固体超强酸S2O催化制备生物柴油

3452007JOURNALOFBEIJINGUNIVERSITYOFCHEMICALTECHNOLOGYVol.34,No.52007S2O2-8/Fe2O32ZrO22La2O31122(11,100029;21,102500):S2O2-8/Fe2O32ZrO22La2O3,XRDFTIR,FeZrLa1014201075,,2%,121,220,10h,9013%550h,83%GC2MS:;;;:TQ51712:2007203208:,1963,,E2mail:[e-mail],,[1],,[2],,[3],[4],,[528],Furuta[9210]WO3/ZrO2SO2-4/ZrO2TiO2/ZrO2(Ti11%)Al2O3/ZrO2(Al216%),25020h,Al2O3/ZrO2(Al216%)95%Sreeprasanth[11](DMC),Kulkarni[12],,,,/,La2O3,La2O3/,3S2O2-8/Fe2O32ZrO22La2O3,,1111,;,;(Fe2Cl36H2O),,;(ZrOCl28H2O),,;(LaCl3nH2O),La2O345%,,;,,;,,GSHA21,,;pH/IonAnalyzer,Schwerzen2bach,Switzerland;D/max2500VB2+/PCX2,,Rigaku;Nico2letAvatar370MCTFTIRSpectrometer;6809N/59732,Agilent112(80g),800g,28%pH9,,Cl-(0105mol/LAgNO3),,11024h,100,0175mol/L12h,,,1104h,5004h,S2O2-8/Fe2O32Zr2O32La2O3113S2O2-8/Fe2O32ZrO22La2O3S2O2-8/Fe2O32ZrO22La2O3X2(XRD)FTIRXRD,CuK(=0115418nm),1090FTIR4cm-1,KBr500114200g,,,,,,,,,011MPa,230270,,,,:CHOOCR2CH2OOCR1CH2OOCR3+3CH3OHCHOHCH2OHCH2OH+RnCOOCH3n=1,2,31152HP5,230,110mL/min(),70eV,500,2002211S2O2-8/Fe2O32ZrO22La2O3SO2-4/Fe2O32ZrO22La2O3,11,500,,,1Table1EffectofcatalystcalcinationtemperatureonyieldofbiodieselT//%T//%40078.050085.560083.270077.62121S2O2-8/Fe2O32ZrO22La2O3XRD,1,,,,1S2O2-8/Fe2O32ZrO22La2O3XRDFig.1XRDpatternofS2O2-8/Fe2O32ZrO22La2O32La2O33S2O2-8/Fe2O32ZrO22La2O3FTIR,2,b122011351047cm-1,a,,S2O2-82,1200cm-1,[13]b1222cm-15455:S2O2-8/Fe2O32ZrO22La2O3ac,ac,La2O3,,La2O3,n(Fe)n(Zr)n(La)a10140115;b1014201075;c10142010382S2O2-8/Fe2O32ZrO22La2O3FTIRFig.2FTIRspectraofS2O2-8/Fe2O32ZrO22La2O3213La2O3S2O2-8/Fe2O32ZrO22La2O3,,2%,121,2208h,,2Fe2O3La2O3,La2O3;S2O2-8/Fe2O32ZrO2,;S2O2-8/Fe2O32ZrO2La2O3,,,FeZrLa1014201075,S2O2-8/Fe2O32ZrO22La2O3,2Table2Comparisonofcatalyticactivitiesofdifferentsolidsuperacidcatalystsn(Fe)n(Zr)n(La)/%S2O2-8/Fe2O310077.4S2O2-8/Fe2O32La2O3100.03878.6S2O2-8/Fe2O32La2O31007579.5S2O2-8/Fe2O32ZrO210142073.1S2O2-8/Fe2O32ZrO22La2O3()101420103878.2S2O2-8/Fe2O32ZrO22La2O3()101420107585.5S2O2-8/Fe2O32ZrO22La2O3()10.420.1581.7La2O3,,FTIR,La2O3,ZrO2214SO2-4/Fe2O32ZrO22La2O3(),,4,3,L9(34),,33Table3TableoforthogonaltestresultsABCD/%11(1)1(9:1)1(200)1(6)51.521(1)2(12:1)2(220)2(8)77.331(1)3(15:1)3(240)3(10)84.942(2)1(9:1)2(220)3(10)78.952(2)2(12:1)3(240)1(6)76.862(2)3(15:1)1(200)2(8)68.073(3)1(9:1)3(240)2(8)71.283(3)2(12:1)1(200)3(10)74.993(3)3(15:1)2(220)1(6)80.4K1213201194209K2223229237217K3226233233239k1=K1/371.27.264.869.6k2=K2/374.676.378.972.2k3=K3/375.577.877.679.6R4.3010.614.110.0Sj30.1197364161fj2222Sj/fj15.198.618280.8Fj=Sj/S()1.006.5312.15.35Aw