2023年6月24日发(作者：)

第42卷第10期2014年10月燃料化学学报JournalofFuelChemistryandTechnologyVol．42No．10Oct．20142409（2014）10-1160-07文章编号：0253-Sulfurremovalandreleasebehaviorsofsulfur-containingmodelcompoundsduringpyrolysisunderinertatmospherebyTG-MSconnectedwithPy-GC2GUOHui-qing1，，XIELi-li1，WANGXin-long1，LIUFen-rong1，WANGMei-jun3，HUＲui-sheng1（1．CollegeofChemistryandChemicalEngineering，InnerMongoliaUniversity，Hohhot010021，China；2．SchoolofPharmaceuticalScience，InnerMongoliaMedicalUniversity，Hohhot010110，China；3．KeyLaboratoryofCoalScienceandTechnology，TaiyuanUniversityofTechnology，Taiyuan030024，China）Abstract：Sulfurcontainingmodelcompounds，tetradecylmercaptan，dibutylsulfide，phenylsulfide，2-methylthiophene，benzothiopheneanddibenzothiophene，wereselectedtoinvestigatetheirsulfurremovalandreleasebehaviorsduringpyrolysisunderinertatmospherebythermo-gravimetricanalyzerwithmassspectrometer（TG-MS）andpyrolysisconnectedwithgaschromatogram（Py-GC）．Itwasfoundthattheorderofsulfurremovalwastetradecylmercaptan＞dibutylsulfide＞2-methylthiophene＞benzothiophene＞phenylsulfide＞dibenzothiophene．Exceptforphenylsulfide，thisruleiscontrarytothedecompositiontemperatureorderofthesulfurfunctionalgroups．SO2evolutionwasdetectedbyMSandGCforallthosemodelcompoundsandCOSevolutionwasalsofoundexceptforphenylsulfideanddibenzothiophene；whileH2Sevolutionwasmeasuredonlyfortetradecylmercaptan，dibutylsulfideand2-methylthiophene．However，SO2contentwasmuchhigherthanH2SandCOSinpyrolysisgasforeachmodelcompound，whichmaybecausedbythatindigenoushydrogenwasmuchlessthanindigenousoxygenunderinertatmosphere，whenmostofsulfurradicalscanconnectwithindigenousoxygenandreleaseintheformofSO2．activedcarbonwasusedascarrier．Thus，Forphenylsulfide，benzothiopheneanddibenzothiophene，astheirindigenoushydrogenwasnotenoughtoreactwithsulfurradicals，noH2Swasdetectedduringpyrolysisunderinertatmosphere，whileSO2wasfoundanditscontentwasveryhighinpyrolysisgas．Keywords：pyrolysis；sulfurrelease；sulfur-containingmodelcompounds；TG-MS；Py-GCCLCnumber：TQ53Documentcode：ASO2andothersulfur-containinggasesreleasefromcoal-combustionandrefineryoperationshavebeenimplicatedasacauseofsomeairpollution（asacidrain）relatedproblems［1］．ＲationalutilizationofcoalresourcesisthemajorrequirementsofthestrategyofChinesesustainabledevelopment［2～4］．Thus，theresearchprojectscanbeputforwardtoatthesametime．ThatishowwecaneffectivelycontrolthedischargeofSOxandinvestigatethecleancoalutilizationtechnology．Thesulfurreleaseduringcoalpyrolysisprocessisverycomplicated，soitisdifficulttomakeanexactexplanation．Now，therearedifferentexplainsaboutthesulfurreleasemechanismduringcoalpyrolysisprocess．Someresearchers［5］consideredthatthesulfurcompoundsfirstlybrokeintosulfurfreeradicals，andthensulfurradicalscombinedwithinternalorexternalhydrogentoevolveH2S．Yanetal［6］proposedthatthesulfur-containingcompoundsofcoalfirstlycrackedandreleasedsulfurhydrogenfreeradicals，andthesubsequentreactionandconclusionwereＲeceiveddate：2014-05-20；Ｒeceivedinrevisedform：2014-08-08．