费托合成产物分布的实验研究

6：2016-03-17；：(863)(2011AA05A205)；：（1991-），，，[e-mail]；*：，，010-81292208，[e-mail],[e-mail]。、[1,2]。，，、，C70～C120()。[3]，：(1)；(2)，；(3)。、、，、，[4-8]。：(1)；(2)；(3)，；(4)，，。，。，、，Aspenplus。11.11。，[9-12]：(1)，；(2)（），，，；(3)，1,3，3*，2,3，2,3，2,3，2,3，1*（1.，102617；2.,030001；3.，101407）：，（C1～C30），（C10～C70），。，、，。，Aspenplus。，；C10～C20，。：；；；：TQ529.2：A：1001-9219(2016)06-15-06：15ChaoXing201641·C1（300℃），，Agilent；(4)，（），。CO(99.99%)H2（99.95%）（、、、），10%（Ar，99.999%）。Brooks5850E。，（80～100，0.5g）SiC（10/1）、。1.，、、、；2.；3.；4.；5.；6.1.2，COH2、Ar、N2、CO2、C1～C30（）C1～C20。，（GC1GC2）。GC1：TCD1CO，H2，CO2，ArN2；FID1-1C5+C3+；FID1-2C1C2。GC2：TCD2Ar、CON2；FID2C1～C4。C10～C70（），24h36h，。，C14。：(1)0.02%C14，CS2；(2)0.1g，20g，、，；(3)，[13]。1.3COCOCO：（1）（、）CO：（2）（i=1,2,3，，；j=1,2,3…nC）：(j=1,2,3…nC）（3）：（j≥2）（4）（%），：（5）22.12.1.1（C9），（）。1Fig.1Schematicdiagramofthetubularfixed-bedreactorforFTS16ChaoXing6，。2a，，C25C30，（300℃）。N2，。24h，，，。2a10h20h，2bAr，。，，。a.；b.：T=260℃，p=3MPa，GHSV=24000mL/(g·h)，V(H2)/V(CO)=4，X(CO)=60.55%2.1.2，。3、，（），[3,6,14]。4，。：T=260℃，p=3MPa，GHSV=24000mL/(g·h)，V(H2)/V(CO)=4，X(CO)=60.55%：T=260℃，p=3MPa，GHSV=24000mL/(g·h)，V(H2)/V(CO)=4，X(CO)=60.55%，αASF。，HuffSatterfieldα[14]，,。，mnn，2Fig.2Accuracyandreliabilityofgascomponentsonlineanalysis3Fig.3DetailedFTSproductdistributionwithincreasingcarbonnumber4Fig.4Ratioofolefintoparaffinwithincreasingcarbonnumber：17ChaoXing201641·C1α1α22，xα1。，α1=0.55，α2=0.90，x=0.61。2.2，。，，。，[3,6,14]（，），，。，。Aspenplus，5。2.2.15，AspenplusFLASH，RK-SOAVE，25℃0.1MPa，5WAX，3MPa，。WAX-GWAX-L，WAX-G。6a，。WAX-G，6b，。，，。a.；b.。：T=260℃，p=3MPa，GHSV=24000mL/(g·h)，V(H2)/V(CO)=4，X(CO)=60.55%2.2.2，，，。。，、、。FEED，5，Aspenplus5AspenPlusFig.5ModelingofFTSproductseparationbasedonAspenPlus6Fig.6Flashlosssimulationduringproductcollectionatcurrentoperatingconditions18ChaoXing6SEPA，RK-SOAVE。SEPA，WATER、WAXTAIL-GAS。WATER。760～180℃、0.5～5MPa。，（）。：T=260℃，p=3MPa，GHSV=5000mL/(g·h)，V(H2)/V(CO)=4，X(CO)=68.07%，。，，，。85000mL/(g·h)、3MPa140℃，C10～C20。，，、，。，，、。。3，（C1～C30）、，（C10～C70）。，，。Aspenplus，，。[1]XuJ,YangY,LiY-W.RecentdevelopmentinconvertingcoaltocleanfuelsinChina[J].Fuel,2015,152:122-130.[2]DryME.TheFischer-Tropschprocess:1950-2000[J].CatalToday,2002,71:227-241.