,the
readerisurgedtoreviewandevaluatetheinformationprovidedinthepackageinsertorinstructionsfor
eachchemical,pieceofequipment,reagent,ordevicefor,amongotherthings,anychangesinthe
instructionsorindicationofusageandforaddedwarningsandprecautions.Whilethepublisherand
authorshaveusedtheirbesteffortsinpreparingthisbook,theymakenorepresentationsorwarranties
(cid:2) withrespecttotheaccuracyorcompletenessofthecontentsofthisworkandspecificallydisclaimall (cid:2)
warranties,includingwithoutlimitationanyimpliedwarrantiesofmerchantabilityorfitnessfora
particularpurpose.Nowarrantymaybecreatedorextendedbysalesrepresentatives,writtensales
materialsorpromotionalstatementsforthiswork.Thisworkissoldwiththeunderstandingthatthe
publisherisnotengagedinrenderingprofessionalservices.Theadviceandstrategiescontainedhereinmay
notbesuitableforyoursituation.Youshouldconsultwithaprofessionalwhereappropriate.Neitherthe
publishernorauthorshallbeliableforanylossofprofitoranyothercommercialdamages,includingbut
notlimitedtospecial,incidental,consequential,orotherdamages.Thefactthatanorganization,website,
orproductisreferredtointhisworkasacitationand/orpotentialsourceoffurtherinformationdoesnot
meanthatthepublisherandauthorsendorsetheinformationorservicestheorganization,website,or
productmayprovideorrecommendationsitmaymake.Further,readersshouldbeawarethatwebsites
listedinthisworkmayhavechangedordisappearedbetweenwhenthisworkwaswrittenandwhenitis
read.Neitherthepublishernorauthorsshallbeliableforanylossofprofitoranyothercommercial
damages,includingbutnotlimitedtospecial,incidental,consequential,orotherdamages.
Forgeneralinformationonourotherproductsandservicesorfortechnicalsupport,pleasecontactour
CustomerCareDepartmentwithintheUnitedStatesat(800)762-2974,outsidetheUnitedStatesat(317)
572-3993orfax(317)572-4002.
Wileyalsopublishesitsbooksinavarietyofelectronicformats.Somecontentthatappearsinprintmaynot
beavailableinelectronicformats.FormoreinformationaboutWileyproducts,visitourwebsiteat
ww.wiley.com.
LibraryofCongressCataloging-in-PublicationDataisappliedfor
ISBN:978-1-119-73000-2
CoverDesign:Wiley
CoverImage:Gaspumpnozzle©CoronaBorealisStudio/Shutterstock,Oliveoil©Valentyn
Volkov/Shutterstock,Buckyball©maggio07/GettyImages,NpmAmethyltransferase©LAGUNA
DESIGN/SciencePhotoLibraryRF/GettyImages
Setin9.5/12.5ptSTIXTwoTextbyStraive,Chennai,India
10 9 8 7 6 5 4 3 2 1
(cid:2)
(cid:2)
v
Contents
Preface xv
ListofContributors xix
1 Biodiesel:DifferentFeedstocks,ConventionalMethods,andFactors
AffectingitsProduction 1
HosseinEsmaeiliandSajadTamjidi
1.1 Introduction 1
1.2 DifferentFeedstocksforBiodieselProduction 3
1.2.1 VegetableSources 3
(cid:2) 1.2.2 WasteOils 3 (cid:2)
1.2.3 AnimalFats 5
1.2.4 MicroalgaOil 6
1.3 ConventionalMethodsofBiodieselProduction 8
1.3.1 Microemulsion 8
1.3.2 PyrolysisorThermalCracking 8
1.3.3 Transesterification 8
1.4 CatalystsUsedinBiodieselProduction 9
1.4.1 HomogeneousCatalysts 9
1.4.1.1 HomogeneousAlkalineCatalysts 9
1.4.1.2 HomogeneousAcidicCatalysts 9
1.4.2 HeterogeneousCatalysts 10
1.4.2.1 HeterogeneousAlkalineCatalysts 10
1.4.2.2 HeterogeneousAcidCatalysts 10
1.4.3 EnzymaticCatalysts 11
1.4.4 Nanocatalysts 12
1.5 EffectsofDifferentFactorsonBiodieselProductionYield 15