similartotheformer．Mullensetal［7］usedTPD-MS/TPO-MStostudythealiphaticsulfur-containingmodelcompoundsbenzylsulfideandbenzyl-dryldisulfide．Itshowedthatthetwocompoundsbegantoreleasegasat215℃underatmospherepressureandstoppedtoreleaseat310℃underhelium．Thesulfur-containinggaswasmainlyH2S，COSandSO2．Basedonthecomplexityofsulfurreleasingmechanismduringcoalpyrolysis，many［8～10］researchersstudiedreleasebehaviorofsulfur-containingmodelcompoundsinsteadofcoal．Somein-depthunderstandingofthesulfurreleasingbehaviorhasbeenattainedduringpyrolysis，butasthestrongstabilityofthiophenestructuremodelcompounds（suchasdibenzenethiophene）withmuchhigherdecompositiontemperaturewaseasilyvolatilizedbeforedecomposition，itisstillhardtocarrythrough11～17］theresearch［5，．Therefore，itisveryimportanttochooseanappropriatecarriertoloadsulfurmodelcompoundsforfurtherstudyingsulfurreleasebehavior．Foundationitem：SupportedbyNaturalScienceFoundationofChina（21466025），theNaturalScienceFoundationofInnerMongolia（2013MS0205）andtheStateKeyLaboratoryBreedingBaseofCoalScienceandTechnologyCo-foundedbyShanxiProvinceandtheMinistryofScienceandTechnology，TaiyuanUniversityofTechnology（2014）．471-4992981；E-Correspondingauthor：Tel/Fax：+86-mail：fenrongl@163．com，nmgwmj1985@163．com．本文的英文电子版由Elsevier出版社在ScienceDirect上出版（http：//www．sciencedirect．com/science/journal/18725813）。第10期GUOHui-qingetal：Sulfurremovalandreleasebehaviorsofsulfur-containing．．．．．．1161Previouslystudiesshowedthatactivatedcarbonhasbetteradsorptionpropertiescomparedwithsilicaandalumina．Theadsorptionabilityofacetonewasbetterthantoluene［18］．Inthisstudy，severalsulfur-containingmodelcompounds，tetradecylmercaptan，dibutylsulfide，phenylsulfide，2-methylthiophene，benzothiopheneanddibenzothiophene，wereselectedtoinvestigatethesulfurremovalandreleasebehaviorsbyTG-MSandPy-GCduringpyrolysis．Thus，moreinformationaboutsulfurreleasebehaviorofmodelcompoundscanbeattained，whichwasveryhelpfulforstudyingthesulfurreleasemechanismofcoalduringpyrolysis．11．1ExperimentalSamplesEachmodelcompoundincludingtetradecylmercaptan，dibutylsulfide，phenylsulfide，2-methylthiophene，benzothiopheneanddibenzothiophene，wasloadedontoactivatedcarboncarrier．Briefly，underair-freeconditions，thesulfur-containingmodelcompound（themasswasdeterminedbyitssulfurcontentandthedesiredsulfurcontent）wasplacedintoabeakerwith5mLacetonesolutionandthoroughlyresolved．Thenthesolutionwaspouredintoanotherbeakerwhereabout1gactivatedcarbonhadbeenadded．Thesampleswerestirredbyultrasonicationfor20min，driedatroomtemperatureforabout48h，andthencollectedforfurtherexperimentation．Theautomaticsulfurdeterminationanalyzer（XK-5000）wasusedtomeasuresulfurcontentofeachmodelcompoundbeforeandafterpyrolysisinthisstudy，andthesulfurcontentofTable1ModelcompoundSulfur-contentbeforpyrolysisw/%Sulfur-contentafterpyrolysisw/%Weightlossw/%Desulfurizationratio/%Tetradecylmarcaptan3．100．7134．6377．062-methylthiophene2．321．5714．5132．10modelcompoundsareshowninTable1．1．2Py-GCequipmentPyrolysiswascarriedoutinaquartztubefixedbedreactor（i．d．5mm，length60cm）．About0．5gcoalwaspyrolyzedunderN2atthetemperaturerangefromroomtemperatureto800℃withgasflowrateof75mL/minatheatingrateof10℃/min．H2S，COSandSO2wereanalyzedbygaschromatography（GC）withFPD．Thecolumnanddetectortemperatureswere90and250℃，respectively．Afterpyrolysis，thesamplewascoldedandcolletedforfurthermeasuringitsweightandsulfurcontent．Thus，theweightloss（%）w=mA/mＲ，wheremAistheweightofsampleafterpyrolysis（g）andmＲistheweightofrawsampel（g）．Thedesulfurizationratiocanbeattainedacordingtotheliterature［19］．AndthedesulfurizationratioandweightlossareshowninTable1．1．3TG-MSequipmentTG-MSequipmentcanbeseenelsewhere［20～23］．About20mgmodelcompoundwasplacedintothequartzreactorandsubsequentlyheatedat10℃/minfromroomtemperatureto800℃inacontinuousflowofpurenitrogenataflowrateof75mL/min．Themassspectrometer（OmnistarTM）wasusedtomeasureH2S，COS，SO2，etc．online．2Ｒesultsanddiscussion2．1SulfurremovalofmodelcompoundsduringpyrolysisTable1istheweightlossofmodelcompoundsandtheirsulfurremovalduringpyrolysisunderinertatmosphereattainedbypyrolysis，respectively．DesulfurizationefficiencyofmodelcompoundsduringpyrolysisBenzothiophene2．992．1717．9527．67Dibutylsulfide2．830．7224．1474．72DibenzothiophenePhenylsulfide3．012．3819．1221．073．032．2524．7125．87AsTable1shows，theweightlossoftetradecylmethylmarcaptan，dibutylsulfide，phenylsulfide，2-thiophene，benzothiopheneanddibenzothiopheneis34．63%，24．14%，24．71%，14．51%，17．95%and19．12%，whilethesulfurremovalis77．06%，74．72%，25．87%，32．10%，27．67%and21．07%，respectively．ComparedwithTable1andFigure1，theresultsofweightlossattainedbyPy-GC（showninTable1）isalmostsametotheonesbyTG（showninFigure1），suchasweigtlossoftetradecylmercaptanis34．63%inTable1andabout35%inFigure1；thatof2-methylthiopheneis14．51%inTable1，whileabout15%inFigure1，andsoon．Itcanbeclearlyseenthattheorderofsulfurremovalistetradecylmercaptan＞dibutylsulfide＞2-methylthiophene＞benzothiophene＞phenylsulfide＞dibenzothiophene．Exceptforphenylsulfide，thisruleiscontrarytothedecompositiontemperatureorderofthesulfurfunctionalgroups，whichisalkylthiols＜arylthiols＜disulfides＜dialkylsulfides＜alkylarylsulfides≈alkylarylsulfoxides≈alkylarylsulfones＜pyrite＜diarylsulfides≈diarylsulfoxides＜diarylsulfones＜1162燃料化学学报第42卷simplethiophenicstructures＜troilite＜inorganicsulfatesandcomplexthiophenicstructure［22～24］．Thiscanfurthervalidatethatthelowerthedecompositiontemperatureofsulfurfunctionalgroupis，thehigheritssulfurremovalis．Butthereisnoenoughinnerhydrogeninactivatedcarbon，phenylsulfideanddibenzothiophene．SulfurradicalsfromthosecompoundsduringpyrolysiscouldnotconnectwithinnerhydrogentoevolveH2S．Therefore，thedesulfurizationefficiencyislowerthansimplemethylthiopheneandthiophenicstructures，suchas2-benzothiophene．attainedbyMSandtheirDTGplotsbyTG．Foractivatedcarbon，noH2Sreleaseisdetectedatthewholetemperaturerange．