,%;Bnn;CT,;Dt,h3,,RS,6452007,,,,,,,,220,,,2%,31,,,,,,,1212,,,,,,,,10h,210%12122010h,,9013%,215,,S2O2-8/Fe2O32ZrO22La2O3,,,35(50h),83%,2164,17,C16C20,3(1)S2O2-8/Fe2O32ZrO22La2O3,3S2O2-8/Fe2O32ZrO22La2O3Fig.3YieldofbiodiselwhenS2O2-8/Fe2O32ZrO22La2O3catalystisreusedinfivesuccessiverunsof10heach4Fig.4Gaschromatographofthebiodieselsamplen(Fe)n(Zr)n(La)1014201075,,(2)S2O2-8/Fe2O32ZrO22La2O32%12122010h9013%50h,83%(3)S2O2-8/Fe2O32ZrO22La2O3,3,,:[1]MAF,HANNAMA.Biodieselproduction:Areview[J].BioresourceTechnology,1999,70(1):1-15.[2]VICENTEG,MARTINEZM,ARACILJ.Integratedbiodieselproduction:Acomparisonofdifferenthomoge2neouscatalystssystems[J].BioresourceTechnology,2004,92(3):297-305.[3],,,.[J].,2006,26(2):124-126.[4]GRYGLEWICZS.Rapeseedoilmethylestersprepara27455:S2O2-8/Fe2O32ZrO22La2O3tionusingheterogeneouscatalysts[J].BioresourceTech2nology,1999,70:249-253.[5],,.S2O2-8/Zr2O32SiO22Sm2O3[J].,2006,27(2):8-11.[6],.[J].,2004,110(11):12-13.[7],,.SO2-4/Fe2O32MoO3[J].,2006,30(1):23-26.[8],.SO2-4/ZrO22TiO212[J].,2006,35(5):483-487.[9]FURUTAS,MATSUHASHIH,ARATAK.Biodieselfuelproductionwithsolidsuperacidcatalysisinfixedbedreactorunderatmosphericpressure[J].CatalysisCommu2nications,2004,5(12):721-723.[10]FURUTAS,MATSUHASHIH,ARATAK.Biodieselfuelproductionwithsolidamorphous2zirconiacatalysisinfixedbedreactor[J].Biomass&Bioenergy,2006,30(10):870-873.[11]SREEPRASANTHPS,SRIVASTAVAR,SRINIVASD,etal.Hydrophobic,solidacidcatalystsforproductionofbiofuelsandlubricants[J].AppliedCatalysisA:Gen2eral,2006,314(2):148-159.[12]KULKARNIMG,GOPINATHR,METHERLC,etal.Solidacidcatalyzedbiodieselproductionbysimultane2ousesterificationandtransesterification[J].GreenChemistry,2006,8(12):1056-1062.[13],,,.SO2-4/SnO22TiO2[J].,2006,18(5):510-514.SynthesisofbiodieselcatalyzedbyanS2O2-8/Fe2O32ZrO22La2O3solidsuperacidWANGZhiHua1SUNXiaoMan1SUNGuiFang2LIUGuoWen2(11StateKeyLaboratoryofChemicalResourceEngineering,BeijingUniversityofChemicalTechnology,Beijing100029;21BeijingFeiyanPetrochemicalEnvironmentalProtectionScienceandTechnologyDevelopmentCompanyLimited,Beijing102500,China)Abstract:BiodieselhasbeensynthesizedfromvegetableseedoilandmethanolusinganS2O2-8/Fe2O32ZrO22La2O3solidsuperacidcatalystinapressurekettle.TheS2O2-8/Fe2O32ZrO22La2O3solidsuperacidwaspreparedbyaprecipitation2impregnationmethodandwascharacterizedbyXRDandFTIR.Theeffectsofcatalystsyn2thesisandtransesterificationconditionsontheyieldofbiodieselwereinvestigated.Theresultsshowedthatthemaximumbiodieselyieldof9013%wasobtainedwhentheFe/Zr/Laatommolarrat