1.5.1 ReactionTemperature 15
1.5.2 AlcoholtoOilMolarRatio 16
1.5.3 ReactionTime 17
1.5.4 CatalystDosage 17
1.5.5 pH 17
1.5.6 MixingRate 17
(cid:2)
(cid:2)
vi Contents
1.5.7 FattyAcids 18
1.5.8 WaterContent 18
1.6 PhysicalPropertiesofBiodiesel 18
1.7 Conclusions 19
References 20
2 Nano(Bio)Catalysts:AnEffectiveTooltoUtilizeWasteCookingOilfor
theBiodieselProduction 31
RushikeshFopase,SwatiSharmaandLalitM.Pandey
2.1 Introduction 31
2.2 WasteCookingOils 33
2.3 PretreatmentofWCOs 33
2.4 TransesterificationProcess 34
2.4.1 KineticsofTransesterification 36
2.5 EnzymaticBiocatalysts 37
2.5.1 Lipases 38
2.5.1.1 ExtracellularLipases 38
2.5.1.2 IntracellularLipases 39
2.6 EnzymeImmobilizationTechniques 41
2.7 PhysicalMethods 42
2.7.1 Adsorption 42
(cid:2) 2.7.2 Encapsulation 45 (cid:2)
2.7.3 Entrapment 46
2.8 ChemicalMethods 47
2.8.1 CovalentBonding 47
2.8.2 Cross-Linking 49
2.8.3 Summary 50
2.9 Conclusions 50
References 51
3 AReviewontheUseofBio/NanostructuredHeterogeneousCatalysts
inBiodieselProduction 59
SamuelSantos,JaimePuna,JoãoGomesandJorgeMarchetti
3.1 Introduction 59
3.2 UseofMicro-andNanostructuredHeterogeneousCatalystsinBiodiesel
Production 62
3.2.1 MicrostructuredHeterogeneousCatalysts 62
3.2.1.1 SolidAcidCatalysts 62
3.2.1.2 SolidBaseCatalysts 63
3.2.2 NanostructuredHeterogeneousCatalysts 65
3.2.2.1 GasCondensation 65
3.2.2.2 VacuumDeposition 65
3.2.2.3 ChemicalDeposition 66
3.2.2.4 Sol-GelMethod 66
(cid:2)
(cid:2)
Contents vii
3.2.2.5 Impregnation 67
3.2.2.6 Nanogrinding 68
3.2.2.7 Calcination-Hydration-Dehydration 68
3.3 EnzymaticCatalysis 69
3.3.1 HeterogeneousBiocatalysts(Lipases)andTheirImmobilization 69
3.3.1.1 PhysicalAdsorption 70
3.3.1.2 Entrapment 70
3.3.1.3 CovalentBonding 71
3.3.1.4 Cross-Linking 72
3.3.2 Nano(Bio)Catalysts:ImmobilizationofEnzymesonNanosupports 73
3.3.2.1 Nanoparticles 73
3.3.2.2 CarbonNanotubes 75
3.3.2.3 Nanofibers 76
3.3.2.4 Nanocomposites 76
3.4 Conclusions 77
References 78
4 Calcium-BasedNanocatalystsinBiodieselProduction 93
PritiR.PanditandArchitMohapatra
4.1 Introduction 93
4.2 Nanocatalysts 94
(cid:2) 4.3 CaO-BasedNanocatalystsforBiodieselProduction 95 (cid:2)
4.3.1 SynthesisandCharacterizationofCaO-BasedNanocatalystsUsingWaste
Material 99
4.3.2 CaONanocatalystsSupportedwithMetalOxidesforBiodieselProduction 102
4.4 EffectsofDifferentParametersonBiodieselProduction 105
4.4.1 ReactionTime 105
4.4.2 Temperature 105
4.4.3 MethanoltoOilMolarRatio 106
4.4.4 CatalystLoad 106
4.5 ReusabilityandLeachingofNanocatalysts 106
4.6 Conclusions 107
References 107
5 TitaniumDioxide-BasedNanocatalystsinBiodieselProduction 115
ElijahOlawaleAjala,MaryAdejokeAjalaandHarvisBamideleSaka
5.1 Introduction 115
5.2 NaturalOccurrencesofTitania 117
5.2.1 Rutile 117
5.2.2 Anatase 118
5.2.3 RhombicBrookite 118
5.2.4 KaolinClays 118
5.2.5 IlmenitesorManaccanite 120
5.3 PrecursorsUsedfortheSynthesisofTiO NPs 120
2
(cid:2)
(cid:2)
viii Contents
5.3.1 TitaniumTetrachloride 121
5.3.2 TitaniumTetraisopropoxide 121
5.3.3 TitaniumButoxide 122
5.4 MethodsfortheSynthesisofTiO NPs 122
2
5.4.1 PhysicalMethods 122
5.4.1.1 BallMilling 122
5.4.1.2 LaserAblation/Photoablation 123
5.4.1.3 Sputtering 123
5.4.2 ChemicalMethods 123
