Levulinic Acid: A Sustainable Platform Chemical for Value-Added Products

219 Pages·2023·2.519 MB·English

by  Mota C.J.A., de Lima A.L., Fernandes D.R., Pinto B.P.

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LevulinicAcid
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Levulinic Acid
A Sustainable Platform Chemical for Value-Added Products
Claudio J.A. Mota
Ana Lúcia de Lima
Daniella R. Fernandes
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Bianca P. Pinto
FederalUniversityofRiodeJaneiro
InstituteofChemistry
RiodeJaneiro
Brazil
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Thiseditionfirstpublished2023
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LibraryofCongressCataloging-in-PublicationData:
Names:Mota,ClaudioJ.A.,author.|Lima,AnaLúciade,author.|
Fernandes,DaniellaR.,author.|Pinto,BiancaPeres,author.
Title:Levulinicacid:asustainableplatformchemicalforvalue-added
products/ClaudioJ.A.Mota,AnaLúciadeLima,DaniellaR.Fernandes,
BiancaP.Pinto.
Description:Hoboken,NJ:Wiley,2023.|Includesbibliographical
referencesandindex.
Identifiers:LCCN2022038112(print)|LCCN2022038113(ebook)|ISBN
9781119814665(cloth)|ISBN9781119814689(adobepdf)|ISBN
9781119814696(epub)
Subjects:LCSH:Ketonicacids.
Classification:LCCQD341.K2M782023(print)|LCCQD341.K2(ebook)|
DDC547/.036–dc23/eng20221123
LCrecordavailableathttps://lccn.loc.gov/2022038112
LCebookrecordavailableathttps://lccn.loc.gov/2022038113
CoverDesign:Wiley
CoverImages:©tchara/AdobeStockPhotos;©Peggy_Marco/pixabay;©ybernardi/pixabay;
©stokpic/pixabay;MolecularStructures:CourtesyofDaniellaR.Fernandes
Setin9.5/12.5ptSTIXTwoTextbyStraive,Chennai,India
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v
Contents
AbouttheAuthors ix
Preface xi
1 LevulinicAcid–History,Properties,GlobalMarket,Direct
Uses,Safety 1
1.1 HistoryandProperties 1
1.2 GlobalMarket 8
1.3 DirectUses 10
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1.4 ToxicityofLevulinicAcidandInorganicLevulinates 12
1.5 ConcludingRemarks 13
References 15
2 ProductionandTechnologicalRoutes 19
2.1 ProductionandTechnologicalRoutesfromBiomass 19
2.2 PretreatmentofLignocellulosicBiomass 23
2.2.1 PhysicalPretreatment 23
2.2.1.1 Mechanical 24
2.2.1.2 Microwave 25
2.2.1.3 Ultrasound 25
2.2.2 ChemicalPretreatment 25
2.2.2.1 AcidHydrolysis 25
2.2.2.2 AlkalineHydrolysis 26
2.2.2.3 IonicLiquids 27
2.2.2.4 Organosolv 27
2.2.3 PhysicochemicalPretreatment 28
2.2.3.1 SteamExplosion(SE) 29
2.2.3.2 LiquidHotWater(LHW) 29
2.2.3.3 AmmoniaFiberExpansion(AFEX) 30
2.2.3.4 SupercriticalCO Explosion 30
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vi Contents
2.2.4 BiologicalPretreatment 31
2.3 ProductionofLevulinicAcidfromLignocellulosicBiomass 32
2.3.1 ProcessesforLAProduction:HomogeneousCatalysts 35
2.3.2 ProcessesforLAProduction:HeterogeneousCatalysts 38
2.3.3 ProcessesforLAProduction:BiphasicSystems 40
2.3.4 TheBiofineProcessofLAProduction 41
2.3.5 DownstreamProcessofLARecovery 42
2.4 CommercialPlantsfortheProductionofLA 44
2.5 Conclusion 47
References 47
3 LevulinateDerivatives–MainProductionRoutesandUses
ofOrganicandInorganicLevulinatesDerivatives 65
3.1 MainProductionRoutes 65
