綠色化學(xué)第二章

Chapter2GreenChemistry

2.1

TheconceptofGreenChemistry

2.2PromotingthedevelopmentofGreenChemistry

2.3AtomEconomyofchemistryreaction

2.4AtomEconomyandenvironmentaleffects

2.5Researchareaofgreenchemistry

2.6Twelveprinciplesofgreenchemistry

References2.1TheconceptofGreenChemistryGreenChemistryisinvestigatedworld-widelyCountriesandareaswithGreenChemistryinvestigationchaptersNoyori:ImportanceofGreenChemistryWithoutGreenChemistry,chemicalmanufacturingwillbeunabletosurviveintothe22ndcentury.

GreenChemistryTheconnotationofGreenChemistryAdeeperviewofGreenChemistryGreenChemistryisrealizableGreenChemistryisdifferentfromenvironmentalcontrol

Theconnotation(內(nèi)涵)ofGreenChemistry

Greenchemistryisanactiveintercrossing(交叉)researchareaintheworld,itdealswiththefrontierofchemicalresearch.

Thetraditionalwaysofenvironmentalprotectionjustbringusabouttemporary(暫時(shí)的)solutionsforenvironmentalproblemswhileGreenChemistryprovidespermanent(永久的)cures.TheconnotationofGreenChemistryGreenChemistryprovideswaystoreduceoreliminateenvironmentalpollutionfromthebeginning,whichcouldhaveeternal(永遠(yuǎn)的)benefits.TheprinciplesofGreenChemistrycouldandshouldbeusedtoalldomain(領(lǐng)域)ofchemistryandchemicalengineering.TheconnotationofGreenChemistryNopollutionshouldbeaccompaniedinchemicalprocesses,thisistosay,eliminatethepotential(潛力)ofpollutionbeforeitoccurs.Therealizationofthisgoalmeansnoenvironmentalcontrolisneeded,becausetherewillbenopollution.TheGoalofGreenChemistry:TheconnotationofGreenChemistryGreenChemistryistheutilizationofasetofprinciplestoreduceoreliminatetheuseofhazardous(危險(xiǎn)的)materialsinthedesign,manufactureanduseofchemicals,andthesechemicals

themselvesshouldbeeconomicallyandenvironmentallybenign(仁慈的).Itdealsalsowiththereductionandeliminationoftheuseofhazardousmaterialsinthedesignanduseofchemicalprocesses.GreenChemistryTheconnotationofGreenChemistryGreenChemistryistheapplicationofchemicalprinciples,chemicaltechnologiesandchemicalmethodstoallchemicalsandchemicalprocessestoreduceoreliminatetheuseofhazardousstartingmaterials,hazardousprocesses,hazardoustargetproducts,hazardousauxiliarysubstances(suchassolvents,separationagents)intheproductionanduseofchemicals.GreenChemistryTheconnotationofGreenChemistryHazardousorpotentiallyhazardousprocessesshouldalsobereducedoreliminated.By-productsareexpectedtobeavoidedasthoroughlyaspossibleandthestartingmaterialsbeutilizedascompletelyaspossiblethussatisfyingasustainablecivilization.GreenChemistryTheconnotationofGreenChemistryGreenchemistryisthesciencewhichuseschemicalprinciplesandmethodstoreduceoreliminatetheuseofhazardousstartingmaterials,catalysts,solvents,reactionagents,targetproducts,by-products,etc.,whicharetoxicorharmfultohumanbeingsandenvironment.Itisthechemistrywhichcouldreduceandeliminatepollutionfromtheverybeginningandcurepollutioneternally.Environment&resourceSimultaneouslygiveoutGreenChemistrySolutionRecyclableeconomySustainabledevelopmentCrisesRequirementGreenChemistryGreenChemistryTheconnotationofGreenChemistryAdeeperviewofGreenChemistryGreenChemistryisrealizableGreenChemistryisdifferentfromenvironmentalcontrol

GreenChemistryisrealizableThegoalofgreenchemistryistoseekforperfection(byovercomingdifficulties).Synthesisefficiencyishighlythoughtofingreenchemistry.Oppositeopinions:itisdifficulttoquantify

thetoxicity(毒性)andharmfulness(危害)ofasubstancetohumanbeingsandtoenvironment.

