四川大學(xué)綠色化學(xué)課件第二章

Chapter2GreenChemistryScience,Vol.310,2005,1884(23DECEMBER,2005)

2.1TheconceptofGreenChemistryGreenChemistryisinvestigatedworld-widelyCountriesandareaswithGreenChemistryinvestigationchaptersNoyori:ImportanceofGreenChemistry

WithoutGreenChemistry,chemicalmanufacturingwillbeunabletosurviveintothe22ndcentury.野依良治RyojiNoyori(1938-)，日本名古屋大學(xué)2001，NobelPrizeGREENCHEMISTRY

Greenchemistryisanactiveintercrossing(交叉)researchareaintheworld,itdealswiththefrontierofchemicalresearch.

Thetraditionalwaysofenvironmentalprotectionjustbringusabouttemporary(暫時(shí)的)solutionsforenvironmentalproblems,whileGreenChemistryprovidespermanent(永久的)cures.

Theconnotation(內(nèi)涵)ofGreenChemistryGreenChemistryprovideswaystoreduceoreliminate(消除)environmentalpollutionfromthebeginning,whichcouldhaveeternal(永遠(yuǎn)的)benefits.TheprinciplesofGreenChemistrycouldandshouldbeusedtoalldomain(領(lǐng)域)ofchemistryandchemicalengineering.

Theconnotation(內(nèi)涵)ofGreenChemistryNopollutionshouldbeaccompaniedinchemicalprocesses,thisistosay,eliminatethepotentialofpollutionbeforeitoccurs.Therealizationofthisgoalmeansnoenvironmentalcontrolisneeded,becausetherewillbenopollution.

TheconnotationofGreenChemistryGreenChemistryistheutilizationofasetofprinciplestoreduceoreliminatetheuseofhazardous(危險(xiǎn)的)materialsinthedesign,manufactureanduseofchemicalsAndthesechemicalsshouldbeeconomicallyandenvironmentallybenign(仁慈的).Itdealsalsowiththereductionandeliminationoftheuseofhazardousmaterialsinthedesignanduseofchemicalprocesses.

TheconnotationofGreenChemistryGreenChemistryistheapplicationofchemicalprinciples,chemicaltechnologiesandchemicalmethodstoallchemicalsandchemicalprocessestoreduceoreliminatetheuseofhazardousstartingmaterials,hazardousprocesses,hazardoustargetproducts,hazardousauxiliarysubstances

(suchassolvents,separationagents)intheproductionanduseofchemicals.

TheconnotationofGreenChemistryHazardousorpotentiallyhazardousprocessesshouldalsobereducedoreliminated.By-productsareexpectedtobeavoidedasthoroughlyaspossible,andthestartingmaterialsbeutilizedascompletelyaspossible,thussatisfyingasustainablecivilization.

TheconnotationofGreenChemistryGreenchemistryisthesciencewhichuseschemicalprinciplesandmethodstoreduceoreliminatetheuseofhazardousstartingmaterials,catalysts,solvents,reactionagents,targetproducts,by-products,etc.,whicharetoxic(有毒的)orharmfultohumanbeingsandenvironment.Itisthechemistrywhichcouldreduceandeliminatepollutionfromtheverybeginningandcurepollutioneternally.

TheconnotationofGreenChemistryGREENCHEMISTRYGreenChemistryRequirementCrises

GreenChemistryisrealizable

GreenChemistryisrealizableThegoalofgreenchemistryistoseekforperfection(byovercomingdifficulties).Synthesisefficiencyishighlythoughtofingreenchemistry.Oppositeopinions:itisdifficulttoquantifythetoxicity(毒性)andharmfulness(危害)ofasubstancetohumanbeingsandtoenvironment.Examplesalreadyrealizedgiveevidencesstronglytoillustratethatgreenchemistryisrealizable.Relationshipbetweenstructureandproperties——givesuscluetopredicttheharmfulnessofsubstances.Wecouldcompareandselectthemostfavorablesubstanceandmethodunderspecifiedconditions.