Thus，H2Sreleaseofmodelcompoundsisunrelatedtoactivatedcarboncarrier．Figure2H2SevolutionlinesandDTGplotsofdifferentmodelcompoundsFigure1TGplotsofdifferentsulfur-containingmodelcompoundsInaddition，benzothiopheneanddibenzothiopheneareeasilyvolatilizedbeforedecompositionduringpyrolysis．Thus，itssulfurremovalmaybecausedbyitsvolatilization，notbyitsdecomposition．Thiscanbefurthertestifiedbyitssulfur-containinggasesevolutionduringpyrolysis．2．2Ｒeleaseofsurfur-containinggasesofmodelcompoundsduringpyrolysisInthisstudy，Py-GCandTG-MSwereusedtoinvestigatethereleaseofsulfur-containinggasesduringpyrolysis，suchasH2S，COSandSO2，etc．2．2．1H2SreleaseofmodelcompoundsduringpyrolysisFigure2isH2SevolutionofactivatedcarbonanddifferentmodelcompoundsloadedonactivatedcarbonFortetradecylmercaptan，therearetwoobviousH2Sevolutionpeaksfrom250to450℃inFigure2andH2SisalsoobservedbyGCwithFPDinthistemperatureregion（Figure3）．Thefirstpeakshouldbeattributedtodecompositionoftetradecylmarcaptanitself，andthesecondonemayberelatedtodecompositionofitstransformationcompounds，e．g．alkylsulfide．AsshowninFigure2，theweightlossrateisveryhighbefore300℃andthendecreases．AndtheDTGpeakiscoincidedtothefirstpeakofH2S，whichindicatestheweightlossiscausedbythedecompositionoftetradecylmarcaptan．ButbeforeH2Sevolution，theweightlosshasalreadystarted，whichmaybemainlycausedbylosingsomealkylsorvolatilizationoftetradecylmarcaptan．AsnosaturatedCH-chainscompoundwasdetectedbyMSbefore400℃asshowninFigure4，theweightlossbeforeH2Sevolutionisexactlyresultedfromitsvolatilizationratherthanlosingsomealkyls，whileafterH2Sevolution，itisjustcausedbydecompositionoftetradecylmarcaptan．Assomealkylradicals，hydrogenradicalsandsulfur-containingradicalscouldbeproducedduringpyrolysis，theycanconnectwitheachothertoevolveH2S，somesmallalkycompoundsandalkylsulfide．Comparisontothetwo第10期GUOHui-qingetal：Sulfurremovalandreleasebehaviorsofsulfur-containing．．．．．．1163peaks，thefirstoneissmallerthanthesecond．Thus，themostofsulfurcomesfromtransformationcompoundoftetradecylmarcaptanratherthanitself．inFigure3）．However，themaximumpeaktemperatureisalmostclosetothesecondoneoftetradecylmarcaptan，whichfurthertestifiesthattetradecylmarcaptancantransformtoalkylsulfide．ItsH2Sevolutionbeginsnearly275℃，whiletheweightlossstartsbefore100℃．ThismustbecausedbythedecompositionofdibutylsulfideassomesaturatedcarbonhydrogencompoundswerealsocheckedattheweightlossregionasshowninFigure5，likemethane，ethane，butane，andsoon．Thus，thesulfurremovalisresultedfromitsdecompositionratherthanitsvolatilization．Figure3H2SreleasingpeaksofdifferentmodelcompoundsbyGCFigure5EvolutionofsaturatedCH-chainscompoundsfordibutylsulfideFigure4EvolutionofsaturatedCH-chainscompoundsfortetradecylmercaptanFordibutylsulfide（C4H9-S-C4H9），onlyoneH2SevolutionpeakcanbeclearlyseeninFigure2，whichissimilartotheresultsattainedbyGC（shownThereisalsoonepeakfor2-methylthiophene，andnopeakforbenzothiophene，phenylsulfideanddibenzothiophene，respectivelyinFigure2．