GreenChemistryisrealizableWecouldcompareandselectthemostfavorablesubstanceandmethodunderspecifiedconditions.Examplesalreadyrealizedgiveevidencestoillustratestronglythatgreenchemistryisrealizable.Relationshipbetweenstructureandproperties——givesuscluetopredicttheharmfulnessofsubstances.GreenchemistrywayBringaboutatemporarysolutionTreattheexistedwasteTreatwasteProvideapermanentcureEliminatewastefromtheoriginNowasteproducedNotneedforwastetreatmentTraditionalwayWasteproducedthentreatFacingtheincreasingenvironmentalpollutionGreenChemistryTheconnotationofGreenChemistryAdeeperviewofGreenChemistryGreenChemistryisrealizableGreenChemistryisdifferentfromenvironmentalcontrolDeeperView

GreenChemistryisoneoftheconcreteembodiment(體現(xiàn))oftheViewpointofScientificDevelopment(科學(xué)發(fā)展觀).

GreenChemistryprovidesbasicscientificprinciplesandtechnologiestosupporttheViewpointofScientificDevelopmentandRecyclableEconomy(循環(huán)經(jīng)濟(jì)).Deeperviewpointson

GreenChemistry

Scientificviewpoints:GreenChemistryconcernsnewresearchareaofchemistry.Itrejuvenates(更新)thecontentsofchemistry.

EnvironmentallybenignStartingmaterialsTargetproductsHighselectivity,atomeconomy(原子經(jīng)濟(jì)性)Deeperviewpointson

GreenChemistryEconomicalviewpoint:GreenChemistryprovidesfundamentalprinciplesandtechniquestoutilizeeffectivelythestartingmaterials(resources)andenergymeanwhilethecostoftheproductionisreducedthussatisfyingtherequirementsofsustainabledevelopment.Deeperviewpointson

GreenChemistryEnvironmentalviewpoint:GreenChemistryprovidesnewprinciplesandtechniquestocutdownpollutionoriginally(從源頭上)andeternally.

2.1

TheconceptofGreenChemistry

2.2

PromotingthedevelopmentofGreenChemistry

2.3AtomEconomyofchemistryreaction

2.4AtomEconomyandenvironmentaleffects

2.5Researchareaofgreenchemistry

2.6Twelveprinciplesofgreenchemistry

ReferencesWhy2.2PromotingthedevelopmentofGreenChemistrySatisfyingthedemandforsustainabledevelopmentofhumansocietySatisfyingtherequirementofscienceandeconomy

StronglydevelopgreenchemistrytosatisfythedemandforsustainabledevelopmentofhumansocietyTraditionalchemicalIndustryisaccompaniedbyunexpectedharm(3aspects)NootheralternativesexistGreenchemistryistheuniquesolutionEnvironment&resourceSimultaneouslygiveoutGreenChemistrySolutionRecyclableeconomySustainabledevelopmentCrisesRequirementGreenChemistrySatisfyingtherequirementforthedevelopmentofscienceandeconomy

Chemistryitselfdevelopsinaccordancewiththechangeofresourcesandofthesocialrequirement.Itshouldalsoberenewedinmethodologyandcontent.

Greenchemistryappears.Scientifically:SatisfyingtherequirementforthedevelopmentofscienceandeconomyChemicalindustryplaysanimportantroleintheindustrialensembleBritain,Germany,USAChemicalenterprisesmakegreateffectstoreducetheircost,andincreasetheircostbytreatingthepollutantstheyproduced.Greenchemistryprovidesnewwayswhichcouldsatisfyboththedemandsofchemicalproduction.Economically

2.1

TheconceptofGreenChemistry

2.2PromotingthedevelopmentofGreenChemistry

2.3

AtomEconomyofchemistryreaction

2.4AtomEconomyandenvironmentaleffects

2.5Researchareaofgreenchemistry

2.6Twelveprinciplesofgreenchemistry

References2.3AtomEconomyofChemicalReaction(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

HCNTraditionalwayTraditionalwayheldCH3C(CN)(OH)CH3CH3COCH3+HCNAhsskaCH3OOC(CH3)C=CH2+NH4HSO4CH3OH,H2SO4CH3COCH3+HCN+CH3OH+H2SO4CH3OOC(CH3)C=CH2+NH4HSO4AA100+115╳

100%==a58a273298100115100115╳

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

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-productformedThus,nowastefortreatmentNopollutionProblemThetypesoforganicreactions:PleaseanswerWhichkindsareatomicallyeconomical?ExampleThesynthesisofhaloalkane

鹵代烴Atomeconomy:100%Noby-productNopollutionTheconsumptionofresourceisminimized。3molestargetmolecules/1moleby-product,Wasteresourcesandtheby-productisakindofpollutant3ROH+PX3

3RX+H3PO4RX’+NaXRX+NaX’R’CH=CH2+HX

RX1moletargetmolecules/1moleby-product，Wasteresourcesandtheby-productisakindofpollutantUsethenaturalresourcemoreefficiently,prolongtheirlifetime.

