大三下册复习合集8环境化工旧

绿色化学工艺学2016-2017刘昌俊天津大学化工学院绿色化学原理的提出与发展PaulHermannMüller瑞士化学家。1948年获得诺贝尔生理学或医学奖1970年ThelatesixtiesandearlyseventiesweretimeswhentheenvironmentreceivedagreatdealofattentionincludingtheformationoftheEnvironmentalProtectionAgency(EPA)andthecelebrationofthefirstEarthDay,bothofwhichoccurredin1970.Intheinterveningyearsinexcessof100environmentallawshavebeenpassed.

thetwelvemajorlaws1970CleanAirAct.Regulatesairemissions.1972NationalEnvironmentalPolicyAct.RequiresinpartthatEPAreviewenvironmentalimpactstatementsofproposedmajorfederalprojects(e.g.highways,buildings,airports,parksandmilitarycomplexes).1972CleanWaterAct.EstablishesthesewagetreatmentconstructiongrantsprogramandaregulatoryandenforcementprogramfordischargesofpollutantsintoU.S.waters.1972FederalInsecticide,Fungicide&RodenticideAct.Governsdistribution,saleanduseofpesticideproducts.Allpesticidesmustberegistered(licensed)byEPA.1972OceanDumpingAct.Regulatestheintentionaldisposalofmaterialsintooceanwaters.1974SafeDrinkingWaterAct.Establishesprimarydrinkingwaterstandards.

thetwelvemajorlaws1976ToxicSubstancesControlAct.Requiresthetesting,regulating,andscreeningofallchemicalproducedorimportedintheU.S.1976ResourceConservation&RecoveryAct.Regulatessolidandhazardouswasteform“cradletograve.”1976EnvironmentalResearch&DevelopmentDemonstrationAct.AuthorizesallEPAresearchprograms.1980ComprehensiveEnvironmentalResponse,Compensation&LiabilityAct,betterknownasSuperfund.Providesforafederal“superfund”tocleanupabandonedhazardouswastesites,accidentalspillsandotheremergencyreleasesofpollutantsintheenvironment.EmergencyPlanning&CommunityRight-to-KnowAct.Requiresthatindustriesreporttoxicreleasesandencouragesplanningbylocalcommunitiestorespondtochemicalemergencies.1990PollutionPreventionAct.Seekstopreventpollutionbyencouragingcompaniestoreducethegenerationofpollutantsthroughcost-effectivechangesinproduction,operation,andrawmaterialuse.Alloftheseacts,withoneexception,dealwithpollutionafteritisformed.Theselawsareingeneralfocusedonthetreatmentorabatementofpollutionandhaveeknowas“commandandcontrol”laws.Inmanyinstancestheselaws,whichwerepassedbytheUScongress,placelimitsonpollutionandtimetablesforcompliance,withlittleregardtowhetherthescience/technologycouldattainthesegoalsandwithlittleregardtotheeconomiccostsoftheselaws.RiskassociatedwithatoxicchemicalisafunctionofHazardandExposure.The“endofthepipe”lawsattempttocontrolRiskbydealingwiththepreventionoftheExposuretotoxichazardouschemicals.OfcoursealltooftenpreventionofExposurehasfailed.Risk=f(Hazard,Exposure)Whiletheselawshaveplishedagreatdealintermsofimprovingourenvironmentbycontrollingourexposuretohazardoussubstances,westillhavealongwaytogo.ForexampleundertheToxicReleaseInventory(TRI),whichispartoftheEmergencyPlanningandCommunityRighttoKnowAct(EPCRA),companiesarerequiredtoreporttheuseand/orreleaseofcertainhazardoussubstances.In1997industriesreportedthat23.85billionpoundsofhazardoussubstancesweretreated,recycled,usedforenergyproduction,disposedoforreleasedtotheenvironment.Thisactcoversonly650ofthe75,000chemicalsinuseinUScommercetodayandonlycompaniesthatmanufactureorprocessmorethat25,000poundsorusemorethan10,000poundsofalistedsubstancearerequiredtoreport.

Companiestraditionallyhaveviewedenvironmentalregulationswithdisdainandasaneconomichardship.InordertocomplywithenvironmentalregulationsitisestimatedtocostU.S.industriesbetween$100to150billionperyear.SincetheEPAischargedwiththeimplementationandenforcementoftheselaws,therelationshipbetweenindustryandtheEPAhasbeenadversarialandoneofmistrust.

InthelastdecadeanewparadigmhasemergedattheEPA,usheredin,inpartbythePollutionPreventionActof1990.Thisisthefirstandonlyactthatisfocusedonpollutionpreventionratherthanthetypicaltreatmentandremediation.TheEPAisnowattemptingtopartnerwithindustrytofindmoreflexibleandcosteffectivewaysofnotonlymeetingexistingregulationsbutalsopreventingpollutionatthesource.In1991greenchemistrybecameaformalfocusofEPA(greenchemistryatEPA).GreenChemistryorenvironmentallybenignchemistryisthedesignofchemicalproductsandprocessesthatreduceoreliminatetheuseandgenerationofhazardoussubstances.ThusinsteadoflimitingRiskbycontrollingourexposuretohazardouschemicals,greenchemistryattemptstoreduceandpreferentiallyeliminatethehazardthusnegatingthenecessitytocontrolexposure.Thebottomlineis,ifwedon'tuseorproducehazardoussubstancesthentheRiskiszero,andwedon'tnothavetoworryaboutthetreatmentofhazardoussubstancesorlimitingourexposuretothem.THETWELVEPRINCIPLESOFGREENCHEMISTRY1AnastasandWarnerhavedevelopedtheTwelvePrinciplesofGreenChemistrytoaidoneinassessinghowgreenachemical,areactionoraprocessis.1.Itisbettertopreventwastethantotreatorcleanupwasteafteritisformed.2.Syntheticmethodsshouldbedesignedtomaximizetheincorporationofallmaterialsusedintheprocessintothefinalproduct.3.Whereverpracticable,syntheticmethodologiesshouldbedesignedtouseandgeneratesubstancesthatpossesslittleornotoxicitytohumanhealthandtheenvironment.4.Chemicalproductsshouldbedesignedtopreserveefficacyoffunctionwhilereducingtoxicity.5.Theuseofauxiliarysubstances(e.g.solvents,separationagents,etc.)shouldbemadeunnecessarywheneverpossibleand,innocuouswhenused.6.Energyrequirementsshouldberecognizedfortheirenvironmentalandeconomicimpactsandshouldbeminimized.Syntheticmethodsshouldbeconductedatambienttemperatureandpressure.7.Arawmaterialfeedstockshouldberenewableratherthandepletingwhenevertechnicallyandeconomicallypractical.8.Unnecessaryderivatization(blockinggroup,protection/deprotection,temporarymodificationofphysical/chemicalprocesses)shouldbeavoidedwheneverpossible.9.Catalyticreagents(asselectiveaspossible)aresuperiortostoichiometricreagents.10.Chemicalproductsshouldbedesignedsothatattheendoftheirfunctiontheydonotpersistintheenvironmentandbreakdownintoinnocuousdegradationproducts.11.Analyticalmethodologiesneedtobefurtherdevelopedtoallowforreal-timein-processmonitoringandcontrolpriortotheformationofhazardoussubstances.12.Substancesandtheformofasubstanceusedinachemicalprocessshouldchosensoastominimizethepotentialforchemicalaccidents,includingreleases,explosions,andfires.