2-methylthiophenestartstodecomposeabout100℃andthemaximumpeaktemperatureisabout200℃，whichissimilartotheresultsattainedbyGC，butthreeobviouspeaksweredetectedbyGC，whilenopeaksobservedbyMSafter400℃．ThedifferencemaybecausedbythedifferentsensitivityofGCandMSequipmentordifferentsamples’weightduringexperiment．However，theDTGplotisalmostcoincidedtotheH2Sevolutionpeak，indicatingthattheweightlossmaybemainlycausedbyitsdecomposition．Inaddition，methaneandethanearealsofoundatthetemperaturerangeofweightloss1164燃料化学学报第42卷（showninFigure6），whichcanfurthertestifythehypothesis．Figure7COSreleasingpeaksofdifferentmodelcompoundsattainedbyMSFigure6EvolutionofsaturatedCH-chainscompoundsfor2-methylthiopheneHowever，forbenzothiophene，phenylsulfideanddibenzothiophene，noH2SwasalsodetectedbyGC，andthustheirweightlossshouldbecausedbytheirvolatilizationorbyCOSandSO2evolution．2．2．2COSandSO2releaseofmodelcompoundsduringpyrolysisFigures7and8showCOSreleasingpeaksofdifferentmodelcompoundsattainedbyMSandbyGC，respectively．ItisclearlyseenthatthereisalsonoCOSmeasuredbyMSorGCforactivatedcarbon，phenylsulfideanddibenzothiophene．ThetemperaturerangeofCOSevolutionisverysimilartoH2Sevolutionfortetradecylmercaptan，dibutylsulfideand2-methylthiophene．Butforeachoftetradecylmercaptan，dibutylsulfideand2-methylthiophene，COSconcentrationismuchlowerthanH2Sconcentration，e．g．，themaximumCOSconcentrationislowerthan1×10－6，0．－6－63×10and10×10（Figure8），whileH2Sconcentrationcanattainabout50×10－6，10×10－6andhigherthan15×10－6（Figure3），respectively．Forbenzothiophene，COSwasalsodetectedatthetemperaturerangefrom200to600℃byMSand400to500℃byGC，whichisverydifferentfromitsH2Sevolution，asnoH2SwasfoundwhetherbyMSorbyGCduringpyrolysis．Figure8COSreleasingpeaksofdifferentmodelcompoundsattainedbyGCExceptforactivatedcarbon，SO2wasdetectedbyMSandGCforallofthosesulfurcontainingcompoundsandtheresultsareshowninFigures9and10，respectively．第10期GUOHui-qingetal：Sulfurremovalandreleasebehaviorsofsulfur-containing．．．．．．1165ItcanbeclearlyseenthattheSO2evolutionprofilesarealmostcoincidedwithH2SandCOS，showingthatsulfurcontainingradicals，whichcomefromsulfurcontainingcompoundsduringpyrolysis，canequallyreactwithindigenoushydrogenandoxygen［21］．Underinertatmosphere，asactivatedcarbonwasusedascarrier，indigenoushydrogenismuchlessthanindigenousoxygen．Thus，mostofsulfurradicalscanconnectwithindigenousoxygenandreleaseSO2．Forphenylsulfide，benzothiopheneanddibenzothiophene，astheirindigenoushydrogenisnotenoughtoreactwithsulfurradicals，noH2Swasfoundduringpyrolysisunderinertatmosphere，whileSO2wasdetectedanditscontentisveryhighinpyrolysisgas．Forothercompounds，theSO2contentasshowninFigure10isalsomuchhigherthanH2SandCOS．3Figure9SO2releasingpeaksofdifferentmodelcompoundsattainedbyMSConclusionsFigure10SO2releasingpeaksofdifferentmodelcompoundsattainedbyGCInthisstudy，sulfurcontainingmodelcompoundswasusedtoinvestigatetheirsulfurremovalandsulfurreleasebehaviorduringpyrolysisunderinertatmosphere．