3.1.1 EsterificationofLevulinicAcid 65
3.1.2 DirectProductionfromtheAlcoholysisofPolyschacarides 71
3.1.3 AlcoholysisofFurfural 76
3.1.4 Alcoholysisof5-HydroxymethylFurfural 82
3.1.5 ProductionofLevulinateInorganicSalts 86
3.2 ImportanceandMarketoftheLevulinateDerivatives 87
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3.3 UsesofOrganicLevulinateDerivatives 88
3.3.1 FoodandCosmetic 88
3.3.2 FuelAdditives 89
3.3.3 Plasticizers 90
3.3.4 Solvents 91
3.4 UsesofInorganicLevulinateDerivatives 93
3.4.1 AntifreezeAdditive 93
3.4.2 Cosmetic,Pharmaceutical,andFood 93
3.4.3 MiscellaneousApplications 94
3.5 Conclusion 95
References 96
4 LevulinicAcidHydrogenation 107
4.1 LevulinicAcidHydrogenationProducts 107
4.1.1 γ-Valerolactone(GVL) 107
4.1.1.1 GVLVersusEthanol 111
4.1.1.2 2-Methyl-tetrahydrofuran(2-MTHF) 111
4.1.1.3 1,4-Pentanediol(1,4-PDO) 112
4.1.1.4 AlkylValerates 113
4.2 PerformanceofGVLasFuelAdditive 113
4.3 LevulinicAcidtoγ-Valerolactone 114
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Contents vii
4.3.1 ConversionofGVLinto1,4-PDOand2-MTHF 115
4.3.2 GVLtoButenesandHydrocarbons 117
4.4 HomogeneousandHeterogeneousCatalystsfortheEfficient
ConversionofLAtoGVL 121
4.4.1 PreciousMetalCatalysts 121
4.4.2 NonpreciousMetalCatalyst 125
4.4.2.1 Copper-BasedCatalysts 125
4.4.2.2 Nickel-BasedCatalysts 127
4.4.2.3 Zirconium-BasedCatalysts 130
4.4.2.4 Iron-BasedCatalysts 130
4.5 HeterogeneousCatalystsfortheConversionofLAandGVLto
1,4-PDOand2-MTHF 132
4.6 TypesofHydrogenatingAgents 135
4.7 PatentSearchofLAHydrogenation 137
4.8 Conclusion 138
References 138
5 CarbonylReactionsofLevulinicAcid–KetalsandOther
DerivativesFormedUponReactionwiththeCarbonylGroup
ofLevulinicAcid.ProductionRoutes,Technologies,andMain
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Uses 149
5.1 LevulincAcidEsterKetalsMainRoutes 150
5.1.1 LevulinicAcidEsterKetalsMainUses 153
5.2 SuccinicAcid 158
5.2.1 PetrochemicalandBiotechnologicalRoutes 158
5.2.2 LevulinictoSuccinicAcid 163
5.2.3 SuccinicAcidMainUses 164
5.3 δ-AminolevulinicAcid(DALA)MainRoutes 167
5.3.1 δ-AminolevulinicAcidMainUses 169
5.4 5-Methyl-N-Alkyl-2-PyrrolidoneMainRoutes 171
5.4.1 5-Methyl-N-Alkyl-2-PyrrolidoneMainUses 177
5.5 DiphenolicAcidMainRoutes 179
5.5.1 DiphenolicLevulinicAcidMainUses 181
5.6 Conclusion 185
References 185
6 LevulinicAcidintheContextofaBiorefinery 197
6.1 Biorefinery 197
6.2 Sugar-BasedBiorefinery 198
6.3 LevulincAcidandLevulinatesfromaSugarCaneBiorefinery 200
6.4 Productionofγ-ValerolactoneinaSugarCaneBiorefinery 201
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viii Contents
6.5 LAintheContextofaBiodieselPlant 204
6.6 Conclusions 206
References 207
Index 209
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ix
About the Authors
ClaudioJ.A.Motaholdsadegreeinchemical
engineering from the Federal University of
Rio de Janeiro (UFRJ), where he also obtained
his PhD in chemistry. He is full professor of
chemistry and chemical engineering, as well
as director of the Institute of Chemistry of the
UFRJ. He is a research fellow from CNPq and
state scientist from FAPERJ. He is member of
theBrazilianChemicalSociety(SBQ),Brazilian
Catalysis Society (SBCat), American Chemical