5.4.2.1 Microemulsion 123
5.4.2.2 Precipitation 124
5.4.2.3 Sol-Gel 124
5.4.2.4 Hydrothermal 125
5.4.2.5 Solvothermal 125
5.4.2.6 Electrochemical/Deposition 125
5.4.2.7 Sonochemical 126
5.4.2.8 DirectOxidation 126
5.4.3 BiologicalMethods 126
5.4.3.1 GreenSynthesisUsingPlantExtracts 126
5.4.3.2 MicrobialSynthesis 128
5.4.3.3 Enzyme-MediatedSynthesis 129
(cid:2) 5.5 MethodsfortheSynthesisofTiO -BasedNanocatalysts 130 (cid:2)
2
5.5.1 WetImpregnation 130
5.5.2 DryImpregnation 131
5.6 TiO -BasedNanocatalystsforBiodieselProduction 131
2
5.6.1 SulfatedTiO Nanocatalysts 131
2
5.6.2 AlkalineTiO Nanocatalysts 133
2
5.6.3 Co-TransitionTiO Nanocatalysts 133
2
5.6.4 AlkaliTiO Nanocatalysts 134
2
5.6.5 BimetallicTiO Nanocatalysts 135
2
5.6.5.1 TiO -Pd-Ni 135
2
5.6.5.2 TiO -Au-Cu 135
2
5.7 OtherTiO NanocompositeCatalysts 135
2
5.8 Conclusions 136
References 136
6 Zinc-BasedNanocatalystsinBiodieselProduction 143
AvinashP.Ingle
6.1 Introduction 143
6.2 FeedstocksUsedforBiodieselProduction 144
6.2.1 VegetableOils 144
6.2.2 MicrobialOils 145
6.2.3 AnimalFats 145
6.2.4 WasteOils 145
(cid:2)
(cid:2)
Contents ix
6.2.5 Biomass 146
6.3 ConventionalMethodsofBiodieselProduction 146
6.3.1 Pyrolysis 146
6.3.2 Transesterification 146
6.3.2.1 HomogeneousAcidandBase(Alkali)-CatalyzedTransesterification 146
6.3.2.2 HeterogeneousAcidandBase(Alkali)-CatalyzedTransesterification 147
6.3.2.3 EnzymaticTransesterification 147
6.4 NanotechnologyinBiodieselProduction 148
6.5 Zinc-BasedNanocatalystsinBiodieselProduction 148
6.6 Conclusions 151
References 152
7 Carbon-BasedNanocatalystsinBiodieselProduction 157
RahulBhagat,HarrisPanakkal,IndarchandGuptaandAvinashP.Ingle
7.1 Introduction 157
7.2 FeedstocksUsedforBiodieselProduction 158
7.2.1 VegetableOils 158
7.2.2 Algae 159
7.2.3 AnimalFats 160
7.2.4 WasteCookingOils 160
7.3 ConventionalHeterogeneousCatalysts 160
(cid:2) 7.4 Carbon-BasedHeterogeneousNanocatalysts 164 (cid:2)
7.4.1 CarbonNanotubes 166
7.4.2 SulfonatedCarbonNanotubes 167
7.4.3 Graphene/GrapheneOxide-BasedNanocatalysts 168
7.4.4 CarbonNanofibersandCarbonDots 169
7.4.5 CarbonNanohorns 170
7.4.6 OtherCarbon-BasedNanocatalysts 171
7.5 Conclusions 174
References 174
8 FunctionalizedMagneticNanocatalystsinBiodieselProduction 183
KalyaniRajkumariandLalthazualaRokhum
8.1 Introduction 183
8.2 RelevanceofHeterogeneousCatalysisinBiodieselProduction 185
8.3 SurfaceModificationandFunctionalizationofNPs 186
8.4 ApplicationsofFunctionalizedMagneticNanocatalystsinBiodiesel
Production 186
8.4.1 Acid-FunctionalizedMagneticNanocatalysts 186
8.4.2 Base-FunctionalizedMagneticNanocatalysts 189
8.4.3 MagneticNanocatalystsFunctionalizedwithWasteMaterials 190
8.4.4 IonicLiquid-ImmobilizedMagneticNanocatalysts 192
8.5 Conclusions 194
References 195
(cid:2)
(cid:2)
x Contents
9 Bio-BasedCatalystsinBiodieselProduction 201
UmerRashid,Shehu-IbrahimAkinfalabi,NaeemahA.IbrahimandChawalit
Ngamcharussrivichai
9.1 Introduction 201
9.2 Biodiesel:APotentialSourceofRenewableEnergy 204
9.2.1 ProgressinBiodieselDevelopment 204
9.2.2 DevelopmentofBiodieselinMalaysia 205
9.2.3 BiodieselFeedstocks 206
9.2.3.1 PFADasaBiodieselFeedstock 207
9.2.4 CommonMethodsUsedforBiodieselReaction 208
9.2.4.1 Esterification 209