GreenChemistryisrealizableGREENCHEMISTRYGreenchemistrywayBringaboutatemporarysolutionTreattheexistedwasteTreatwasteProvideapermanentcureEliminatewastefromtheoriginNowasteproducedNotneedforwastetreatmentTraditionalwayWasteproducedthentreatFacingtheincreasingenvironmentalpollutionGREENCHEMISTRYGreenChemistryisoneoftheconcreteembodiment(體現(xiàn))oftheViewpointofScientificDevelopment(科學(xué)發(fā)展觀).GreenChemistryprovidesbasicscientificprinciplesandtechnologiestosupporttheViewpointofScientificDevelopmentandRecyclableEconomy(循環(huán)經(jīng)濟(jì)).DeeperviewpointsonGreenChemistry

Scientificviewpoints:GreenChemistryconcernsnewresearchareaofchemistry.Itrejuvenates(更新)thecontentsofchemistry.

EnvironmentallybenignStartingmaterials,TargetproductsHighselectivity,atomeconomy(原子經(jīng)濟(jì)性)DeeperviewpointsonGreenChemistryEconomicalviewpoint:GreenChemistryprovidesfundamentalprinciplesandtechniquestoutilizeeffectivelythestartingmaterials(resources)andenergy,meanwhilethecostoftheproductionisreduced,thussatisfyingtherequirementsofsustainabledevelopment.DeeperviewpointsonGreenChemistryEnvironmentalviewpoint:GreenChemistryprovidesnewprinciplesandtechniquestocutdownpollutionoriginally(從源頭上)andeternally.DeeperviewpointsonGreenChemistryWhy2.2PromotingthedevelopmentofGreenChemistrySatisfyingthedemandforsustainabledevelopmentofhumansocietySatisfyingtherequirementofscienceandeconomy

Chemistryitselfdevelopsinaccordancewiththechangeofresourcesandofthesocialrequirement.Itshouldalsoberenewedinmethodologyandcontent.Greenchemistryappears.Scientifically:SatisfyingtherequirementforthedevelopmentofscienceandeconomyChemicalindustryplaysanimportantroleintheindustrialensembleBritain,Germany,USAChemicalenterprisesmakegreateffectstoreducetheircost,andincreasetheircostbytreatingthepollutantstheyproduced.Greenchemistryprovidesnewwayswhichcouldsatisfyboththedemandsofchemicalproduction.Satisfyingtherequirementforthe

developmentofscienceandeconomy2.3AtomEconomyofChemicalReaction(化學(xué)反應(yīng)的原子經(jīng)濟(jì)性)AtomutilizationAtomeconomyofchemicalreactionIncreasetheconversionofthereactants,theselectivityoftheproducts2.3.1.Atomutilization

(原子利用率)

Theconceptwasusedtoquantifythewaste(by-products)formedwhenacertainamountoftargetproductwasmanufacturedinachemicalreaction.RogerA.Sheldon1992R.A.Sheldon,2005.5ZhuhaiAtomutilization==Theamountoftargetproductformed╳

100%TheamountofallproductsformedstoichiometricallyTheamountofreactantsusedTheamountoftargetproductformed╳

100%Atomutilization

Thetwomaincharacteristicsofchemicalreactionwith100%atomutilization:Thereactantscouldbefullyutilized,andtheresourcecouldbemostpossiblyusedeconomicallyThewastecouldbeminimized原子利用率

=目標(biāo)產(chǎn)物的量按化學(xué)計(jì)量式所得所有產(chǎn)物的量之和

=目標(biāo)產(chǎn)物的量各反應(yīng)物的量之和╳

100%╳

100%Examples

Example1：Thepreparationofepoxy-ethane(環(huán)氧乙烷)fromethylene

more

Example2：Thepreparationofepoxy-propane(環(huán)氧丙烷)more

Example3：Thesynthesisofmethylacrylate(丙烯酸甲酯)

moreExample1Thepreparationofepoxy-ethaneTraditionalwayCH2=CH2+Cl2+H2OashsskaClCH2CH2OH+HClashsskaClCH2CH2OH+Ca(OH)2+HClC2H4O+CaCl2+2H2OCH2=CH2+Cl2+Ca(OH)2

C2H4O+CaCl2+H2Oaska2871744411118ashsskaashsska44ashsska111+18=12944111+18+44╳

100%=4428+71+74╳

100%=25%=Disadvantagesofthe

traditionalmethod1.

Theatomutilizationcouldreachonly25%,i.e.,1kgoftargetproduct/3kgofwastes.