Society (ACS), and fellow of the Royal Society
of Chemistry (RSC). He was awarded with the
TWASPrize,givenbytheMexicanAcademyof
Science, the Technology Prize from the Brazilian Association of the Chemical
(cid:2) Industries (ABIQUIM), the Innovation Prize of SBQ, and the Simão Mathias (cid:2)
Medal, the highest honor of the SBQ. He is author of more than 160 scientific
publications,amongarticles,patents,andbooks.Heparticipatesintheeditorial
boards of the Journal of CO Utilization, Journal of Catalysis and ACS Omega,
2
havingalsoestablishedseveralinternationalcollaborations.Hiscurrentresearch
interests are focused on biomass transformation and processes of CO capture
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andconversion,targetingapplicationsinthefuelandchemicalsectors.
Ana Lúcia de Lima received her BA degree
(2011)inChemicalScienceswithTechnological
Assignments in Chemical Sciences from the
FederalUniversityofUberlândia(UFU),Brazil.
ShereceivedherMSc(2013)anddoctoral(2017)
degreesfromFederalUniversityofRiodeJaneiro
(UFRJ), Brazil. She has started postdoctorate
study (2017) at LMCP/IMA/UFRJ on develop-
ment and evaluation of polymeric hydrogels
for compliance control in oil reservoirs. At the
moment,sheisaprofessorattheDepartmentof
Analytical Chemistry at the Institute of Chem-
istry at UFRJ and a researcher at LARHCO/
UFRJwheresheresearchesintheareaofmeso-
porousmaterialswithvariousapplications,suchasheterogeneouscatalystswith
afocusonbiomasstransformationandadsorbentsforCO capture.
2
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x AbouttheAuthors
Daniella R. Fernandes is an adjunct profes-
sor at the Department of Organic Chemistry at
theInstituteofChemistryoftheFederalUniver-
sity ofRio deJaneiro (UFRJ), Brazil. She holds
a degree in chemistry (2001), master’s (2004),
anddoctorate(2009)inchemistryfromthesame
university, all with specialization in petroleum
chemistry. She is a permanent professor in the
ChemistryProfessionalMaster’sPrograminthe
National Network (PROFQUI) at the Institute
of Chemistry, UFRJ. She has been working at
the LARHCO in the environment, energy, and
catalysis areas, especially correlated to biomass
valorization,biofuelsproductionandchemicals,
andmaterialdevelopmentfor CO capture and
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utilization.
BiancaP.Pintograduatedinchemistry(2006)
from the State University of Rio de Janeiro
(cid:2) (UERJ) and obtained her master’s (2009) and (cid:2)
doctoral degrees (2013) in chemistry from the
Federal University of Rio de Janeiro (UFRJ,
Brazil). She continued to work at the same
university for a postdoctoral stay (2014–2021).
Her research focused on the catalytic transfor-
mation of levulinic acid into valerolactone and
otherproducts,andCO captureandconversion.
2
She is also a cofounder of CarbonAir Energy,
carbon capture, and utilization startup. She is
currently a substitute professor at the Depart-
ment of Analytical Chemistry at the UFRJ. She is the author or coauthor of 14
scientificarticlesinindexedjournals,3bookchapters,and2publishedbooks.
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