StudyonatomiceconomicreactionsChiraltechniqueAllatomsfromreactantsenterintothetargetmoleculeAllatomsfromreactantsenterintothetargetmoleculestereo-orientatedlyFacingthedriedupofnaturalresource?2.3.3Increasetheconversionofthereactantsandtheselectivityoftheproductsasthoroughlyaspossible

Atomeconomyisnecessaryforareactiontonotproducewaste,butitisnotenough.LowequilibriumconversionParallelreactions

2.1

TheconceptofGreenChemistry

2.2PromotingthedevelopmentofGreenChemistry

2.3AtomEconomyofchemistryreaction

2.4

AtomEconomyandenvironmentaleffects

2.5Researchareaofgreenchemistry

2.6Twelveprinciplesofgreenchemistry

References2.4.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×QChapter2GreenChemistry

2.1

TheconceptofGreenChemistry

2.2PromotingthedevelopmentofGreenChemistry

2.3AtomEconomyofchemistryreaction

2.4AtomEconomyandenvironmentaleffects

2.5

Researchareasofgreenchemistry

2.6Twelveprinciplesofgreenchemistry

References2.5

ResearchareasofgreenchemistryDesigningsaferandeffectivetargetmolecules

SeekingforsaferstartingmaterialsSeekingforsafersyntheticprocessesSeekingfornewsaferconversionwaysSeekingforsafernewreactionconditionsGreener,Safer2.5.1.DesigningsaferandeffectivetargetmoleculesThetargetmoleculebeing

safe

ispriorto

allconsiderations,anditshouldalsobe

effective.Thedesigningofsaferchemicalsistheuseoftherelationshipbetweenmolecularstructureandproperties

(structure-activityrelationship,SAR)

andmolecularmanipulation(操作)methodtoobtainmoleculeswithmaximizeddesiredfunctionsandminimizedharmfulness.DesigningsaferandeffectivetargetmoleculesIn1983,aseminaronthedesigningofsaferchemicalshasbeenholdinWashington.DesigningsaferandeffectivetargetmoleculesItinvolvestwoaspects:Thedesigningofnewsafeandeffectivemolecules.2.Thedesigningofnewsaferandeffectivemoleculestoreplacethemoleculeswhichexisted

effectivebutnotbenign

Wehavemorethan18,000thousandsofcompoundsuptonow,while600

thousandsofnewcompoundsappeareveryyear.DesigningsaferandeffectivetargetmoleculesDesigningsaferandeffectivetargetmoleculesTraditionalwaysoffindinganeffectivemolecule:PracticalneedssynthesistestsynthesistestNewmoleculardesigningways:TrialanderrorsPracticalneedsdesigningbySARsynthesisGuidedtheoreticallytestWorkingdesk+computer+ventilationcupboardDesigningsaferandeffectivetargetmolecules2.5.2.SeekingforNewstartingmaterials

Seekingnewstartingmaterialstosubstitutetheactuallyusedhazardousandpoisonousmaterials

Example1UsingCO2tosubstitutephosgene

（光氣）inthesynthesisofpolyurethane(聚氨酯)

Example2Eliminationtheuseofhydrocyanicacid（氫氰酸)

Example3Thesynthesisofadipicacid（己二酸）usingnewsafestartingmaterialsExample1EliminatingthepoisonousphosgeneinthesynthesisofpolyurethaneandpolycarbonatePolycarbonate(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)Thefunctionofphosgene:providing-COgroup按照化學(xué)RNH2+CO2RNCO+H2ORNHCO2R1Newgreenerway按照化學(xué)ThesynthesisofisocyanateusingCO2C6H5NH2+CO2