2.

ThereactantCl2isharmful,iterodes(腐蝕)theequipmentandinjures(傷害)humanbeings,thusdemandingspecialequipmentandspecialprotectionmeasure.

3.

Separationandpurification(純化)processesarenecessarytoobtainusefulproduct.Ifeverystepcouldobtain100%selectivityand100%yield,thenSilvercatalyst

isusedtoconvertethylenedirectlytothetargetmoleculebyusingoxygenastheoxidant,whichgives100%atomutilization.NewgreenerwayCH2=CH2+1/2O2ashsska44C2H4O2816ashsska440ashsska4428+16=╳

100%╳

100%=44ashsska44=100%

Highatomeconomy

(100%)

Oxygen

is

safe

tohumanbeingsandtoenvironment.

Noseparationorpurification

isneeded.Advantagesofthe

newgreenermethodIftheselectivityofthereactioncouldreach100%Example2Thepreparationofepoxy-propaneka4271587411118ashsskaashaashaasha58asha111+18=12958111+18+58╳

100%=5842+71+74╳

100%=31%

C3H6O+CaCl2+H2OCH3CH=CH2+Cl2+Ca(OH)2

=TraditionalwayDisadvantagesofthe

traditionalmethod1.

Theatomutilizationcouldreachonly31%,i.e.,1kgoftargetproduct/2kgofwastes.

2.

ThereactantCl2isharmful,iterodestheequipmentandinjureshumanbeings,thusdemandingspecialequipmentandspecialprotectionmeasure.

3.

Separationandpurificationprocessesarenecessarytoobtainusefulproduct.Ifeverystepcouldobtain100%selectivityand100%yield,thenDirectoxidationcatalyzedbytitania-silicaNewgreenerwayka42345818ashsskaashaasha

C3H6O+H2OCH3CH=CH2+H2O2

AshsskaTitania-sillicamolecularsieveashsska5818asha5858+18╳

100%=5842+34╳

100%=76%=aTheamountoftargetproductformed

Theatomutilizationishigh

(76%)

Theby-product----waterisenvironmentallybenign.

Hydrogenperoxide

issaferthanchlorinetohumanbeingsandtoenvironment.Advantagesofthe

newgreenermethodIftheselectivityofthereactioncouldreach100%Problem?CH3CH=CH2+1/2O2

C3H6OExample3Thepreparationofmethylacrylate(丙烯酸甲酯)

Thisprocessusestheby-productsfromphenol(苯酚)industryandacrylonitrile(丙烯腈):acetoneandhydrocyanicacidH3CCOCH3

HCNTraditionalwayheldCH3C(CN)(OH)CH3CH3COCH3+HCNAhsskaCH3OOC(CH3)C=CH2+NH4HSO4CH3OH,H2SO4CH3COCH3+HCN+CH3OH+H2SO4CH3OOC(CH3)C=CH2+NH4HSO4AA100+115╳

100%==a58a273298100115100╳

100%10058+27+32+98100AAAAAA=46%AA115TraditionalwayDisadvantagesofthe

traditionalmethod1.

Theatomutilizationcouldreachonly46%,i.e.,1kgoftargetproduct/1kgofwastes.

2.

ThereactantHCN

isharmful,iterodestheequipmentandinjureshumanbeings,thusdemandingspecialequipmentandspecialprotectionmeasure.

3.

Separationandpurificationprocessesarenecessarytoobtainusefulproduct.Ifeverystepcouldobtain100%selectivityand100%yield,thenThisprocessutilizestheby-productpropyneCH3C≡CHfromthedissociation(e.g.Pyrolysis(熱解))ofnaphtha(石腦油),andcarbonmonoxide.NewgreenerwayUsingpalladiumacetatePd(OAc)2asthecatalyst，developedin90’sNewgreenerwayPd(OAc)2

Theatomutilizationishigh

(100%)

Carbonmonoxideandmethanol

aresaferthanhydrocyanicacidtohumanbeingsandtoenvironment.

No

waste

producedAdvantagesofthe

newgreenermethodIftheselectivityofthereactioncouldreach100%2.3.2AtomeconomyofchemicalreactionDefinition：

TheratioofatomsappearedinthetargetmoleculestoalltheatomsofthereactantsThereactionwith100%atomutilizationisidealatomeconomicalreaction.

