cuclschiffbase配合物在液相氧化羰化反应中的催化活性 寿命及腐蚀性分析word格式论文.docx

carbonatewasinvestigated.ThekineticequationisenergyEais53.4kJ/mol.?dpcodtco=14.76p1.03andtheactivationHeterogeneouscatalyticsystemshavemanyadvantagescomparedwithhomogeneoussystem inliquid-phasereactions,includingeasyseparationofcatalystsfromreactionmixturesandlowcorrosionrateofcatalysts.Preparationoforganic-inorganichybridmaterial(OIH)supportedCuClcatalystsbysol-geltechnologywasfurtherexplored.AnovelCuCl/Schiffbase/OIHsupportedcatalystwith7.1wt％Culoadingwassynthesizedbyγ-chloropropyltriethoxysilane(CPTES)asaspacer,5-amino-1,10-phenanthroline(NH2-Phen)asanorganicligandandtetraethylorthosilicate(TEOS)asasilicasourceof OIH.ThestructureofintermediatesandsupportedcatalystwerecharacterizedbyEA,FT-IRandNMR(1HNMR,29Si-MAS-NMR).TheeffectsofpreparationconditionsonthesynthesisofOIHwereinvestigated.Theoptimumpreparationconditionswere:theconcentrationofNH2-Phen10mg/mlDMF,molarratioofTEOSandCPTEStoNH2-Phen 6:1.1:1,reactiontemperature343K,reactiontime72h.Thecatalyticactivityof CuCl/Schiffbase/OIHintheoxidativecarbonylationofmethanolwasstudied.Theyieldof dimethylcarbonatewithCuCl/Schiffbase/OIHsupportedcatalystincreased25.0% comparedwithCuClcatalystsunderthereactionconditionsofCuClconcentration0.1 mol/L,reactiontemperature393K,reactionpressure2.4MPa,COandO2partialpressure ratioof2:1,reactiontime2h.Afterrecycling5times,thecatalyticactivityremainedwithaaverageCulossrateof2.2％.TheseresultsindicatedCuCl/Schiffbase/OIHcatalystwassuperiorinthethermalstabilityandCulossrate.ThestabilityofCuCl/Phencatalystinoxidativecarbonylationofmethanolwastestedinabatchreactorundertheconditionof393Kand2.0MPa.ThelifetimeofCuCl/Phencatalystwasmorethan330h.Thechemicalstructureofthecatalystusedbeforeandafter330hinthereactionwerecharacterizedwithEA,XPS,XRD,TG-DTA,AAS.ThereasonforthedeactivationofCuCl/PhencatalystwasthelossofchlorineandthedisproportionationofCu(I).ThedeactivationmechanismofCuCl/Phencatalystintheoxidativecarbonylationwasalsodiscussed.EffectsofSchiffbaseligandsonthecorrosiveperformanceofCuClcata