钴基催化剂F-T合成的产物分布及稳定性研究

206No.6Vol.20200612JournalofChemicalEngineeringofChineseUniversitiesDec.20061003-9015(2006)06-0920-05F-T,,,(,200237)γ-Al2O3Co-RuH2/CO552hC12~C18C19+H2/COC2~C4C5~C11C12~C18C19+H2/CO1.58~2.0453~513K1.0~2.5MPa500~1000h−1H2/CO2.0493K1.5MPa800h−1552hCOC5+80%83%C5~C18C16.94%C2~C46.20%C5~C1133.04%C12~C1831.55%C19+22.27%F-TO643.131TE646TQ546.4ATheHydrocarbonProductsDistributionsandStabilityofCobalt-BasedCatalystforFischer-TropschSynthesisLIChen,ZHANGHai-tao,YINGWei-yong,FANGDing-ye(SchoolofChemicalEngineering,EastChinaUniversityofScienceandTechnology,Shanghai200237,China)Abstract:Usingincipientimpregnationmethod,zirconiamodifiedγ-Al2-O3supportedCo-Rubimetalliccatalystwasprepared.Theeffectsoftheoperationconditions,suchasreactiontemperature,pressure,spacevelocityandH2/COmolarratioinfeed,onproductdistributionwereinvestigatedinafixed-bedreactor,andthe552hstabilitytestofthecatalystpreparedwasalsocarriedout.Theresultsshowthatthelowerreactiontemperature,thehigherpressureandthelowerspacevelocityfacilitatethegrowthofcarbonchains,andtheselectivityofC12~C18dieselfractionandC19+waxareenhanced.IncreasingtheH2/COratioinfeed,theselectivityofC5~C11,methaneandotherlowcarbonnumberhydrocarbonswillincrease,whilethatofC12~C18andC19+willdecrease.UndertheconditionsofH2/COratioinfeed1.58~2.0,reactiontemperature453~523K,pressure1.0~2.5MPaandspacevelocity500~1000h−1,thecatalystpreparedexhibitsexcellentreactivitytoproduceheavyhydrocarbons.AtthereactionconditionofH2/COratioinfeed2.0,493K,1.5MPaand800h−1,astablehydrocarbondistributionoftheproductcanbekeptduringalongrunof552hbyusingthecatalystprepared,duringwhichtheCOconversionisover80%andtheC5+selectivityisover83%.Itindicatesthatthecatalystusingtimeaffectstheproductdistributioninconspicuously,theproducthydrocarbonsmainlyconsistofparaffinandtheaverageselectivityofC1,C2~C4,C5~C11,C12~C18andC19+are6.94%,6.20%,33.04%,31.55%and22.27%,respectively.Keywords:Fischer-Tropschsynthesis;cobalt-basedcatalyst;zirconia;ruthenium;productdistribution;stability1Fischer-Tropsch(F-T)2005-09-222006-02-24(20050251006)(1968-)[e-mail]206F-T921F-TASF(Anderson-Schulz-Flory)F-T[1]γ-Al2O3SiO2TiO2RuCoC5+[2~5]Iglesia[4,5]Co/TiO2Co/SiO2Ru(Ru/Co()0.008)C5+84.5%91.1%RuBruce[6]Co/CeO2RuZrO2Feller[7]ZrO2Co/SiO2F-TZrCoCo-ZrCoC5+ZrCoC5+Ali[8]ZrO2Co/SiO2F-TCORohr[9]ZrO2Co-Ru-ZrO2/γ-Al2O3F-TH2/CO22.1γ-Al2O3100g⋅L−1NH4NO3353~363K2h393K773K6hZr(NO3)4·5H2OCo(NO3)2·6H2ORuCl312h393K10h673K6h20Co-0.5Ru-11.5ZrO2/100γ-Al2O32.2Φ12mm458K273K2mL(1.5g)0.175~0.246mmSiO2:SiO2=1:20.5MPaH22700h−10.5K⋅min−1693K6h423K0.5K⋅min−1453K72h2.3H2/CO()=2.0493K1.5MPa800h−12.412h8h30hH2COCH4CO2TDX-01TCDC1~C60.53mm×35mAT·Al2O3/SFIDDexsil-300FID9222006123F-TCHxH2CO[10]ASF(Anderson-Schulz-Flory)[1]2log(/)loglog(1)/nwnnααα=+−ppt/()rrrα=+nwnnα()rprtαC5+C1C2ASFC5~C93014α10~303.1H2/CO()=2.01.5MPa800h−120Co-0.5Ru-11.5ZrO2/100γ-Al2O3F-T11453K573KCOCH4453K3.09%573K23.77%C5+(F-T)453~513KC5+80%1Malessa[11]COCOα-COα-(C5~C11)C12~C18C19+453~493Kα1F-TTable1EffectofreactiontemperatureoncatalyticperformanceandhydrocarbondistributionforF-TsynthesisHydrocarbonproductsdistribution/%(wt)T/KCOmolarconv./%C1C2-C3C5-C11C12~C18C19~C2526C+002424()/()CCCC==∼∼/mol⋅mol−1α45339.613.0914.9824.0030.4918.488.950.960.8847376.456.597.6927.7827.5219.4810.930.730.9049384.886.255.5833.4032.1016.606.070.120.8651398.3910.057.2036.9230.4711.333.450.080.8253399.4312.3513.0339.7630.184.140.480.040.7155399.7517.9019.4540.1620.831.550.100.020.6557398.9223.7725.8538.1112.010.250.0040.010.54Reactionconditions:H2/COmolarratioinfeed=2.0,GHSV=800h−1,p=1.5MPaF-T[12]F-TCH23.222CO0.5MPa46.37%3.0MPa99.87%C2~C4C5~C11C19+F-TCOCo[13]206F-T9232F-TTable2EffectofreactionpressureoncatalyticperformanceandhydrocarbondistributionforF-TsynthesisHydrocarbonproductsdistribution/%(wt)P/MPaCOmolarconv./%1C24CC∼511CC∼1218CC∼1925CC∼26C+002424()/()CCCC==∼∼/mol⋅mol−1α0.546.3713.7415.3939.2123.756.251.361.160.781.068.458.867.9636.3631.7911.823.210.530.821.584.886.265.5933.4032.1116.606.070.120.862.094.136.705.0127.2832.3018.098.130.080.872.599.556.604.9426.3929.3719.2410.000.050.893.099.876.354.7527.6232.4518.178.170.030.87Reactionconditions:H2/COmolarratioinfeed=2.0,T=493K,GHSV=800h−13.3CO3493K1.5MPaCO2100h−1500h−1CO74.89%CH4C2~C4C5~C11C19+C12~C18500h−1800h−1CO3F-TTable3EffectofspacevelocityoncatalyticperformanceandhydrocarbondistributionforF-TsynthesisHydrocarbonproductsdistribution/%(wt)GHSV/h−1COmolarconv./%1C24CC∼511CC∼1218CC∼1925CC∼26C+002424()/()CCCC==∼∼/mol⋅mol−1α50099.976.825.1027.0830.5918.548.980.090.8880084.886.265.5933.4032.1116.606.070.120.86100069.7610.049.0134.2630.9011.493.490.270.82150057.1114.9913.5038.1727.964.650.650.710.73210025.0817.1413.4541.3526.871.150.041.380.60Reactionconditions:H2/COmolarratioinfeed=2.0,T=493K,p=1.5MPa4H2/COF-TTable4EffectofH2/COratioinfeedoncatalyticperformanceandhydrocarbondistributionforF-TsynthesisHydrocarbonproductsdistribution/%(wt)H2/COratioinfeedCOmolarconv./%1C24CC∼511CC∼1218CC∼1925CC∼26C+002424()/()CCCC==∼∼/mol⋅mol−1α0.9846.082.758.7020.3225.9121.3513.81.350.92