1991，BarryM.Trost1996,ThePresidentialGreenChemistryChallengeAwardofUSAHowtodesign

atomeconomicalreactions如何設(shè)計(jì)原子經(jīng)濟(jì)反應(yīng)?DeficiencyofthetraditionalsyntheticwaysA+BC＋DwasteTargetmoleculeForatargetmoleculeC:

Ifthetraditionalwayis

A+BC+D

Thisprocessinevitablyproducestheby-product

D,whichshouldbetreatedandcouldbeconsideredaswaste.Becausethisisthechemicalreaction,ifwewanttousethisreaction,wecouldnotavoidthisdilemma.AtomiceconomicreactionsE+FCTargetproductThusweshoulddesignnewatomeconomicalreactionsas

E+FCAdvantages:

alltheatomsinthereactants

EandFenteredinthetargetmoleculeC,makingtheatomutilizationbe100%.Noby-productformed.Thus,nowastefortreatment.Nopollution.ProblemThetypesoforganicreactions:PleaseanswerWhichkindsareatomicallyeconomical?ExampleThesynthesisofhaloalkane

鹵代烴Facingthedriedupofnaturalresource?2.3.3Increasetheconversionofthereactantsandtheselectivityoftheproductsasthoroughlyaspossible

Atomeconomyisnecessaryforareactiontonotproducewaste,butitisnotenough.LowequilibriumconversionParallelreactions2.4.AtomEconomyandenvironmentaleffects2.4.1.Environmentalfactor

Itisusedtoquantifytheeffectsofproductionprocesstotheenvironment.

Idea:AllothercompoundsformedotherthanthetargetproductareconsideredtobeWASTE.RogerA.Sheldonin1992EnvironmentalfactorE=TheamountofwasteTheamountoftargetproductThelargerEThemorewasteformedThemoreseriousthepollutionIftheatomUtilization=100%E=0Theenvironmentalfactorofseveralindustries

Industries

Production/t

EPetrol106~108

~0.1

FundamentalChemicals104~1061~5Finechemicals102~1045~50Pharmacy10~10325~100Buttheenvironmentalpollutionisstronglyassociatedwiththeharmfulperformanceofthewaste.2.4.2.Environmentalquotient(EQ)TheE

factorjustgivestheratioofthewasteandthetargetproduct.Environmentalquotient

E-----EnvironmentalfactorQ-----Theextentofhazardousnessofthewastetotheenvironmentobtainedfromtheperformanceofthewasteintheenvironment.EQ＝E×Q2.5

ResearchareasofgreenchemistryGreener,Safer2.5.1.DesigningsaferandeffectivetargetmoleculesThetargetmoleculebeing

safe

ispriorto

allconsiderations,anditshouldalsobe

effective.Thedesigningofsaferchemicalsistheuseoftherelationshipbetweenmolecularstructureandproperties

(structure-activityrelationship,SAR)

andmolecularmanipulation(操作)methodtoobtainmoleculeswithmaximizeddesiredfunctionsandminimizedharmfulness.DesigningsaferandeffectivetargetmoleculesIn1983,aseminaronthedesigningofsaferchemicalshasbeenholdinWashington.DesigningsaferandeffectivetargetmoleculesItinvolvestwoaspects:Thedesigningofnewsafeandeffectivemolecules.SAR2.Thedesigningofnewsaferandeffectivemoleculestoreplacethemoleculeswhichexisted

effectivebutnotbenign.

Wehavemorethan18,000thousandsofcompoundsuptonow,while600

thousandsofnewcompoundsappeareveryyear.TraditionalsyntheticmethodtremendousamountofworktodoDesigningsaferandeffectivetargetmoleculesDesigningsaferandeffectivetargetmoleculesTraditionalwaysoffindinganeffectivemolecule:PracticalneedssynthesistestsynthesistestNewmoleculardesigningways:“Trialanderrors”PracticalneedsdesigningbySARsynthesisGuidedtheoreticallytestWorkingdesk+computer+ventilationcupboardfumehoodcomputerlaboratoryfurniture3-in-1modeDesigningsaferandeffectivetargetmoleculesGreener,Safer2.5.2.SeekingforNewstartingmaterials

