环己酮生产工艺及研究进展

谢文莲田爱国(,414007)介绍了国内外环己酮生产工艺技术改进及新技术开发动态,指出通过新的氧化催化体系,可提高环己烷转化率与酮醇选择性,减少环境污染,实现清洁化生产环己酮,工艺技术,发展动态,催化氧化TQ224A1000-6613(2003)04-0420-041环己酮的传统生产工艺,:,90%[1,2]11,,,3~5,140~170,01MPa,95%,,,1974Nypro,,,,12,,,:C6H12+O2C6H11OOHC6H11OOHC6H10O+H2OC6H11OOHC6H11OH+12O2,113()//MPa/min/%KA/%BASF145Co3477Dupont160~180101~122Co20~254~677~80Inventa160~165101~12230~50Co4189~91Stamcarbon150~160081~091Co63~576~78VikerZimmer174213~25310Co34~575~83PetrocarbonDev.157~162096Co10~1885~89Halcon165~170101H3BO33~4387IFP165122H3BO3412~1385~90Stamicarbon165091120H3BO38~1582~88DuPont160~165101Co18316506~081Co+CrRhonePoulenc170~1801824415015~30VRuMo84Stamicarbon160~1801253580~83850415~602~32003-01-20;2003-02-17(1965),,,0730-8501434!420!2003224CHEMICALINDUSTRYANDENGINEERINGPROGRESS121,Co2++ROOHCo3++RO!+OH-Co3++ROOHCo2++ROO!+H+(KA)65∀35122,2030,,,Halcon/SDIFP(InstituteFrancaisPetrole)StamicarbonHalcon19708,700~750ktKA,,,123Rhone-Ponlene,,,,,10%~15%,,3KA,KA,KA2现有工艺技术的改进,,,,21,,,,,,,,,(),,,Co2+,,4~6HEDP,19894,22DSM,,,,,,,,,,,,;,,23,,,,,(Na+)5g!g-1,,3新工艺技术的开发!421!4:,,31[3],ZSM-5,50%~60%,80%,,22/100~180100~130/MPa3~74/%50~6010/%8099/%99992080,1990860kt/a,1997100kt/a66,199828#104t,;,,32[6],MAPO-36(065nm#075nm)[7]MAPO-VF(12nm)[8]MAPO-18(038nm)[11]MAPO-5(073nm)[12]MAPO-31[13]TS-1Fe-(CH3O)3Si(CH2)NH2-MCM-41NaGe-X(TBA)4HPW11Fe(H2O)O392H2OYFe3+-picolinate[10],TS-1,80,TS-1,TS-1:(1),(20~100);(2),;(3),Spinace[7]ClericiTS-1,:TS-1,,TS-1,TS-12,6--4-,,TS-1,CH33,(hemocyanin),,,,,1979,Groves[9]--,P-450,[4,5],,4g!g-114508MPa,7%,85%,:,,,,,,,,,!422!20032234BASFMo,130~200,05~25MPa,039%,578%,203%,935%,091%UBEN-,160,601%,228%,39%(Daicel)N-(NHPI),N-943∀160∀60,160,40MPa2h,11%,49%,40%,,11%,()95%[14];Co(20nm)10~15h,41%,80%,/02[15];Fe2O3(8~10nm),165%,90%,/04[16]4结语,,,,,,,1.[J].,1992,1:49~532,,.[J].,1999,1:29~313.[J].,1992,6:49~534.[J].,1999,85.[J].,1999,36,,.[J].,1999,30(8):1~47SpinaceEV,PastoreHO,SchuchardtU.[J].J.Catal.,1995,157:6318SchuchardtU,etal.[J].Applied.Catalysis.A,General,2001,211:1~179GovesJT,NemoTE.[J].J.Am.Chem.Soc.,1979,101:103210ParvulescuVI,DumitriuD,PonceletG.[J].J.Mol.Catal.A,1999,140:9111LunaFJUkawaSE,WallauM,SchuchardtU.[J].J.Mol.Catal.A,1997,117:40512[J].CatalysisLetters,2001,75(3-4):159~16213[J].AccountofChemicalResearch,2001,34:19114[J].J.Am.Chem.Soc.,1992,114:791315[J].AngewandteChemie-internationalEditioninEnglish,1999,38(23):352116[J].PureandAppliedChemistry,2001,73(1):85ProcessTechnologyandAdvancementofCyclohexanoneProductionXieWenlian,TianAiguo(TechnologyDevelopmentDivisionofBalingCompany,SINOPEC,Yueyang414007)AbstractTheexistingprocessanddevelopmentofcyclohexanoneproductionbothinhomeandoverseasareintroduced.Itshowstheimprovementinconversionrateofcyclohexaneandselectivityofcyclohexanoneorcyclohexanol,reductionpollutionandrealizationincleanproductionwhileusingthenewcatalysissystemofoxidation.Keywordscyclohexanone,progresstechnology,developingtrends,catalyzingoxidation!423!4: