管壳型固定床费托合成反应器的数学模拟

Vol.36No.5201010()JournalofEastChinaUniversityofScienceandTechnology(NaturalScienceEdition):20100119:(863)(2006AA05A111):(1979),,,,::,Email:[e-mail]:10063080(2010)05060307鲁丰乐,张海涛,应卫勇,房鼎业(华东理工大学化学工程联合国家重点实验室,大型工业反应器工程教育部工程研究中心,上海200237):根据集总思想,利用蛋壳型钴基催化剂动力学方程,建立了管壳型固定床费托合成反应器的一维拟均相数学模型对合成油试验装置进行工况模拟,得到的管壳型固定床反应器催化床层中的温度分布CO转化率出口组成C+5的质量分数和时空产率的模型计算值与试验值吻合良好讨论了反应器进口温度操作压力气体体积空速和沸腾水温度对反应结果的影响,结果表明:提高反应器进口温度沸腾水温度操作压力使催化床层温度升高,CO转化率升高,C+5的质量分数降低和C+5的时空收率增大;增大气体体积空速使催化床层温度降低,CO转化率降低,C+5的质量分数升高和C+5的时空收率增大:费托合成;管壳型固定床反应器;数学模型;工况模拟:TQ018:AMathematicSimulationofaTubeShellTypeFixedBedReactorforFischerTropschSynthesisLUFengle,ZHANGHaitao,YINGWeiyong,FANGDingye(StateKeyLaboratoryofChemicalEngineering,EngineeringResearchCenterofLargeScaleReactorEngineeringandTechnologyoftheMinistryofEducation,EastChinaUniversityofScienceandTechnology,Shanghai200237,China)Abstract:BasedonthelumpingtheoryandthekineticsmodeloftheeggshellCobaltbasedcatalyst,theonedimensionalpseudohomogeneousmodelofthetubeshelltypefixedbedreactorforFischerTropschsynthesiswasdeveloped.Thesimulatedoperatingparametersincludingtheprofilesofthecatlystbedtemperature,COconversion,outletcomposition,massfractionofC+5andthespacetimeyieldwereconsistentwellwiththepracticaldata.Effectsofthereactorinlettemperature,spacevelocity,operatingpressureandtheboilingwatertemperatureonthereactionresultswerestudied.Itdemonstratedthattheincreaseoftheinlettemperature,operatingpressureandtheboilingwatertemperatureenhancedthecatalystbedtemperature,COconversionandthespacetimeyieldofC+5whiledecreasedthemassfractionofC+5.TheincreaseofspacevelocityresultedinthedecreaseofthecatalystbedtemperatureandCOconversionaswellastheincreaseofthemassfractionandspacetimeyieldofC+5.Keywords:FischerTropschsynthesis;tubeshelltypefixedbedreactor;mathematicmodel;modesimulation603(GTL)(CTL),,[1],AtwoodBennett[2],Bub[3],Jess[4],,Maretto[5],,Wang[6],,Cai[7],,[8][9],[10],,,1,,,,2.0~5.0MPa,210~2502,,[11],CO2,CH4H2O,:CO+3H2=CH4+H2O(1)3CO+7H2=C3H8+3H2O(2)10CO+21H2=C10H22+10H2O(3)22CO+45H2=C22H46+22H2O(4),,CO,(CH4)(C3H8)(C10H22)(C22H46),,2.1[12],25,1,CO:rco=1.0628107exp(-76.01103RT)pH2pCO1+0.3899exp(-1.789103RT)p1/2H2+0.9853exp(-16.13103RT)pCO+0.1715exp(-1.240103RT)pCOp1/2H22(5)=1.6438p0.06492(T273)-1.2317(GHSV1000)-0.00819R-0.055651R0.01602(6),10%,CO,COrCO,CH4C3H8C10H22C22H46:604()36rCH4=wCH416wCH416+wC3H8443+wC10H2214210+wC22H4631022rCO(7)rC3H8=wC3H844wCH416+wC3H8443+wC10H2214210+wC22H4631022rCO(8)rC10H22=wC10H22142wCH416+wC3H8443+wC10H2214210+wC22H4