铝镓合金制氢技术

..摘要新能源技术的提出早已有之，其中太阳能、地热能、风能等早就被人类利用，但是，对这些新能源进展大规模的开发利用的技术还不成熟。氢能作为新能源的一种，也处于这样的为难局面之中。阻碍氢能大规模开发利用的关键障碍就是氢气的快速制取和平安储运。以铝为根底制备出氢能的能源和转换材料是解决这一问题的新思路。但是铝由于其性质活泼，在空气中会形成一层致密的氧化膜，使纯铝在水中几乎不发生反响。实现铝水解制氢的关键就是要破坏这层氧化膜。本论文主要采用向Al中添加Ga、In、Sn、Li等活泼金属制备出铝合金这一技术来破坏这层氧化膜，提高Al的反响活性，到达快速制氢的目的。通过对制备出的Al-Ga、Al-Ga-In-Sn、Al-Ga-Li合金在不同成分和温度下的制氢检测实验，我们发现用真空碳管电阻炉制备出的Al-Ga合金，即使在Ga含量高达30%时，最大的产氢效率也只有6%。而Al-Ga-In-Sn合金那么能与水剧烈反响，在综合考虑生产能耗、本钱和产氢效果等因素下，Al90-Ga7-In2-Sn1合金的制氢效果最令人满意，可以到达100%的制氢量，更是可以在5分钟左右就可以反响完毕。向Al-Ga系材料中添加活性金属可以提高铝水解的活性，是获得较好制氢效果的有效方法。关键词：氢能，水解制氢，Al-Ga合金、Al-Ga-In-Sn合金、Al-Ga-Li合金..AbstractWhilethenewenergytechnologieshavelongbeenproposed,andsolarenergy,geothermalenergy,windenergyandsoonhavebeenhumanusedforalongtime,thesenewenergydevelopmentandutilizationoflarge-scaletechnologyisnotmatureyet.Hydrogen,oneofthenewenergy,isalsoinsuchembarrassingsituation.Fastgeneration,safestorageanddeliveryofhydrogenhavebeethemainobstacle,whichrestricthydrogenenergydevelopmentandutilization.AnewideatosolvethisproblemistopreparedaAl-basedmaterialasamaterialforenergyreservesandconversion.Aluminumisthematerialofperfectchoiceforhydrolysishydrogenproduction.However,alayerofinertthinoxidefilmiseasilyformedonthealuminumsurfacebecauseofitslivelynature,whichpreventswaterfromcontactingwithAImetalsurface.ThekeyofhydrogengenerationbysplittingwaterwithAIistodestroytheinertthinoxidefilm.Todestroythislayeroftheoxidefilm,improvingthereactivityofAl,andachieverapidhydrogenproductionpurposes,inthethesis,weprepareanaluminumalloybyaddingactivemetalsinAlsuchasGa,In,Sn,Li,etc.BytheexperimentdetectingtheabilityofAl-Ga,Al-Ga-In-Sn,Al-Ga-Lialloyatdifferentponentandtemperatures,wefoundthattheAl-Gaalloy,preparedbythevacuumcarbontuberesistancefurnace,iscapableofhydrolyzinghydrogenproduction,butwithalittlehydrogenproduction,evenwhenGacontentis30%.However,Al-Ga-In-Snalloypreparedbythevacuumcarbontuberesistancefurnacehaveawater-stronglyhydrolyzablehydrogenproduction.Inconsideringtheproductionofenergy,costs,effectandotherfactors,theAl90-Ga7-In2-Sn1alloyhasthemostsatisfactoryresults,themaximumhydrogenyieldcanreach100%,andthereactiontimeonlyneed5minutes.AddingtotheactivemetalintheAl-Ga-basedmaterialcanincreasetheactivityofthehydrolysisofaluminum,whichisaneffectivemethodtoobtainabettereffectinhydrogengeneration.Keywords:hydrogen,hydrolysisofhydrogenproduction,Al-Gaalloy,Al-Ga-In-Snalloy,Al-Ga-Lialloy..目录TOC\o"1-3"\h\u26723摘要 ⑷综合考虑生产能耗、本钱和产氢效果等因素，发现Al90-Ga7-In2-Sn1合金配比最适宜工艺制氢技术。4.2铝基合金制氢的前景与展望和传统方法相比，采用铝基合金作氢能的储能和能源转换材料有着无可比较的优势，但仍需进一步研究。寻找更廉价的合金添加剂，制备出更高效、快捷的铝基合金有待后来人的继续努力。..参考文献[1]宋永臣，宁亚东，金东旭.氢能技术.：科学，2009.20~50[2]毛宗强.氢能--21世纪的绿色能源.：化学工业，2005.1~30[3]WangHZ,LeungDYC,LeungMKH,etal.Areviewonhydrogenproductionusingaluminumandaluminumalloys.RenewableandSustainableEnergyReviews,2009.13(4):845-853[4]欧训民.氢能制取和储存技术研究开展综述.能源研究与信息，2009.25〔1〕：1~4[5]SimPsonAP,LutzAE.ExergyanalysisofhydrogenProductionviasteammethanereforming.InternationalJoumalofHydrogenEnergy,2007.32(18):4811~4820[6]NiM,LeungMKH,LeungDYC,etal.Areviewandrecentdevelopmentsinphotocatalyticwater-splittingusingTiO2forhydrogenproduction.RenewableSustainableEnergyReviews,2007.11(3):401~425[7]RamB.GuPta.HydrogenFuel:Produetion,TransportandStorage.BocaRaton:CRCPress,Taylor&FrancisGroup,2009.3~32[8]吴涛，会生.重整制氢技术及其研究进展.能源技术，2006.27(4):161~164[9]Evangelostzimsa,StathisD.Peteves.Theimpactofcarbonsequestrationontheproductioncostofelectricityandhydrogenfromcoalandnatural-gastechnologiesinEuropeinthemediumterm[J].Energy,2005.30(14):2672~2689.