沸石催化剂上甲醇和叔丁醇合成甲基叔丁基醚

苟蔚勇(神华宁夏煤业集团煤炭化学工业公司)研究了HHYHZSM-5及HM四种沸石催化剂上由甲醇和叔丁醇合成甲基叔丁基醚的反应结果表明,H因具有三维交叉的大孔结构及高的结晶外比表面而表现出最高的醚化反应活性以AlF3为参照催化剂,进一步分析了催化剂表面酸性质和催化活性的关系,认为该反应虽为质子酸催化反应,但L酸的存在对反应物分子有溶剂化作用,催化剂的高反应活性与其表面B酸与L酸的合理调配有关沸石催化剂甲基叔丁基醚合成DOI:10.3969/j.issn.1007-3426.2010.05.005(MTBE)[1,2],[3],3000104t,,MTBE,,30~100,,MTBE,C4,,(TBA)MTBE[4,5],,HHYHZSM-5HM[6-10],,,A.A.Nikolopoulos[6]Collignon[7],,,,HHYHZSM-5HM,1实验部分1.1H(Si/Al19)HZSM-5(Si/Al19),500HY(Si/Al10)HM(Si/Al20)Na100(10%(w))HY1.2N2,BETNH3-TPD100mg,5002h120,30min,10/min387第39卷第5期CHEMICALENGINEERINGOFOIL&GAS,14mg,13mm5000.133Pa4h,1h150,1.3(i.d.6mm,l.200mm)0.5mL,2cm90~160,(4!1),GC1102,OV103,2结果与讨论2.1MTBE,(1)MTBE,[8],MTBE,,∀23/,,MTBE;,MTBE,(3),,MTBE,MTBE1h-1~2h-1,MTBE2.2HHYHZSM-5HM,H:HHYHZSM-5HM(4)(90),H97%,12098%,,MTBE(5)HHY90MTBE,HZSM-5HMMTBE100110,-MTBE,H,90MTBE388201048.8%2.3,,MTBE[11],,,,1,H,,,,(900)MTBEZSM-5,,HZSM-5,HM,HM,,HM12[12],,1Si/Alcc/g,m2/gSextSporeH190.1767.55.76.55.6152.42406.2412HY100.1897.446.17699.1312HZSM-5190.1395.65.35.55.181.29258.4610HM200.1847.06.55.72.633.28366.3512Sext:沸石的外表面积;Spore:沸石的孔道表面积YH,,2.4NH3-TPD2,:HMHZSM-5HY#H,,(tL),(tH),Y,,BL(2),2tL,ALtH,AHAB/ALH2100.4023450.5981.45HY2200.3173000.7562.47HZSM-52040.2684201.593.91HM2241.0875101.3585.2AlF3//3502.50AL:弱酸数量;AH:强酸数量;AB/AL:B酸与L酸酸量比值389第39卷第5期CHEMICALENGINEERINGOFOIL&GASHMB,HZSM-5YB,LLHHYHZSM-5HM,BLAB/ALHHYHZSM-5HM,,LL,LAlF3,6,MTBE,L2.5,,B,LL,L[14],L[13],,,∀MTBE,M.Matouq[15]-[(CH3)3COH]H+,:,,,,L,∀,,H+,L,3结论(1)HHYHZSM-5HM,H;(2)H,;(3)B,L,1KogelbauerA,OecalM,NikolopoulosAA,GoodwinJrJG,MarcelinG.J.Catal.1994,148:1572KaziAM,GoodwinJrJG,MarcelinG,OukaciR.Ind.Eng.Chem.Res.1995,34:7183,..,1993:1944YadavGDandKirthivadsanN.J.Chem.Soc.,Chem.Commun.,1995,2035MatouqM,TagawaTandGotoS.J.Chem.Eng.Jpn.,1993,26:2546NikolopoulosAA,KogelbauerA,GoodwinJrJG,MarcelinG.J.Catal.1996,158:767CollignonF,MarianM,MorenoS,RamyM,PouceletG.J.Catal.1997,166:538VilaM,CunillF,IzquierdoJ-F,GonzalezJ,HernandezA.Appl.Catal.A:General,1994,117:L999TakesonoT,FujiwaraY.USPatent4182913,198010CollignonF,MarianiM,MorenoS,RemyM,PonceletG.J.Catal.1997,166:5311P.Chu,G.H.Kuhl,Ind.Eng.Chem.Res.26(1987)365-36912,,..,1987:3513.,1999,4:314Corma.Chem.Rev.,1995,95:57415MatouqM,TagawaT,GotoS.J.Chem.Eng.Jpn.,1993,26:254-258:,1966:0951-6975023,:[e-mail]:2010-04-08;:2010-05-12;:3902010ABSTRACTSExperimentonPhaseEquilibriumofCarbonDioxideandMethaneMixedHydratesJiangChengming,YangTao,GuoKaihua(EngineeringCollegeofZhongshanUniversity,Guangzhou510006).CHEMICALENGINEERINGOFOIL&GAS,VOL.39,NO.5,pp371~