天然气现场制氢新工艺的研究ppt-中国气体分离设备商务网

天然气现场制氢新工艺的研究学生汪丛伟导师王树东研究员2019年10月4日内容纲要•天然气现场制氢的意义及优势•天然气现场制氢的新工艺•总结与展望研究背景分散站制氢规模集中制氢ON-BOARDFUELPROCESSINGGO/NO-GODECISIONDOEDECISIONTEAMCOMMITTEEREPORT,August2004车载制氢设备投资大氢气储运、分配困难启动时间(10min)启动能量(7MJ/50kw）天然气现场制氢优势原燃料比较充足（天然气水合物）天然气清洁,能量密度大供给方便(完善的输运管道)制氢成本低，是目前最廉价的制氢方式之一天然气水蒸汽转化CO高温变换CO低温变换CO甲烷化CO2脱除H2分离天然气水蒸汽重整制氢（大规模）US$3.66~5/kgH2天然气水蒸汽重整制氢(小规模)US$12/kgH2目前天然气水蒸汽规模制氢与现场制氢的成本比较高成本高成本现有天然气水蒸汽重整工艺用于现场制氢是极其昂贵的，开发现场制氢新工艺与新技术已成为当务之急！！！重点：1.产氢,纯化一体化,技术集成,缩短工艺流程;2.装置投资小,生产成本低;天然气水蒸汽重整CH4+H2O=CO+3H2，△H298K=206kJ/molCH4+2H2O=CO2+3H2，△H298K=165kJ/molCH4+2O2=CO2+2H2O，△H298K=-804kJ/mol天然气自热重整CH4+0.5O2=CO+2H2，△H298K=-36kJ/molCH4+H2O=CO+3H2，△H298K=206kJ/molCH4+2H2O=CO2+3H2，△H298K=165kJ/mol天然气现场制氢的技术路线产氢纯度高，分离相对易，但能效相对不高能量效率高，但分离能耗相对较大天然气现场制氢新工艺集成换热式(反应耦合）循环利用热流：壁式反应器，两段式反应器，多层套筒式反应器降低传热传质阻力：板式反应器，微通道反应器净化纯化式制备高纯度H2：膜反应器降低CO排放：双层催化剂无CO反应器壁式反应器TheophilosIoannides,XenophonE.Verykios,Developmentofanovelheat-integratedwallreactorforthepartialoxidationofmethanetosynthesisgas,CatalysisToday46(1998)71-81UniversityofPatras,Greece•反应器由陶瓷管组成，陶瓷管内表面沉积燃烧催化剂层，外表面沉积重整催化剂层•原料从里面的管子进入后被外层的出口气体预热，在反应区发生反应，放出的热量通过管壁传到外层，在那里发生吸热的重整反应。循环利用热流Ⅰ两段式重整反应器FraunhoferInstitute，Germany•甲烷和水作为冷料通入换热器中与燃烧尾气换热，被加热至450－600℃•进入一次重整器中进行重整反应（热量来自燃烧尾气的对流换热）•进入二次重整，热量来自陶瓷燃烧器的直接热辐射Vogel,B.,G.Schaumberg,A.Schuler,1998,.HydrogenGenerationTechnologiesforPEMFuelCells,.1998FuelCellSeminarAbstracts,November16-19,1998,PalmSprings,CA,pp.364-367.循环利用热流Ⅱ多层套筒式重整反应器Anovelsteamreformingreactorforfuelcelldistributedpowergeneration,CaliforniaEnergyCommission,May2000存在问题：传热阻力较大系统较庞大循环利用热流Ⅲ板式反应器•催化剂层＆板的厚度很薄,大大提高了反应器的结构紧凑性,降低了传热与传质阻力•板式反应器的效率比传统水蒸汽重整器高一个数量级，而体积和催化剂重量低2个数量级•板式反应器的换热效率提高。壁面和气相截面温度分布更均匀M.Zanir,A.Gavriilidis,Catalyticcombustionassistedmethanesteamreforminginacatalyticplatereactor,ChemicalEngineeringScience58(2003)3947–3960存在问题：催化剂涂覆困难降低传热传质阻力Ⅰ微通道反应器PictureofaVelocy’smanufacturingscale-upmicrochannelreactor(PacificNorthwestNationalLaboratory)•微通道可把传热传质速率提高1～2个数量级•由于过程强化降低了操作成本•均匀布氧，先部分氧化后完全燃烧为原料预热和重整供热A.Y.Tonkovicha,S.Perrya,W.A.Rogers,Microchannelprocesstechnologyforcompactmethanesteamreforming,ChemicalEngineeringScience59(2004)4819–4824存在问题：反应器加工成本高通道阻力降大降低传热传质阻力Ⅱ集成化膜反应器Yu-MingLin,Min-HonRei,ProcessdevelopmentforgeneratinghighpurityhydrogenbyusingsupportedpalladiummembranereactorassteamReformer,InternationalJournalofHydrogenEnergy25(2000)211±219CH4存在问题：钯膜具有氢脆现象，如何增强稳定性？