甲基丙烯酸甲酯合成及生产

:2004-05-05:(1968-),,,,,(150040):7,:C4,,,,:;;:TQ32517:A:1001-0017(2005)01-0057-04SynthesisandProductionofMethylMethacrylateLIANGXi-liang,WANGSu-yiandXUHong(HeilongjiangReseerehInstituteofPetrochemistry,Harbin,150040,China)Abstract:Sevenmethodsforproducingmethylmethacrylate(MMA)werereviewedinthispaper,amongwhichisobuteneoxidationroutewasbelievedtobeoneofthemostcompetitivetechnologies.Keywords:methylmethacrylate;isobutene;acetonecyanohydrin(MMA),(PMMA)[1][2](PMMA),,,[3,17]11865E1FrrankLandB1F1Duppa,1910OttoRohm(PMMA),MMA,1934,ICI(ACH)80(),BASF,MMA1989ACH(MGC),[4]111[4-8]ACH,,11111:CCH3OCH3+HCNNaOHCCH3OHCH3CN(ACH)2,1atm,11,NaOHCH3COCH3=0100581(mol),135minACH9215%111122-,,,CCH3OHCH3CN+H2SO4CuSO4130CCH3OSO3HCH3CN+H2O752005271CHEMISTRYANDADHESION018MPa,COSO3HCH3CNCH39311%CCH3OSO3HCH3CN+H2SO4CCH3OSO3HCH3C+NHHSO-4(ACH)+H2OCCH3OSO3HCH3CONH2H2SO4+H2SO411113(MMA):CCONH2H2SO4+CH3OHCH2CH3110,019MPa115hCCOCH3+NH4HSO4CH2CH3(99%)CCONH2H2SO4+H2OCH2CH3CCO2H+NH4HSO4CH2CH3CCO2H+CH3OHCH2CH3CCO2CH3+H2OCH2CH3(MMA)11114:,,,NH4HSO4ACH,,,,,SO2N2,,MMA112ACH[112]ACH(MGC)ACHMMA,ACH,ACH(HBD),(HBM),HBM(AI2O3/SiO2)MMA,,ACH,ACH,,,,,,,113[9],,40000,11311,;[14,15,16]:CCH3CH3CH3+O2CCH2CH3CHO+H2OCCH2CH3CHO+1/2O2CCH2CH3COOHCCO2H+CH3OHCH2CH3H2SO4CCOOCH3+H2OCH2CH3,,11Table1Conditionofcatalyticactivityandselectivity/mol%48/mol%540O2/C424/300400/s15C4/mol%95/mol%(+)8287,C495%,,1:,[12,13]4m2/g,014um285,Vol.27.No.1,20051Fig.1Conversionandselectivityasafunctionofvolumeconcentrationofisobutene2Table2Conditonofisobutene-aldehydeoxidation/mol%23/mol%1040O2/()24/270350/s25/mol%7090/mol%808511312,,,,,114,,,MMA11411[10](TBA)(TBA)SBB[C4:i-C4=(45%)n-C4=(37%)(16%)]i-C4=,,SBBi-C4=i-C4=9315%,n-C4=012%,0106%TBA,TBA:;;MAA();;,-11412[11415111]BASF,MMA,,4MMACOCH3OHMMA:CH2CH2+CO+H2O+CH3OHMMA+H2OMMA3:;;[18]CH2=CH2+H2+CO+1/2O2CH3-CH2-COOHCH3CH2COOH+HCHOCCH2CH3COOH+H2OCCOOH+CH2OHCH2CH3CCH2CH3COOCH3,11413[5]MMA,:,:H2OCO=111(mol),1molHF,Zr+(Rh+),,15%Co(CO)8,8615%,1412%Mo-PMo-P-V,100%,75%MMA,MMA;MMA,,[1]952005271CHEMISTRYANDADHESION2MMAFig.2ProcessofMMApreparationfrompropene11414[416],,MMAACH,,,,,,,2(MMA),MMA,ACH[4],:C4,,,,ACH,,,:[1].MMA[J].,1996,4(7):31-34.[2].2-[J].,1996,(2):23-27.[3].PMMA[J].,2001,(25):10.[4].[J].,1993,(3):5-8.[5].[J].,1994,(10):687-693.[6].[M].(),:.1989:498-512.[7]SHIRAISHIT,KISHIWADAS.Catalyticprocessforthepreparationofmethacrolein[P].US3928462,1975-12-23.[8]SHIRAISHIT,KISHIWADAS.Processforproductionofarylicacid[P].US4092354,1978-05-30.[9].[J].,1990,(3):35-41.[10].C4[J].,1987,16(2):123-126.[11].[J].,1987,(3):1-4.[12]TAKAHASHIYOSHIYUKI,KITADARITSUO.Oxidationcatalystandprocessforpreparationthereof[P],EP0043100,1982-01-06.[13]PEDERSENSVENDERIK,PAPARIZOSCHRISTOS.Processfortheproductionofmethacrylicacidfromisobutyraldehydeemployingacat2alyst[P].EP0060066,1982-09-15.[14]MATSUMOTOMUTSUMI,SUDOATSUSHI.Aprocessforproducingmethacroleinandmethacrylicacid[P].EP0005769,1979-12-12.[15]ONODATAKERU,OTAKEMASAYUKI,ManufactureofMethacrylicacid[P].US4061673,1977-12-06.[16]NIPPONKAYAKUKk.Processforproducingmethacroleinandmethacrylicacid[P].GB2045635,1980-11-05.[17]LIJIE,ZHAOJIANQING,SHENJIARUI.Microwave-initiatedBulkPolymerizationofMMA;ChinaSyntheticRubberIndustry[J].1997,20(1):53-55.[18]SPIVEYJAMESJ,GOGATEMAKAPANDR,ZOLLERJOSEPHR,etal.NovelcatalystsfortheenvironmentallyfriendlysysthsisofmethylMethacrylate[J].Jnd.Eng.chem.Res.1997,36(11):4600-4608.05-020[,(A),2080,3;(B):--CaCO3SumitexResinM3();(JISA5403);20100%450N/cm2]YamamotoYusuke()1JP(K)2004161910A2,2004-06-10105-021[,,,;;,,50m]FukuokaMasateru,HataiMunehiro,HayashiSatoshi,etal()1JP(K)2004186281A2,2004-07-02)06,Vol.27.No.1,2005