Seekingnewstartingmaterialstosubstitutetheactuallyusedhazardousandpoisonousmaterials

Example1UsingCO2tosubstitutephosgene(COCl2光氣)inthesynthesisofpolyurethane(聚氨酯)andpolycarbonate(聚碳酸酯)

Example2Eliminationtheuseofhydrocyanicacid（氫氰酸)changingtheprocess

Example3Thesynthesisofadipicacid（己二酸）usingnewsafestartingmaterialsEliminatingthepoisonousphosgene

inthesynthesisofpolyurethaneandpolycarbonateExample1Polycarbonate(聚碳酸酯)Phosgeneiswidelyusedfortheproductionof:isocyanate(異氰酸酯)polyurethane(聚氨酯)Isocyanateisfirstsynthesizedbythereactionofphosgeneandamine,andthenusingisocyanatetoproducepolyurethane.Traditionalway按照化學(xué)RNH2+COCl2RNCO+2HClRNHCO2R1Thesynthesisofisocynate(異氰酸酯)Whatkindsof

functionalgroup

would

phosgene

provideinachemicalreaction?

Whichkindofcompoundcouldbeemployedtosubstitutephosgene?providing-COgroupCarbondioxideisusedtosubstitutephosgeneintheproductionofisocyanate(providingcarbonylgroup)按照化學(xué)RNH2+CO2RNCO+H2ORNHCO2R1Newgreenerway按照化學(xué)ThesynthesisofisocyanateusingCO2C6H5NH2+CO2

C6H5N(H)CO2HC6H5N=C=O–H2O苯胺異氰酸苯酯按照化學(xué)2CH3OH+COCl2CH3OOCOOCH3+2HCl2CH3OH+CO+?O2CH3OOCOOCH3+H2OCatalyst2CH3OH+CO2CH3OOCOOCH3+H2OThermodynamics,Catalyst,Reactionconditions:temperature/pressureThesynthesisofdimethylcarbonate(碳酸二甲酯,DMC)TraditionalwayNewgreenerways?*OrganicSncompounds,130-190oC,60-220mol%(basedonSn)TheeliminationoftheuseofHCN

(hydrocyanicacid)

(hydrogencyanide,prussicacid)bychangingtheprocessExample2

Hexanedinitrile(己二腈);Seriesofmethylpropenoicacid(甲基丙烯酸系列);Seriesofintermediatechemicalssuchaschelator/chelatingagent(螯合劑),methionine(蛋氨酸)etc.Hydrocyanicacid(HCN)iswidely

usedfortheproductionof:Thesynthesisofsodiumiminodi-acetate(亞氨基二乙酸二鈉)Traditionalwayinvolvestwosteps:按照化學(xué)NH3+2HCHO+2HCN—①NCCH2NHCH2CN—②+2NaOH→NaO2CCH2NHCH2CO2Na+NH3*exothermicreaction,unstableintermediate,processisdifficulttocontrol

Anewstartingmaterial

HOCH2CH2NHCH2CH2OH

(diethanolamine,二乙醇胺)isused.

Newgreenerway1996,ThePresidentialGreenChemistryChallengeAwardofUSA*one-step,highyield,friendlyH2,noseparation,nowasteCatalyticdehydrogenationIndustrialapplication:Cu-basedcatalysts:primaryalcoholstocarboxylicacids

ReplacingHCN

Thesynthesisofadipicacid(hexanedioicacid己二酸)andhexamethylenediamine(己二胺)CH2=CHCH=CH2+HCNNCCH2CH2CH2CH2CNHOOC(CH2)4COOHH2N(CH2)6NH2TraditionalmethodH2hydrolysisNylon,polyamidesC6H10TheoxidationofCyclohexane(環(huán)己烷):HOOC(CH2)COOHThehydrocarbonylationofbutadiene:(氫甲?；?(丁二烯)CH2=CHCH=CH2+2CO+2H2OHC(CH2)4CHOHN=CH(CH2)4CH=NHH2N(CH2)6NH2HOOC(CH2)COOHO2catalyst2NH3-2H2O2H2NewgreenermethodsOxidationH2O2ReplacingHCNThesynthesisofphenylaceticacid(苯乙酸):C6H5CH2Cl+HCNC6H5CH2CN+HCl

C6H5CH2COOHH2OC6H5CH2Cl+COC6H5CH2COOHTraditionalwayNewgreenerway①OH–/H2O②HClKeyissue:selectionandrecoveryofthecatalystCanwedesignanothergreenwaytosynthesizephenylaceticacidwithethylbenzeneandoxygenasreactant?C6H5CH2CH3+O2C6H5CH2COOHIfcan’t,why?Example3ThesynthesisofadipicacidbychangingstartingmaterialTraditionalwayCouldanyonetellmethe

disadvantagesofthismethod?