净化纯化式Ⅰ两层催化剂无CO水蒸气制氢反应器VladimirGalvitaa,KaiSundmacher,Hydrogenproductionfrommethanebysteamreforminginaperiodicallyoperatedtwo-layercatalyticreactor,AppliedCatalysisA:General289(2005)121–127MaxPlanckInstituteforDynamicsofComplexTechnicalSystems,Magdeburg,GermanyStep1:ReductionPt-CeO2-ZrO2Fe3O4-CeO2-ZrO2CH4CO+H2H2O+CO2H2H2OH2O+H2Pt-Ce2O3-ZrO2Fe-Ce2O3-ZrO2Step2:Re-oxidation存在问题：催化剂表面沉积碳，实际应用?净化纯化式Ⅱ总结与展望将重整制氢,供热,纯化一体化,实现过程强化、系统高度集成是降低制氢成本的出路集成换热式(热量耦合）净化纯化式（降低成本）现场制氢新工艺要真正走向实际应用，还需切实解决自身的关键技术，扬长避短谢谢大家!参考文献1.ON-BOARDFUELPROCESSINGGO/NO-GODECISION,DOEDECISIONTEAMCOMMITTEEREPORT,August20042.TheophilosI,XenophonE.Verykios,Developmentofanovelheat-integratedwallreactorforthepartialoxidationofmethanetosynthesisgas,CatalysisToday46(1998)71-813.M.Zanir,A.Gavriilidis,Catalyticcombustionassistedmethanesteamreforminginacatalyticplatereactor,ChemicalEngineeringScience58(2003)3947–39604.Vogel,B.,G.Schaumberg,A.Schuler,andA.Henizel,1998,.HydrogenGenerationTechnologiesforPEMFuelCells,.1998FuelCellSeminarAbstracts,November16-19,1998,PalmSprings,CA,pp.364-367.5.A.Y.Tonkovicha,S.Perrya,W.A.Rogersa,Microchannelprocesstechnologyforcompactmethanesteamreforming,ChemicalEngineeringScience59(2004)4819–48246.VladimirG,KaiS,Hydrogenproductionfrommethanebysteamreforminginaperiodicallyoperatedtwo-layercatalyticreactor,AppliedCatalysisA:General289(2005)121–1277.Anovelsteamreformingreactorforfuelcelldistributedpowergeneration,CaliforniaEnergyCommission,May2000参考文献(续)8.YuML,MinHR,ProcessdevelopmentforgeneratinghighpurityhydrogenbyusingsupportedpalladiummembranereactorassteamReformer,InternationalJournalofHydrogenEnergy25(2000)211-2199.SLin,YChen,CLee,Dynamicmodelingandcontrolstructuredesignofanexperimentalfuelprocessor,InternationalJournalofHydrogenEnergy(inpress)10.SheldonLee,,DanielV.A,ShabbirA,Hydrogenfromnaturalgas:partI—autothermalreforminginanintegratedfuelprocessor,InternationalJournalofHydrogenEnergy30(2005)829–84211.A.Siddle,K.D.Pointon,R.W.JuddandS.L.Jones,FUELPROCESSINGFORFUELCELLS–ASTATUSREVIEWANDASSESSMENTOFPROSPECTS现场制氢的市场需求分析加氢站分散电站其他工业半导体，电子行业高纯氢军事电源：战地指挥、潜水艇应急电源：要害部门如银行、医院、证券交易所