以模型化合物吡啶研究煤中氮转化成HCN和NH3的机理

:2005204204;:2005205226:(G1999022101);(20276046);2003:(1977),(),,,E2mail:[e-mail]26320058JournalofChineseMassSpectrometrySocietyVol.26No.3Aug.2005HCNNH31,2(1.,102413;2.,030024):,6001300,2HCNNH3,2,42,22:HCN,NH3:;;HCN;NH3;2(GC/MS);:O657163;TQ53419:A:100422997(2005)032138204FormationMechanismofHCNandNH3duringCoalPyrolysisandGasificationfromFuel2NUsingModelCompoundsPyridineQIAOJin2hong1,ZHAOWei2(1.ChinaInstituteofAtomicEnergy,Beijing102413,China;2.TaiyuanUniversityofTechnology,Taiyuan030024,China)Abstract:PyridinewasusedasamodelcompoundtostudyontheformationmechanismofHCNandNH3fromcoal2N.Someexperimentswerecarriedoutinatubularquartzreactoratthetemperatureof60021300,andgaschromatography2massspectrometry(GC/MS)wasusedtomeasuretheliquidproductsfromexperiments.Someusefulresultsandconclu2sionswereacquiredasfollowing:2,42pentadlenenitrilecouldbedetectedinthesamplesofpyridineexperiments;andthe22methoxy2pyridinecanbedetectedinthesampleofpyridinegasification.AlloftheresultsseemlyrevealthatHCNcomesfromthethermalcrackingofpyridineandNH3istheproductofthehydrolyzationofnitrile.Keywords:coal;pyridine;HCN;NH3;gaschromatography2massspectrometry(GC/MS);mechanism,200314,67%[1],2050,3040[2],2NONO2N2O[3,4],,(NH3HCN),NOx,NH30.5%2%[5,6],XPS(X)[79]HCNNH3[10,11],,NOx1111HP6890/59732:(Hewlett2Packard);:;;13()1121910mm700mm,;Gilsonmodel30340.010.99mL/hSY202A50.1mL/h;D070200mL/min;9DL211Fig.1Diagramofexperimentalapparatus1(Carriergascylinder);2(Filter);3(Flowindicatingcontroller);4(Syr2ingepump);5(Pillarplugpump);6(Temperatureindicatingcontroller);7(Pre2heatingoven);8(Quartzreactor);9(Heatoven);10(Bubbler)113,,,,,2(GC/MS)114,200,,,,115GC/MS1.5.1:HP190912S433;250;1.0mL/min;:100,1min,15/min250,5min;;60kPa;1.0L;,501;15min1.5.2(EI);70eV;185;1.3310-3Pa;m/z20500;50002(HPG1033A),,,12,4232,,,,2,42,,HCN,HCN,21,9313:HCNNH32,42,HCN1GC/MSTable1AnalysisresultsofpyridinepyrolysisliquidsamplebyGC/MSNo.tR/minCompoundSimilarity/%13.459pyridine9126.5602,422,42pentadlenenitrile9637.1372222methyl2pyridine9647.8113232methyl21H2pyrrole9358.126ethylbenzene9068.1432222ethynylpyridine8378.2743232methyl2pyridin,9388.530benzonitrile9099.0463232aminopyrazole621010.1832222ethenyl2pyridine931110.537naphthalene941210.617azulene951311.8922222pyridinecarbonitrile961414.072isoquinoline961514.091quinoline941614.471bithenylene931715.509acenaphthylene931816.1302,322,32dipyridyl901923.1734242phenyle2pyridine902GC/MSTable2IdentifiedcomponentsofpyridinegasificationliquidsamplebyGC/MSNo.tR/minCompoundSimilarity/%13.459pyridine9125.3632,422,42pentadlenenitrile9636.2972222methyl2pyridine9747.9923232aminopyrazole5359.2012222methoxy2pyridine97611.381N212methyl21H2pyrazole81712.284benzonitrile87812.509bithenylene93912.9902222pyridinecarbonitrile951014.5072222ethenyl2pyridine901116.6444242pyridinecarbonitrile951218.430indene971318.0513232Pyridinecarbonitrile931419.4634242methyl2benzonitrile911521.348indole951621.4831,521,52naphthyridene901722.411biphenylene871822.620benzene931922.89612naphthalenecarbonitrile932023.2031212isoquinolinecarbonitrile8704126,,,NH3,3HCNNH3,2,42,;:,,C2NHCN,2,42HCN:2,42,,HCNNH3NH3HCNHCN,CONH3:,,,,HCNNH3:[1],,,.[J].(),2003,16(1):815.[2].[M].:,1999.3455.[3],,.SO2,NO[J].,1998,26(4):356361.[4]EmiIkeda,JohnC,Macke.ThermalDacomposi2tionofTwoCoalModelCompounds2Pyridineand22Picoline[J].JAnalApplPyrol,1995,34(4):4763.[5],,,.[M].:,1989.6397.[6].[J].,1988,17(4):2026.[7].[M].:,1959.7778.[8],,,..[J].,2001,29(2):124128.[9],,,.X[J].,2001,35(7):661665.[10],,,.[J].,2002,30(5):408412.[11],,,.[J].,2002,30(6):519522.[12],,./[J].,1996,15(3):5860.1413:HCNNH3