9.2.4.2 Transesterification 210
9.3 HomogeneousCatalysisinBiodieselProduction 211
9.4 HeterogeneousCatalysisinBiodieselProduction 213
9.5 CatalystSupports 215
9.5.1 Alumina 216
9.5.2 Silicate 216
9.5.3 ZirconiumOxide 217
9.5.4 ActivatedCarbon 217
9.6 HeterogeneousBio-BasedAcidCatalysts 217
9.7 SynthesisofBio-BasedSolidAcidCatalysts 218
9.7.1 PalmTreeFrondsandSpikelets 219
(cid:2) (cid:2)
9.7.2 Jatrophacurcas 219
9.7.3 CoconutShells 220
9.7.4 RiceHusks 220
9.7.5 Bamboo 221
9.7.6 CocoaPodHusks 221
9.7.7 Hardwoods 222
9.7.8 PeanutHulls 222
9.7.9 WoodMixtures 223
9.7.10 PalmKernelShells 223
9.8 MagneticBio-BasedCatalystsforBiodieselProduction 224
9.9 CharacterizationofBio-BasedCatalysts 228
9.9.1 FieldEmissionScanningElectronMicroscopy(FESEM) 228
9.9.2 FourierTransformInfrared(FT-IR) 229
9.9.3 X-RayDiffraction(XRD) 229
9.9.4 ThermogravimetricAnalysis(TGA) 230
9.9.5 Temperature-ProgrammedDesorption–Ammonia(TPD-NH ) 231
3
9.9.6 Brunauer–Emmett–Teller(BET)Analysis 231
9.10 ReactionParametersAffectingBiodieselProduction 232
9.10.1 ReactionTime 232
9.10.2 CatalystConcentration 232
9.10.3 MethanoltoFat/OilMolarRatio 232
9.10.4 ReactionTemperature 233
9.10.5 MixingRate 235
9.11 Conclusions 235
References 236
(cid:2)
(cid:2)
Contents xi
10 HeterogeneousNanocatalyticConversionofWastetoBiodiesel 249
NilutpalBhuyan,ManashJ.Borah,NeelamBora,DipankaSaikia,DhanapatiDeka
andRupamKataki
10.1 Introduction 249
10.2 RoleofCatalystsinBiodieselProduction 250
10.3 FeedstocksforBiodieselProduction 251
10.3.1 First-GenerationFeedstocksorEdibleOils 251
10.3.2 Second-GenerationFeedstocksorNon-EdibleOils 252
10.3.3 Third-GenerationFeedstocksorAlgae 252
10.3.4 OtherFeedstocks 253
10.4 BiodieselProductionProcess 253
10.4.1 Acid-CatalyzedTransesterification 254
10.4.1.1 MechanismofAcid-CatalyzedTransesterification 256
10.4.2 Alkali-orBase-CatalyzedTransesterification 256
10.4.2.1 MechanismofAlkali-orBase-CatalyzedTransesterification 258
10.4.3 OtherTypesofTransesterification 258
10.5 VariablesAffectingTransesterification 259
10.6 HeterogeneousNanocatalystsforBiodieselProduction 260
10.7 CharacterizationofNanoparticlesUsedforBiodieselProduction 262
10.7.1 X-RayDiffraction(XRD) 262
10.7.2 ScanningElectronMicroscopy(SEM) 262
(cid:2) 10.7.3 EnergyDispersiveX-RayAnalysis(EDX) 262 (cid:2)
10.7.4 TransmissionElectronMicroscopy(TEM) 264
10.7.5 AtomicForceMicroscopy(AFM) 264
10.7.6 RamanSpectroscopy 264
10.7.7 FourierTransformInfraredSpectroscopy(FT-IR) 264
10.7.8 X-RayPhotoelectronSpectroscopy(XPS) 264
10.7.9 ThermogravimetricAnalysis(TGA) 265
10.8 InfluenceofNanoparticlePropertiesonBiodieselProduction 265
10.9 SafetyIssuesAroundtheApplicationofNanocatalystsinBiodiesel
Production 267
10.10 FuturePerspectives 267
10.11 Conclusions 268
References 269
11 ApplicationofRareEarthCation-ExchangedNanozeoliteasa
SupportfortheImmobilizationofFungalLipaseandtheirUsein
BiodieselProduction 279
GuilhermedePaulaGuarnieri,AdrianodeVasconcellos,FábioRogériodeMoraes
andJoséGeraldoNery
11.1 Introduction 279
11.2 CaseStudy 282
11.2.1 OriginsofMaterialsandEnzymes 282
11.2.2 PreparationofNa-FAUNanozeolites 282
11.2.3 Ion-ExchangeExperiments 283
11.2.4 EnzymeImmobilizationontoNanozeoliticSupports 283
(cid:2)