[10]艳，伟，周理.氢燃料.：化学工业，2005.2~20[11]M.Momirlan,T.veziroslu.Recentdirectionsofworldhydrogenproduction[J].RenewableandSustainableEnergyReviews,1999,3:219~231[12]周洁，颖平，吉虹.制氢技术研究进展及在燃料电池中的应用前景.化工时刊，2007,21(5):71~75[13]Abdel-aalHk,Kyu-SungSim.JournalofHydrogenEnergy1992,18:359~367[14]TzimasE,FiliouC,PetevesSD,Veyret.Hydrogenstorage:Stateoftheartandfutureperspective.Europeanmission,DirectorateGeneralJointResearchCentre,InstituteforEnergy,Petten,theNetherlands.Availableat<ie.jrc.ec.europa.eu/publications/scientific_publications/2003/P2003-181=EUR20995EN.pdf>;2003[15]尚福亮，海涛.氢能的制备、存储与应用.化工，2006,33(2):7~9[16]尚福亮，海涛，海涛.多孔吸附储氢材料研究进展[J].化工时刊，2006，20(3)：58—61．[17]白朔，侯鹏翔，月英等.材料研究学报，2001,30:77[18]FanYY.LiaoB.LiuMHydrogenuptakeinvapor-growncarbonnanofibers1999[19]ToribioJ,KharinV.Effectofresidualstress-strainprofilesonhydrogen-inducedfractureofpretressingsteelwires[J].MaterSci,2006,42(2):263[20]MaximilianFichtner,JensEngel,OlafFuhr,etal.Nanocrystallinealuminiumhydridesforhydrogenstorage[J].MaterSciEng,2004,B108:42[21]DedrickDE,KanouffMP,ReplogleBC,etal.Thermalpropertiescharacterizationofsodiumalanates[J].JAlloysp,2005,389:299[22]OzolinsV,MajzoubEH,UdovicTJ.ElectronicstructureandrietveldrefinementparametersofTi-dopedsodiumalanates[J].JAlloysp,2004,375:1[23]伊.铝的亲氧性及酸碱两性解析.文理学院学报，2008,15:157~15938(1928):179~186[24]WangHZetal.Areviewonhydrogenproductionusingaluminumandaluminumalloys[J].RenewableandSustainableEnergyReview,2009,13:845~853[25]SHKOLNIKOVEetal.2Wpowersourcebasedonair-hydrogenpolymerelectrolytemembrancefuelcellsandwater-aluminumhydrogenmocro-generator[J].JPowerSources,2008,185:967~972[26]UEHARAK,TAKESHITAH,KOTAKAH.Hydrogengasgenerationinthewetcuttingofaluminumanditsalloys[J].JMaterialsProcessingTechnology,2002,127:174~177[27]KANAMESetal.Amethodofgeneratinghydrogengasbyaluminumdissolutioninwater[J].TechnologyReportsoftheOsakaUniverisity,1989[28]HirakiT,TakeuchiM,HisaM,etal.HydrogenProduetionfromwastealuminumatdifferenttemperatures,withLCA.Materialstransactions,2005,46(5):1052~1057[29]LawsonRT.Aluminumcorrosionstudies.I.Potential-PHtemperaturediagramsforaluminum.AustralianJournalofChemistry,1974,27(1):105~127[30]AleksandrovYA,TSyganovaEI,PisarevAL.ReactionofaluminumwithdiluteAqueousNaOHsolutions.RussianJournalofGeneralChemistry,2003,73(5):689~694[31]ChakladerACD.Hydrogengenerationfromwatersplitreaction.USPatent,6582676,2003-06-24[32]Parmuzina,O.Kravchenko.Activationofaluminiummetaltoevolvehydrogenfromwater[J].InternationalJournalofHydrogenEnergy,2008,33(12):3073~3076[33]Kravchenko,K.Semenenko,B.Bulychev,andK.Kalmykov.Activationofaluminummetalanditsreactionwithwater[J],JournalofAlloysandpounds,2005,397(1):58~62[34]M.Q.Fan,F.Xu,andL.X.Sun.StudiesonhydrogengenerationcharacteristicsofhydrolysisoftheballmillingAl-basedmaterialsinpurewater[J],InternationalJournalofHydrogenEnergy,2007,32(14):2809~2815[35]M.V.Trenikhin,A.V.Bubnov,A.I.Nizovskii,andV.K.Duplyakin,ChemicalinteractionoftheIn-GaeutecticwithAlandAl-basealloys[J],InorganicMaterials,2006,42(3):256~260[36]N.A.Plakhotnikova,V.G.Gopienko,A.A.Kolpachev,andG.A.Reznikova.Chemicalreactionofaluminumalloypowderswithwater[J],PowderMetallurgyandMetalCeramics,1988,27(8):605~608.[37]REBOULMC,GIMENEZH,RAMEAUIJ.AproposedactivationmechanismforAlanodes[J].Corrosion,1984,40:366~371[38]NagiraK,ShimizuT.MethodofProducingHydrogenandMaterialUsedTherefore.USPatent,4752463,1988-06-21[39]VillarsP,PrinceA,OkamotoH.Ga-In-SnPhaseDiagram.HandbookofTernaryAlloyPhaseDiagrams,ASMIntern