C6H5N(H)CO2HC6H5N=C=O–H2OAniline按照化學(xué)2CH3OH+COCl2CH3OOCOOCH3+2HCl2CH3OH+CO+?O2CH3OOCOOCH3+H2OCatalyst2CH3OH+CO2CH3OOCOOCH3+H2OThermodynamics,Catalyst,Reactionconditions:temperature/pressureThesynthesisofdi-methylcarbonate

碳酸二甲酯TraditionalwayNewgreenerways?Example2TheeliminationoftheuseofHCN(hydrocyanicacid)

(hydrogencyanide,prussicacid)bychangingtheprocessHydrocyanicacidHCNiswidely

usedfortheproductionof:

Hexanedinitrile(己二腈);Seriesofmethylpropenoicacid(甲基丙烯酸系列);Seriesofintermediatechemicalssuchaschelator/chelatingagent(螯合劑),methionine(蛋氨酸)etc.Thesynthesisofsodiumiminodi-acetate(亞氨基二乙酸二鈉)Traditionalwayinvolvestwosteps:按照化學(xué)NH3+2CH2O+2HCN—①NCCH2NHCH2CN—②+2NaOH→NaO2CCH2NHCH2CO2Na+NH3Anewstartingmaterial

HOCH2CH2NHCH2CH2OH

(diethanolamine,二乙醇胺)isused

NewgreenerwayReplacingHCN

Thesynthesisofadipicacid(/hexanedioicacid己二酸)andhexamethylenediamine(己二胺)CH2=CHCH=CH2+HCNNCCH2CH2CH2CH2CNHOOC(CH2)4COOHH2N(CH2)6NH2TraditionalmethodReplacingHCNC6H12TheoxidationofCyclo-hexane(環(huán)己烷)OxidationHOOC(CH2)COOHThehydrocarbonylationofbutadiene

氫甲酰化丁二烯CH2=CHCH=CH2+2CO+2H2OHC(CH2)4CHOHN=CH(CH2)4CH=NHH2N(CH2)6NH2HOOC(CH2)COOHO2catalyst2NH3-2H2O2H2NewgreenermethodsReplacingHCNThesynthesisofphenylaceticacid

苯乙酸C6H5CH2Cl+HCNC6H5CH2CN+HCl

C6H5CH2COOHH2OC6H5CH2Cl+COC6H5CH2COOHOH–/H2OTraditionalwayNewgreenerwayCanwedesignanothergreenwaytosynthesizephenylaceticacidwithethylbenzeneandoxygenasreactant?C6H5CH2CH3+O2C6H5CH2COOHIfcan’t,why?Example3ThesynthesisofadipicacidbychangingstartingmaterialTraditionalwayCouldanyonetellmethe

disadvantagesofthismethodDisadvantagesofthe

traditionalmethod

PhotochemicalsmogDepletionofozone,AcidrainThestartingmaterial(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,industrialorganicchemicalswereallderivedfrombiomassoriginatedfromplantsUsingofrenewablestartingmaterial

Theuseofbiomassasstartingmaterialforenergyandchemicalsproductionregainmuchattention,becauseofitsrenewability.

CoalOilNaturalgas

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

oftonscanbeusedasresourceofenergy./yearInChina,Theburningofstraw:：wasteofresourcewhilepolluting

ThestructureofligninanditseffectonitsdegradationOrientateddegradationtoproducedirectlyusefulchemicalsHandlingandmanipulationofoxygen-richmoleculesTheeffectofimpuritiesonthedegenerationparametersanddistributionoftheproductsUsingofrenewablestartingmaterialFundamentalscientificchallenge:TechnicalchallengesCollectionofbiomassVariationofcompositionsofdifferentkindsofbiomassandgrownfromdifferentareaoftheworldContinuousoperationHandlingofmixturesratherthanpurecompoundUpgradingandSeparationoftheproductsHowtouseeffectivelythebio-productsUsingofrenewablestartingmaterialActualprogressesCrossAgriculturalwaste(polysaccharides多糖)NaturallydegradablepolymerSichuanUniversity,UniversityofScienceandTechnology,ShandongUniversity,ChemicalInstituteAcademyofChina,GuangzhouBiomassAnimalfeedsFuelChemicalsUsingofrenewablestartingmaterialHaltzapplefromTexasA&Muniversity1996,ThepresidentialGreenChemistryAward

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/M3Efficiencyofenergyconversi