鋁鎵合金制氫技術(shù)

摘要新能源技術(shù)的提出早已有之，其中太陽(yáng)能、地?zé)崮堋L(fēng)能等早就被人類(lèi)利用，但是，對(duì)這些新能源進(jìn)行大規(guī)模的開(kāi)發(fā)利用的技術(shù)還不成熟。氫能作為新能源的一種，也處于這樣的尷尬局面之中。阻礙氫能大規(guī)模開(kāi)發(fā)利用的關(guān)鍵障礙就是氫氣的快速制取和安全儲(chǔ)運(yùn)。以鋁為基礎(chǔ)制備出氫能的能源和轉(zhuǎn)換材料是解決這一問(wèn)題的新思路。但是鋁由于其性質(zhì)活潑，在空氣中會(huì)形成一層致密的氧化膜，使純鋁在水中幾乎不發(fā)生反應(yīng)。實(shí)現(xiàn)鋁水解制氫的關(guān)鍵就是要破壞這層氧化膜。本論文主要采用向Al中添加Ga、In、Sn、Li等活潑金屬制備出鋁合金這一技術(shù)來(lái)破壞這層氧化膜，提高Al的反應(yīng)活性，達(dá)到快速制氫的目的。通過(guò)對(duì)制備出的Al-Ga、Al-Ga-In-Sn、Al-Ga-Li合金在不同成分和溫度下的制氫檢測(cè)實(shí)驗(yàn)，我們發(fā)現(xiàn)用真空碳管電阻爐制備出的Al-Ga合金，即使在Ga含量高達(dá)30%時(shí)，最大的產(chǎn)氫效率也只有6%。而Al-Ga-In-Sn合金則能與水劇烈反應(yīng)，在綜合考慮生產(chǎn)能耗、成本和產(chǎn)氫效果等因素下，Al90-Ga7-In2-Sn1合金的制氫效果最令人滿意，可以達(dá)到100%的制氫量，更是可以在5分鐘左右就可以反應(yīng)結(jié)束。向Al-Ga系材料中添加活性金屬可以提高鋁水解的活性，是獲得較好制氫效果的有效方法。關(guān)鍵詞：氫能，水解制氫，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,safestorageanddeliveryofhydrogenhavebecomethemainobstacle,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-Lialloyatdifferentcomponentandtemperatures,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目錄TOC\o"1-3"\h\u26723摘要 ⑷綜合考慮生產(chǎn)能耗、成本和產(chǎn)氫效果等因素，發(fā)現(xiàn)Al90-Ga7-In2-Sn1合金配比最適宜工藝制氫技術(shù)。4.2鋁基合金制氫的前景與展望和傳統(tǒng)方法相比，采用鋁基合金作氫能的儲(chǔ)能和能源轉(zhuǎn)換材料有著無(wú)可比擬的優(yōu)勢(shì)，但仍需進(jìn)一步研究。尋找更廉價(jià)的合金添加劑，制備出更高效、快捷的鋁基合金有待后來(lái)人的繼續(xù)努力。參考文獻(xiàn)[1]宋永臣，寧亞?wèn)|，金東旭.氫能技術(shù).北京：科學(xué)出版社，2009.20~50[2]毛宗強(qiáng).氫能--21世紀(jì)的綠色能源.北京：化學(xué)工業(yè)出版社，2005.1~30[3]WangHZ,LeungDYC,LeungMKH,etal.Areviewonhydrogenproductionusingaluminumandaluminumalloys.RenewableandSustainableEnergyReviews,2009.13(4):845-853[4]歐訓(xùn)民.氫能制取和儲(chǔ)存技術(shù)研究發(fā)展綜述.能源研究與信息，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]吳濤，張會(huì)生.重整制氫技術(shù)及其研究進(jìn)展.能源技術(shù)，2006.27(4):161~164[9]Evangelostzimsa,StathisD.Peteves.Theimpactofcarbonsequestrationontheproductioncostofelectricityandhydrogenfromcoalandnatural-gastechnologiesinEuropeinthemediumterm[J].Energy,2005.30(14):2672~2689.[10]孫艷，蘇偉，周理.氫燃料.北京：化學(xué)工業(yè)出版社，2005.2~20[11]M.Momirlan,T.veziroslu.Recentdirectionsofworldhydrogenproduction[J].RenewableandSustainableEnergyReviews,1999,3:219~231[12]周潔，鄭穎平，謝吉虹.制氫技術(shù)研究進(jìn)展及在燃料電池中的應(yīng)用前景.化工時(shí)刊，2007,21(5):71~75[13]Abdel-aalHk,Kyu-SungSim.JournalofHydrogenEnergy1992,18:359~367[14]TzimasE,FiliouC,PetevesSD,VeyretJB.Hydrogenstorage:Stateoftheartandfutureperspective.EuropeanCommission,DirectorateGeneralJointResearchCentre,InstituteforEnergy,Petten,theNetherlands.Availableat<http://ie.jrc.ec.europa.eu/publications/scientific_publications/2003/P2003-181=EUR20995EN.pdf>;2003[15]尚福亮，楊海濤.氫能的制備、存儲(chǔ)與應(yīng)用.廣東化工，2006,33(2):7~9[16]尚福亮，楊海濤，韓海濤.多孔吸附儲(chǔ)氫材料研究進(jìn)展[J].化工時(shí)刊，2006，20(3)：58—61．[17]白朔，侯鵬翔，范月英等.材料研究學(xué)報(bào)，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].JAlloysComp,2005,389:299[22]OzolinsV,MajzoubEH,UdovicTJ.ElectronicstructureandrietveldrefinementparametersofTi-dopedsodiumalanates[J].JAlloysComp,2004,375:1[23]李伊.鋁的親氧性及酸堿兩性解析.四川文理學(xué)院學(xué)報(bào)，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],JournalofAlloysandCompounds,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,ASMInternatio