PhotochemicalsmogDepletionofozone,AcidrainWarmgasDisadvantagesofthe

traditionalmethodThestartingmaterial(Benzene)ishazardous(carcinogentic)ThereleaseofnitrogenoxideswhicharemultifunctionalpollutantsUseofheavymetals(cobalt)Eliminationoftheuseofsolvent,theuseofhazardousbenzene;thecorrosivecapacityofhydrogenperoxideisnotassevereasnitricacid,nopollutantsproduced.KamzuhikoSato,1998,Science,281:1646-1647按照化學(xué)Newgreenermethod1Thesynthesismethodiswidened.DrathandFrost,

1990,1991按照化學(xué)Newgreenermethod2Notonlyeliminatetheuseofbenzene,butalsodevelopanewmethodtouserenewablebiomass(glucose).Usingofrenewablestartingmaterial

150yearsago,industrialorganicchemicalswereallderivedfrombiomassoriginatedfromplants.

Theuseofbiomassasstartingmaterialforenergyandchemicalsproductionregainmuchattention,becauseofitsrenewability.

CoalOilNaturalgas

CoalStartingmaterials:BiomassIndustrialrevolutionOnekindofsolarenergyUsingofrenewablestartingmaterialSecurityandEnergyResourcesOil:30-50yearsNaturalGas:50-100yearsCoal:200-400yearsItmustbedegradatedbeforeitcouldbeeffectivelyused.Biomass：Starch(淀粉,amylum)+Lignin(木質(zhì)素,lignine)Lignin：164billionts/yearamountused<1.5%UsingofrenewablestartingmaterialExamplesUsingofrenewablestartingmaterialplants,trees,crops,grasses,aquaticplantsandtheirresiduesorwastematerials.MainFeasibleFormsofSolarEnergyHydraulicEnergy:GreensolarenergyDepleting&RenewableFossilFuel:AccumulatedAncientSolarEnergyDepletingBiomass:RenewableAnimals&plantsconvertedsolarenergyWindOthersFossilEnergyResourcesOilNaturalGasCoalAncientAnimalsandAncientPlantCarbonfixedbyancientlife-activitiesAncientSolarEnergyBiomassResourcesBiomassCarbonFixedbyActualLife-activitiesIncludingAnimals&Plants5hundredsmilliontonsofwheatstraw(麥稈);10milliontonsofricebran(米糠);10milliontonsofcorncob(玉米穗);20milliontonsofricehull(稻殼);7milliontonsofbiogases(沼氣);Usingofrenewablestartingmaterialabout2.8～3.5hundredsmillion

oftonscanbeusedasresourceofenergy./yearInChina,Theburningofstraw:：wasteofresourcewhilepollutingItmustbedegradatedbeforeitcouldbeeffectivelyused.Biomass：Starch(淀粉,amylum)+Lignin(木質(zhì)素,lignine)Lignin：164billionts/yearamountused<1.5%UsingofrenewablestartingmaterialExamplesplants,trees,crops,grasses,aquaticplantsandtheirresiduesorwastematerials.Usingofrenewablestartingmaterial

Thestructureofligninanditseffectonitsdegradation;Orientateddegradationtoproducedirectlyusefulchemicals;Handlingandmanipulationofoxygen-richmolecules;Theeffectofimpuritiesonthedegenerationparametersanddistributionoftheproducts.Fundamentalscientificchallenges:UsingofrenewablestartingmaterialTechnicalchallenges:

Collectionofbiomass;Variationofcompositionsofdifferentkindsofbiomassandgrownfromdifferentareaoftheworld;Continuousoperation;Handlingofmixturesratherthanpurecompounds;UpgradingandSeparationoftheproducts;Howtouseeffectivelythebio-products.ActualprogressesCrossAgriculturalwaste(polysaccharides多糖)NaturallydegradablepolymerSichuanUniversity,UniversityofScienceandTechnology,ShandongUniversity,ChemicalInstituteAcademyofChina,GuangzhouUsingofrenewablestartingmaterialBiomassAnimalfeedsFuelChemicalsHaltzapplefromTexasA&Muniversity1996,ThepresidentialGreenChemistryAwardUsingofrenewablestartingmaterial

Convertingbiomasstofuelandchemicals

Directliquation

BiomassLiquidfuel&chemicals

Indirectconversion

GasificationC3-C4GasesGasfuelCO+H2Liquidfuel&chemicalsCatalyticconversionUsingofrenewablestartingmaterialGasificationreactor(fixedbed)

forbiomassconversiongasifierpurificationfangas

tankNeededByHomebiomass,airGasificationreactor(fluidizedbed)forbiomassconversiongasifierairbiomasstankCO+2H2=CH3OHmethanolCO,H2screwfeederashseparationcatalysisreationbedreformingreactionbedbiomassGasificationreactor(fluidized

bed)forbiomassconversionGasproduction：150M3/hOperationpressure：1MPaHeatcapacity：7MJ/M3Efficiencyofenergyconversion：80%WaysofconvertingbiomasstochemicalsPlantsugarDehydration/hydrogenationUsefulChemicalsligninandCelluloseChemicalconversion

Bio-conversionBio-dieselFruitsBio-ethyleneethanolLeavesandTrunkFundamentalScientificChallengesintheDevelopmentofBiomassEnergyTheconversionofsugartochemicals

hydration/hydrogenationThestructureoflignin(木質(zhì)素)andcellulose：

Chemicalstructure(composition)Stereo-structureSupermolecularstructureConversionwithhighselectivityHighcontentofoxygen/LackofHydrogenTechnicalchallengesforbiomassconversionTroublesofbeingsolid:Badheatandelectricityconductivity;treatmentofsolidotherthanfluids;difficultiestoexertchemicalalterationssuchascatalyticeffectonthesolidetc.VariationofcompositionandstructureDifficultiesforcollectionetc.Researchareapresentlyaddressed:1.Chemistryforbio-dieselproduction2.Chemistryforbio-ethanol(bio-ethylene)production3.ChemistryfortheConversionofsugartousefulchemicals4.Chemistryforhydrogenproductionfrombiomass5.Chemistryforthegasificationofbiomass6.Chemistryforthepyrolyticliquefactionofbiomass7.Chemistryfortheup-gradingofbio-oil

1.Chemistryforbio-dieselproduction

2.Chemistryforbio-ethanol(bio-ethylene)production3.ChemistryfortheConversionofsugartousefulchemicals4.Chemistryforhydrogenproductionfrombiomass5.Chemistryforthegasificationofbiomass6.Chemistryforthepyrolyticliquefactionofbiomass7.Chemistryfortheup-gradingofbio-oil

Researchareapresentlyaddressed:Bio-diesel(生物柴油)CH2-CH-CH2OOROOROOR+3CH3OH3CH3OOR(Bio-diesel)+HOCH2CH(OH)CH2OHEffectiveandenvironmentallybenignCatalystsandCatalyticProcesses???Howtousetheglyceroleffectively???Bio-diesel(生物柴油)RCOOH+CH3OHCH3OOR(Bio-diesel)EffectiveandenvironmentallybenignCatalystsandCatalyticProcesses???Bio-dieselfromAlgaeAlgue“plant”美國(guó)馬薩諸塞州“藻類農(nóng)場(chǎng)”：發(fā)電廠，水，綠藻，CO2廢氣，陽(yáng)光，光合作用，糖類，蛋白質(zhì)和脂肪，生物柴油和乙醇。1.Chemistryforbio-dieselproduction2.Chemistryforbio-ethanol(bio-ethylene)production3.ChemistryfortheConversionofsugartousefulchemicals4.Chemistryforhydrogenproductionfrombiomass5.Chemistryforthegasificationofbiomass6.Chemistryforthepyrolyticliquefactionofbiomass7.Chemistryfortheup-gradingofbio-oil

Researchareapre