Thefollowingconclusionscanbeobtained：Theorderofsulfurremovalwastetradecylmercaptan＞dibutylsulfide＞2-methylthiophene＞benzothiophene＞phenylsulfide＞dibenzothiophene．Exceptforphenylsulfide，thisruleiscontrarytothedecompositiontemperatureorderofthesulfurfunctionalgroups．Itindicatesthatthelowerthedecompositiontemperatureofsulfurfunctionalgroup，thehigheritssulfurremoval．SO2evolutionwasdetectedbyMSandGCforallthosemodelcompounds．COSwasalsofoundexceptforphenylsulfideanddibenzothiophene，whileH2Swasmeasuredonlyfortetradecylmercaptan，dibutylsulfideand2-methylthiophene．Underinertatmosphere，asactivatedcarbonwasusedascarrier，indigenoushydrogenwasmuchlessthanindigenousoxygen．Thus，mostofsulfurradicalscanconnectwithindigenousoxygenandreleaseSO2．Forphenylsulfide，benzothiopheneanddibenzothiophene，astheirindigenoushydrogenwasnotenoughtoreactwithsulfurradicals，noH2Swasdetectedduringpyrolysisunderinertatmosphere，whileSO2wasfoundanditscontentisveryhighinpyrolysisgas．Ｒeferences［1］HUANGC，LINKOUSCA，ADEBIYIO，T-ＲAISSIETA．Hydrogenproductionviaphotolyticoxidationofaqueoussodiumsulfitesolutions［J］．EnvironSciTechnol，2010，44（13）：5283-5288．［2］YUJ，YINF，WANGS，CHANGL，GUPTAS．Sulfurremovalpropertyofactivated-char-supportedFe-Mosorbentsforintegratedcleaningofhotcoalgases［J］．Fuel，2013，108（6）：91-98．［3］YUJ，CHANGL，XIEW，WANGD．CorrelationofH2SandCOSinthehotcoalgasstreamanditsimportanceforhightemperature．KoreanJChemEng，2011，28（4）：1054-1057．desulfurization［J］［4］XUG，YANGY，LUS，LIL，SONGX．Comprehensiveevaluationofcoal-firedpowerplantsbasedongreyrelationalanalysisandanalytichierarchyprocess［J］．EnergyPolicy，2011，39（5）：2343-2351．1166燃料化学学报第42卷［5］ATTAＲA．Chemistry，thermodynamicsandkineticsofreactionsofsulphurincoal-gasreactions：Areview［J］．Fuel，1978，57（4）：201-212．［6］YANJ，YANGJ，LIUZ．SHradical：Thekeyintermediateinsulfurtransformationduringthermalprocessingofcoal［J］．EnvironSciTechnol，2005，39（13）：5043-5051．［7］MULLENSS，YPEＲMANJ，ＲEGGEＲSG，CAＲLEEＲAＲ，BUCHANANA．C，BＲITTPF，ＲUTKOWSKIP，GＲYGLEWICZG．Astudyofthereductivepyrolysisbehaviourofsulphurmodelcompounds［J］．JAnalApplPyrolysis，2003，70（2）：469-491．［8］MAESII，GＲYGLEWICZG，YPEＲMANJ，FＲANCODV，D’HAESJ，D’OLIESLAEGEＲSM，VANPOUKELC．Effectofsideriteincoalonreductivepyrolyticanalyses［J］．Fuel，2000，79（15）：1873-1881．［9］MAESII，YPEＲMANJ，VANDENＲULH，FＲANCODV，MULLENSJ，VANPOUCKELC，GＲYGLEWICZG，WILKP．Studyofcoal-derivedTPＲ）［J］．EnergyFuels，1995，9（6）：950-955．pyriteanditsconversionproductsusingatmosphericpressuretemperature-programmedreduction（AP-［10］YIP，YUQ，ZONGH．Thechemicalthermodynamicsanalysisofpyritedesulfurization［J］．CoalConvers，1999，22（1）：48-52．［11］SUGAWAＲAK，ENDAY，SUGAWAＲAT，SHIＲAIM．XANESanalysisofsulfurformchangeduringpyrolysisofcoals［J］．SynchrotＲadiat，2001，8（2）：955-957．［12］MIUＲAK，MAEK，SHIMADAM，MINAMIH．Analysisofformationratesofsulfur-containinggasesduringthepyrolysisofvariouscoals［J］．Energyfuels，2001，15（3）：629-636．［13］XUL，YANGJ，LIY，LIUZ．