REFERENCESAnastas,PaulT.,andWarner,JohnC.GreenChemistryTheoryandPractice,OxfordUniversityPress,NewYork,1998简化的绿色化学12原则PollutionPreventionAtomEconomyLessHazardousSynthesisDesignSaferChemicalsSaferSolvents&AuxiliariesEnergyEfficiencyRenewableFeedstocksReduceDerivativesCatalysisDesignforDegradationReal-TimeAnalysisAccidentPrevention

绿色化学原则第一节绿色化学定义

绿色化学Greenchemistry,alsocalledsustainablechemistry,isaphilosophyofchemicalresearchandengineeringthatencouragesthedesignofproductsandprocessesthatminimizetheuseandgenerationofhazardoussubstances.[1]1.UnitedStatesEnvironmentalProtectionAgency.2006-06-28..Retrieved2011-03-23.现实：先污染，再设法治理；发展不可持续绿色化学定义是指化学反应和过程以“原子经济性”为基本原则，即在获取新物质的化学反应中充分利用参与反应的每个原料原子，尽可能实现零排放。绿色化学不仅要求充分利用资源，而且要求不产生污染，并采用无毒、无害的溶剂、助剂和催化剂，生产有利于环境保护、社区安全和人身健康的环境友好产品“原子经济性”（Atomeconomy）*最早由美国斯坦福大学的B.M.Trost教授提出（“Theatomeconomy--asearchforsyntheticefficiency.”B.M.Trost,Science254（5037），1471-7，1991常用评价方式：转化率，选择性，产率；经济性指标；存在问题原子经济性考虑的是在化学反应中究竟有多少原料的原子进入到了产品之中，这一标准既要求尽可能地节约不可再生资源，又要求最大限度地减少废弃物排放。理想的原子经济反应是原料分子中的原子百分之百地转变成产物，不产生副产物或废物，实现废物的“零排放”（Zeroemission）化学反应的“原子经济性”则是指在化学反应中原料原子进入到产品的百分比*通常用原子利用率来衡量化学过程的原子经济性*在合成反应中，要减少废物排放的关键是提高目标产物的选择性和原子利用率

原子利用率的定义是目标产物的占反应物总量的百分比。即原子利用率＝（目标产物的量／各反应物的量之和）×100％

原子经济性相关问题原子经济反应是最大限度利用资源、最大限度减少污染的必要条件，但不是充分条件。这是因为某些化学反应中：

1反应平衡转化率很低，反应物与产物分离困难，反应物难于循环使用；

2生产目标产物的反应是原子经济的，但反应物还能同时发生其他平行反应，生产不需要的副产物综合使用转化率和原子利用率其他改进可再生与不可再生按照人的寿命为时间尺度来区分第二节绿色化学十二原则及其简化一、不让废物产生而不是让其生成后再处理

(防止废弃物)二、最有效地设计化学反应过程，最大限度地提高原子经济性

(最大化原子利用率)三、尽可能不使用、不产生对人类健康和环境有毒有害的物质

(尽可能设计无害化学合成)绿色化学十二原则及其简化四、尽可能有效地设计功率卓著而又无毒无害的化学品

(尽可能设计无害化学品)五、尽可能不使用辅助物质，如须使用也是无毒无害的

(使用安全的溶剂和反应条件)六、在考虑环境和经济效益的同时，尽可能使能耗最低

(提高能效)绿色化学十二原则及其简化七、技术和经济上可行时应以可再生资源为原料

(以可再生资源为原料)八、应尽可能避免衍生反应

(避免衍生反应)九、尽可能使用性能优异的催化剂

(使用催化剂)绿色化学十二原则及其简化十、应设计功能终结后可降解为无害物质的化学品

(设计可降解的化学品)十一、应发展实时分析方法，以监控和避免有毒有害物质的生成

(实时分析以防止污染)十二、尽可能选用安全的化学物质,最大程度地减少化学事故发生

(减少事故可能性)要求学习将上述原则用于分析实际问题第二节原子利用率原子利用率=100%目标产物的量各反应物的量之和利用原子利用率可以衡量在一个化学反应中,生产一定量目标产物到底会生成多少废物化学反应的原子利用率反应是否要求附加物质?反应本身决定会产生废弃物?化学反应的原子利用率重排反应消去反应取代反应加成反应氧化与还原反应原子利用率的计算事例第三节化学物质或化学工艺对环境与人口健康影响之评价方式1Howdoesachemistevaluateachemicalproductorprocessforitseffectonhumanhealthandtheenvironment?Startingmaterials/feedstocksReactiontypes