373,2010(ISSN1007-3426,INCHINESE)Abstract:ReplacingofCH4fromhydratewithCO2asanintegratedwayofgreenhousegasstorageandexploitingnatrualgashydratesattractedmoreandmoreattention.ToreplaceCH4fromhydratewithCO2,thephaseequilibriumdataforCO2-CH4mixedhydratesareneeded.Inthispaper,thethree-phase(H-V-LW)lineandupperquadruple(H-LW-LC-V)points(Q2)phaseequilibriumpropertiesofthemixedhydratewithdifferentcompositionweremeasuredbyusingavisualexperimentalapparatusinrangeof273.7K~284.2K.Theresultsofincreasingequilibriumpressurewithmethanecompositionandtheupperquadruplephasecoexistrangewereprovided,andtheupperquadruplestatesofstartandendmeltingfortheCO2-CH4mixedhydrateswereidentified.ItisfoundthattheequilibriumtemperatureandpressurerangeofQ2four-phasecoexistenceareincreasedastheconcentrationofmethaneincreases.Keywords:CO2;CH4;replacement;mixedhydrates;phaseequilibrium;upperquadruplepointsBasicResearchonConversionofGreenhouseGasesbyThermalPlasmaTechniqueSunYanpeng,NieYong,WuAngshan,etal(CollegeofChemicalEngineeringandMaterialsScience,ZhejiangUniversityofTechnology,Hangzhou310014).CHEMICALENGINEERINGOFOIL&GAS,VOL.39,NO.5,pp374~377,2010(ISSN1007-3426,INCHINESE)Abstract:DevelopmentofplasmamethodsforchemicaltransformationofCO2andCH4intousefulcompoundsisofparamountimportancefromtwostandpointsofC1chemistryandso-calledgreenchemistry.Thermalplasmawhichhashightemperatureandhighenthalpywasusedtostudycarbondioxidedecomposition,methanedecompositionandcarbondioxidereformingofmethane.Theresultsshowthatthermalplasmaisaneffectivemeansforcarbondioxideandmethanetransform.ThemutualpromotionbetweencarbondioxideandmethaneinreformingprocessshouldbeconsideredinordertoobtainhighconversionofCH4andCO2,andhighchemicalenergyefficiency.Keywords:thermalplasma;methane;carbondioxide;decomposition;reforming;greenhousegasesGeneralSituationontheResearchofSynthesisandPropertyofSAPO-34MolecularSievesZhuWeiping,YueGuo,XingAihua,etal(ResearchInstituteofChinaShenhuaCoaltoLiquidandChemicalCo.,Beijing100011,China).CHEMICALENGINEERINGOFOIL&GAS,VOL.39,NO.5,pp378~383,2010(ISSN1007-3426,INCHINESE)Abstract:SAPO-34molecularsieveswhichhavethemediumacidicpropertiesanddistinctsmallporestructurecharacteristic,exhibitthebestselectivitytoC2-C3olefins,andhavetheminimumbyproductsofparaffinicandaromaticfortheconversionmethanoltolightolefins.SAPO-34∃scatalyticpropertiesandphysicochemicalcharacteristicsdependonitssynthetictechnique,syntheticconditionandtherawmaterialsselected.Thispaperdiscussedtheeffectfactorssuchasmaterials,synthetic