631022rCO(9)rC22H46=wC22H46310wCH416+wC3H8443+wC10H2214210+wC22H4631022rCO(10)w1Table1DataofthekineticsexperimentsontheeggshelltypeCobasedcatalystNo.T/Kp/MPaGHSV/h-1R1qm/(g!s-1)CH4C3H8C10H22C22H46xCO14631.10868.21.844.407.779.3728.020.4350.84224781.101615.21.847.8022.0520.1844.830.4620.84334933.303613.81.8433.0064.1759.35154.470.6960.87144833.803289.81.8420.0063.4239.5097.400.5640.73954832.951617.91.847.5525.0226.6786.770.7760.74264932.852710.81.8419.0393.7520.4779.400.6880.90374832.052717.71.8416.1047.8712.7358.720.4100.79084782.052235.91.8412.1838.0014.4361.380.4780.78294633.603206.72.6111.6544.8816.0540.950.3370.828104783.601789.22.6116.1045.9716.9567.800.8530.804114782.902629.22.6117.4263.2216.3358.730.5820.796124632.901270.52.619.7228.2210.6235.070.6810.840134832.102062.22.6128.1250.7013.4847.780.6930.852144932.10949.52.6115.8339.827.2026.280.9550.738154931.103108.92.6123.5272.283.2315.570.3690.744164831.101597.52.6115.7346.223.559.400.4760.857174683.802119.52.3811.8813.5819.2083.140.5910.778184783.501630.22.3811.3646.5920.5065.380.8380.796194782.602408.72.3827.3319.3129.5369.400.5790.786204632.601275.62.387.7416.6411.7133.850.5220.775214831.802736.32.3832.6851.3721.6964.280.6170.798224833.501918.21.588.7423.3531.1465.450.5200.785234932.602167.81.5815.1433.1022.0576.410.5140.793244631.801600.81.5813.8215.873.6213.780.2350.844254831.802631.31.5813.5231.0519.1555.750.3460.8266055,:2.2ldl,,N:-dNCOdl=CORAbrCO(11)dNCH4dl=CORAbrCH4(12)dNC3H8dl=CORAbrC3H8(13)dNC10H22dl=CORAbrC10H22(14)dNC22H46dl=CORAbrC22H46(15):dtbdl=[(-!HR)rCO]CORbA-Kbwmt∀da(tb-tw)NCpb(16):-dpdl=fMfu20ds(1-##)(17)RungeKutta,:l=0,NCO=NCO,in,NCH4=NCH4,in,NC3H8=NC3H8,in,NC10H22=NC10H22,in,NC22H44=NC22H44,in,tb=tb,in,p=pin33.1:5175Nm3/h;yH2=0.478,yCO=0.229,yN2=0.059,yCH4=0.203,yC3H8=0.024,yC10H22=0.002,yH2O=0.005;tin=209.50;pin=3.79MPa;tw=201.4,ds=2.5mm,#0.4,COC+5C+525%,COC+5(STY)2Table2Comparisonofcalculatedvaluewithexperimentalvalueqmofthereactoroutlet/(kg!h-1)COH2CH4C3H8C10H22C22H46xCOw(C+5)/(%)STY(C+5)/(g!L-1!h-1)Experimentalvalue1005.76150.00780.16251.77114.14140.800.32082.56112.46Calculatedvalue989.63149.18785.76254.85119.42147.250.33180.53119.36,3,1,thot=215.16,tout=214.25,,,1.06%3.23.2.1反应器进口温度的影响205.50213.50,42,COxCO,,,C+5,C+52,3.2.2操作压力的影响p3.00MPa4.50MPa,5,xCO,,,,,C+5[13],,3,C+5101.73g/(L!h)135.37g/(L!h),,606()363Table3Axialprofilesofthereactantsandproductsincatalystbedofthetubeshelltypefixedbedreactorl/mNi/(kmol!h-1)H2COCH4C3H8C10H22C22H460110.43052.85446.9895.4480.44900.54107.85051.6144