ReagentsSolventsandreactionconditionsChemicalproducts/targetmolecules

1.1Toxicitytohumanswhatisthehazardofthesubstanceitselftherecanbenoriskwithouthazardthequestionofhazardiscentraltoconductingagreenchemistryevaluation

ThenatureoftheeffectThreefactorsthatmustbeconsideredintheevaluationoftoxicitytohumansPotencyofthesubstanceincreatingatoxiceffectSeverityoftheend-pointReversibilityorirreversibilityAnexampleofacomparisonofpotency

chemicalsubstanceXchemicalsubstanceYgreenchemistryevaluationAnexampleofacomparisonofseverity

chemicalsubstanceXchemicalsubstanceYgreenchemistryevaluationAnexampleofacomparisonofreversibility

chemicalsubstanceXchemicalsubstanceYgreenchemistryevaluation1.2toxicitytowildlifeDifficultywiththeevaluationExtrapolations:structure-activitymodels

ProblemsOfaparticularsubstanceonaparticularspecies?DifferenteffectondifferentspeciesEvaluatingtheeffectsofchemistryEffectsonthelocalenvironmentGlobalenvironmentaleffectsSimplified12PrinciplesofGreenChemistryPreventWasteMaximizeAtomEconomyDesignLessHazardousChemicalSynthesesDesignSaferChemicalsandProductsUseSaferSolvents/ReactionConditionsIncreaseEnergyEfficiencyPrinciplesofGreenChemistryUseRenewableFeedstocksAvoidChemicalDerivativesUseCatalysts,NotStoichiometricReagentsDesignChemicalsandProductsthatDegradeAfterUseAnalyzeinRealTimetoPreventPollutionMinimizethePotentialforAccidentsSimplified12PrinciplesofGreenChemistry3Toolsofgreenchemistry绿色化学方法3.1alternativefeedstocks/startingmaterials

改变反应物Muchofthecharacterofareactiontypeorsyntheticpathwayisdeterminedbytheinitialselectionofthestartingmaterials.Theselectionofafeedstockhasamajoreffect:ontheefficacyofthesyntheticpathway;ontheenvironmentalandhealtheffectsoftheprocessEvaluatingfeedstocksOriginsRenewableordepletingHazardousorinnocuousDownstream3.1alternativefeedstocks/startingmaterialsTheselectionofafeedstockforthemanufactureofaproductdetermineswhathazardswillbefacedwhenworkersarehandlingthissubstance,suppliersareproducingit,andshippersaretransportingthesubstance.3.1alternativefeedstocks/startingmaterialsTheselectionofafeedstockisaveryconsequentialpartofthegreenchemistrydecision-makingprocess.3.2AlternativeReagents

改变试剂SelectedfeedstockTargetmoleculeWhentheobjectiveofeachsyntheticstepisclear,thereagentNeededinordertocarryoutthestepmayhaveyettobeselectedBestreagent3.2AlternativeReagentsCriteriaoftheselectionofreagent*Efficiency*Availability*Effect3.3AlternativeSolvents

改变溶剂Animportantareaofgreenchemistryinvestigationshascenteredaroundtheselectionofamediuminwhichtocarryoutasynthetictransformation.3.3AlternativeSolventsChemicalsynthesishasbeenprincipallybasedonthesolutionchemistry.Question:whatsolventshouldbeused?Question:

Shouldasolventbeusedatall?3.3AlternativeSolventsCommonoperation:

Manyofthesolventsusedaresomeofthevolatileorganiccompounds-----somesolventsarehazardoussubstances.3.3AlternativeSolventsInvestigationsarebeingconducted:*Todevelopasolventlesssystemforchemicalsynthesis*Touseanon-hazardoussolvent3.3AlternativeSolventsAlternativeSolvents:AqueoussystemsIonicliquidsImmobilizedDendrimersSupercriticalfluids3.4AlternativeProduct/TargetMolecule

改变产品AlternativeProduct:Chemicalswithaparticularfunctionoracertainperformance3.4AlternativeProduct/TargetMoleculeExample:t