[3]GaoJ,WuB,ZhouL,etal.IrregularitiesinproductdistributionofFischer-Tropschsynthesisduetoexperimentalartifact[J].IndEngChemRes,2012,51:7Fig.7Effectoftemperatureandpressureonwatercondensationinseparator8Fig.8EffectofwatercondensationonFTSproductdistribution：19ChaoXing201641·C1ExperimentalanalysisofFischer-TropschsynthesisproductdistributionLINJin-zhi1,3,ZHOULi-ping3,HAOXu2,3,YANGYong2,3,XIANGHong-wei2,3,LIYong-wang2,3,JINHai-bo1(1.SchoolofChemicalEngineeringBeijingInstituteofPetrochemicalTechnology,Beijing102617,China;2.StateKeyLaboratoryofCoalConversion,InstituteofCoalChemistry,ChineseAcademyofSciences,Taiyuan030001,China;3.NationalEnergyResearchCenterforCoaltoCleanFuels,SynfuelsChinaCo.,Ltd.,Beijing101407,China)Abstract:Thetraditionalmultiple-stepcollectionofFischer-Tropschproductswasreplacedbyanone-stepcoolingmethod.Theproducts(C1-C30hydrocarbonsandalcohols)inthegasphasewereanalyzedbytheon-lineGCswithhigh-temperatureheating,whiletheliquids(C10-C70hydrocarbons)wereanalyzedbytheoff-lineGCs.Thegasesandtheliquidswereaccuratelymeasuredbyusinginternalstandards,respectively.Theworkcheckedtheaccuracyandthestabilityofthehigh-temperatureon-lineanalysisofthegascomponents.Somemorereliableexperimentalresults,e.g.theparaffins,olefinsandalcoholsformationscatalyzedbyanindustrialiron-basedcatalyst,weregivenbythishigh-efficiencyequipment.Acorrelationbetweenthecarbonnumberandthedetailedproductswasdeveloped.Furthermore,theworkestimatedtheflashlossinproductcollectingandalsothewatercondensationintheseparatorwiththevariedoperatingconditionsbyAspenPlusmodeling.Itshowedthattheflashlossisnegligible,andthewatercondensedintheseparator,whichwillbemixedwiththeliquidwax,couldenlargetheyieldsofthecomponentsinC10-C20region.Theseparatorrunningathighertemperatureandlowerpressurewouldbenecessarytoavoidthewatercondensationintheliquidwax.Keywords:Fischer-Tropschsynthesis;iron-basedcatalysts;productdistribution;on-lineanalysis11618-11628.[4]TengBT,ChangJ,ZhangCH,etal.AcomprehensivekineticsmodelofFischer-TropschsynthesisoveranindustrialFe-Mncatalyst[J].ApplCatalA,2006,301:39-50.[5]MasukuCM,ShaferWD,MaW,etal.Variationofresidencetimewithchainlengthforproductsinaslurry-phaseFischer-Tropschreactor[J].JCatal,2012,287:93-101.[6]BukurDB,LangXS.HighlyactiveandstableironFischer-Tropschcatalystforsynthesisgasconversiontoliquidfuels[J].IndEngChemRes,1999,38:3270-3275.[7]TodicB,BhateliaT,FromentGF,etal.KineticmodelofFischer-TropschsynthesisinaslurryreactoronCo-Re/Al2O3catalyst[J].IndEngChemRes,2012,52:669-679.[8]ViscontiC,TronconiE,LiettiL,etal.DetailedkineticsoftheFischer-TropschsynthesisoncobaltcatalystsbasedonH-assistedCOactivation[J].TopCatal,2011,54:786-800.[9]LinghuW,LiX,AsamiK,etal.ProcessdesignandsolventrecycleforthesupercriticalFischer-Tropschsynthesis[J].EnergyFuels,2006,20:7-10.[10]HuangX,RobertsCB.SelectiveFischer-Tropschsynthesisover