Behavioroforganicsulfurmodelcompoundsinpyrolysisundercoal-likeenvironment［J］．FuelProcessTechnol，2004，85（8）：1013-1024．［14］KAＲＲJＲC．Analyticalmethodsforcoalandcoalproducts［J］．AcademicPress，1979，19（3）：588-624．［15］KATSUYASUS，KEIKOA，TAKUOS．Dynamicbehaviorofsulfurformsinrapidpyrolysisofdensity-separatedcoals［J］．Fuel，1995，74（12）：1823-1829．［16］SUGAWAＲAK，TOZUKAY，KAMOSHITAT，TAKUOS，MAＲKAS．Dynamicbehaviourofsulfurformsinrapidpyrolysisofdensity-separatedcoals［J］．Fuel，1994，73（7）：1224-1228．［17］LIUF，LIW，CHENH，LIB．Unevendistributionofsulfursandtheirtransformationduringcoalpyrolysis［J］．Fuel，2007，86（3）：360-366．［18］刘粉荣，［J］．化工进展，2012，31（11）：2570-2573．郭慧卿，胡瑞生，赫淑颖，胡浩权．含硫模型化合物在不同载体上的担载及其燃烧过程硫的释放行为（LIUFen-rong，GUOHui-qing，HUＲu-sheng，HEShu-ying，HUHao-quan．Astudyontheloadingbehaviorofsulfur-containgcompoundsonthedifferentcarriersandsulfurreleasebehaviorduringcombustionprocess［J］．ChemicalIndustryandEngineeringProgress，2012，31（11）：2570-2573．）［19］刘粉荣，李文，李保庆，陈皓侃．氧化性气氛下流化床中煤的热解脱硫及硫的分布［J］．燃料化学学报，2006，34（4）：404-407．（LIUFen-rong，LIWen，CHENHao-kan，LIBao-qing．Sulfurremovalanditsdistributionduringcoalpyrolysisinfluidizedbedreactorunderoxidativeatmospheres［J］．JournalofFuelChemistryandTechnology，2006，34（4）：404-407．）［20］LIUF，LIW，CHENH，LIB．Gasanalysisandsulfurremovalfromcoalduringfluidizedbedpyrolysisunderdifferentoxygencontents［C］．10．2005ICCS＆TOkinawa，2005-［21］刘粉荣，［J］．燃料化学学报，2011，39（2）：81-84．李文，郭慧卿，李保庆，白宗庆，胡瑞生．XPS法研究煤表面碳官能团的变化及硫迁移行为（LIUFen-rong，LIWen，GUOHui-qing，LIBao-qing，BAIZong-qing，HUＲui-sheng．XPSstudyonthechangeofcarbon-containinggroupsandsulfurtransformationoncoalsurface［J］．JournalofFuelChemistryandTechnology，2011，39（2）：81-84．）［22］LIUF，LIB，LIW，BAIZ，YPEＲMANJ．Py-MSstudyofsulfurbehaviorduringpyrolysisofhigh-sulfurcoalsunderdifferentatmospheres［J］．FuelProcessTechnol，2010，91（11）：1486-1490．［23］MAJCHＲOWICZ．B，YPEＲMAN．J，MULLENSJ，VANPOUCKE．L．Automatedpotentiometricdeterminationofsulfurfunctionalgroupsinfossilfuels［J］．AnalChem，1991，63（8）：760-763．［24］YPEＲMANJ，MAESII，VANDELＲULH，MULLENSS，VANAELSTJ，FＲANCOD，JULESM，LUCIENC，POUCKEV．Sulphurgroupanalysisinsolidmatricesbyatmosphericpressure-temperatureprogrammedreduction［J］．AnalChimActa，1999，395（1）：143-155．［25］VANAELSTJ，YPEＲMANJ，FＲANCOD，VANPOUCKEL，BUCHANANA，BＲITTP．Studyofsilica-immobilizedsulfurmodelcompoundsascalibrantsfortheAP-TPＲstudyofoxidizedcoalsamples［J］．EnergyFuels，2000，14（5）：1002-1008．TG-MS与Py-GC相结合法研究惰性气氛下含硫模型化合物热解过程中硫的脱除及释放行为研究1，211131郭慧卿，谢丽丽，王鑫龙，刘粉荣，王美君，胡瑞生（1．内蒙古大学化学化工学院，内蒙古呼和浩特2．内蒙古医科大学药学院，内蒙古呼和浩特010021；030024）010110；3．太原理工大学煤科学与技术重点实验室，山西太原摘MS）和热解-MS）相结合的方法对模型化合物（十四硫醇、要：采用热重-质谱法（TG-气相色谱法（Py-二丁基硫醚、苯硫醚、二甲基噻吩、苯并噻吩和二苯并噻吩等）在惰性气氛下硫的脱除及释放行为进行研究。惰性气氛下硫的脱除顺序为：十四硫醇＞二丁基硫醚＞二甲基噻吩＞苯并噻吩＞苯硫醚＞二苯并噻吩，苯硫醚除外，该顺序与含硫官能团的热分解顺序一致。在热解过程中，所有模型化合物在质谱和气相色谱仪上均被检测到SO2；除苯硫醚和二苯并噻吩外，其他模型化合物中均检测到了COS；而只在十四硫醇、二丁基硫醚和二甲基噻吩中检测到了H2S。且热解气中SO2含量要显著高于H2S和COS。这是由于活性炭作载体时，惰性气氛下内部氢的含量显著小于内部氧的含量，所以大多数的含硫自由基易与内部氧结合以SO2的形式苯并噻吩和二苯并噻吩中没有检测到H2S，是由于内部氢的不足，使得含硫自由基不能与内部氢结合，所逸出。对于苯硫醚、以没有检测到H2S逸出。MS；Py-GC关键词：热解；硫释放；含硫模型化合物；TG-中图分类号：TQ53文献标识码：A