城市生活垃圾焚烧体系化学热力学平衡分析

312003612JOURNALOFFUELCHEMISTRYANDTECHNOLOGYVol131No16Dec12003:025322409(2003)0620584205:2002212216;:2003209205:(19732),,,,E2mail:jli@home1ipe1ac1cn,,(,100080):,(PVC),PVC,PVCHCl,600,HCl;600,HCl,HCl,:;;HCl;:X705:A,,HCl,[1,2],HCl,,,HCl,1111(),,()112Gibbs,FlemmingF[3]MINGSYS(MINimizationofthetotalGibbsenergyforaSYStem),Gibbs:Gibbs,Lagrange[4]1[3],,,,Gibbs1MINGSYSFigure1SchemeofequilibriumsystembyMINGSYSinMSWincinerator(Medenotesmetal)113;();;11311PVC(50%),,PVC,1()1PVCTable1TheultimateanalysisofPVCElementCOHSClPbCaBawP%3516521154184012050161413621090117PVC,2()2Table2TheultimateanalysisofMSWinChinaElementCHONSClAshWaterwP%3612213141311501101515113010113120,014,018,1,112,116,118,1131311013105Pa;3001100PVC,PVC(CaO,4),2211PVC2PVC=0Cl,ClPVCClPVCCaClCaCl2,ClPbCl4,ClHCl700HCl,PbCl4HCl3=1Cl,Cl:ClCl2,Cl2,HClO2,PVCHClO2(1)300G=291494kcalPmol0(G),;600,G0300,Cl2,HCl2=0PVCFigure2PVCsequilibriumpercentageofchlorinespecieswhen=0(g:gaseousstate;cr:crystallinestate;l:liquidstate;cr,l:condensedstate)3=1PVCFigure3PVCsequilibriumpercentageofchlorinespecieswhen=14HCl(g)+O2(g)2Cl2(g)+2H2O(g)(1)4HCl,,1HCl,1O2HCl,Cl24PVCHClFigure4PVCsequilibriumpercentageofHClgasunderdifferent5856:,HCl5CaPCl=4=0Cl,,ClCaCaCl26CaPCl=4=1Cl,=0800HCl,CaOHCl(2)680G0,,O2H2O680,HClCaO(cr)+2HCl(g)CaCl2(cr,l)+H2O(g)(2)7CaPCl=4,HClPVC=0ClCaCaCl2,0680ClHCl,HClPVC,PVCCaOHCl5=0PVCFigure5PVCsequilibriumpercentageofchlorinespecieswhen=0(CaPCl=4)6=1PVCFigure6PVCsequilibriumpercentageofchlorinespecieswhen=1(CaPCl=4)7PVCHClFigure7PVCsequilibriumpercentageofHClgasunderdifferent(CaPCl=4),CaOHCl;PVC,680,CaOHCl,CaO2128Cl015%,=1Cl(NaCl)7915%,360NaCl,150,HCl,250HCl;360,NaClAl2O3Na2O6SiO2(),HCl;800,HClNaCl,HCl[5,6](3)800G0,,HClNaCl8=1Figure8MSWsequilibriumpercentageofchlorinespecieswhen=1685314NaCl(g)+2SO2(g)+O2(g)+2H2O(g)2Na2SO4(cr,l)+4HCl(g)(3)9=0ClHCl(600),NaClAl2O3Na2O6SiO2,9=0Figure9MSWsequilibriumpercentageofchlorinespecieswhen=010HCl,,HCl,=0420=118240,CaO,ClCaCl2,HClHCl=0600=11844010HClFigure10MSWsequilibriumpercentageofHClgasunderdifferent,HCl,;400HCl,800,HClNaCl,,[7]389,600,HCl,HCl;HCl,500()HCl750,CaOCa(OH)2CaCO3HCl:CaCO3(s)+2HCl(g)CaCl2(s)+H2O(g)+CO2(g)CaO(s)+2HCl(g)CaCl2(s)+H2O(g)Ca(OH)2(s)+2HCl(g)CaCl2(s)+2H2O(g),600680720,,600,[8,9]:,550,HCl;HCl,500600,HCl,HCl,,,,HCl,7856:[1],,,1[J]1,2002,30(6):56325681(LIXiao2dong,YANGZhong2can,LUSheng2yong,etal1Studyondeterminationmethodsforchlorinecontentinmunicipalsolidwastes[J]1JournalofFuelChemistryandTechnology,2002,30(6):56325681)[2],1[J]1,2001,29(4):33923421(XUJiang2hua,PANWei2ping1StudyonmechanismforformationofchlorinatedorganicduringcombustionofMSWandcoal[J]1JournalofFuelChemistryandTechnology,2001,29(4):33923421)[3]FlemmingF1Traceelementsfromcoalcombustion[D]1Copenhagen:TechnicalUniversityofDenmark,19951[4],1[M]1:,19871502741(XUZhi2hong,WANGLe2shan1Databaseofinorganicthermochemistry[M]1Beijing:SciencePress,19871502741)[5]UchidaS,KamoH,KubotaH,etal1ReactionkineticsofformationofHClinmunicipalrefuseincinerators[J]1IndEngChemProcDesDev,1983,22(1):14421491[6]UchidaS,KamoH,KubotaH1ThesourceofHClemissionfrommunicipalrefuseincinerators[J]1IndEngChemRes,1988,27(11):2188221901[7],1[J]1,1994,(4):242281(ZHANGHe2sheng,JIANRui2min1High2temperaturecorrosiononheatingsurfaceofmetaltubesinmunicipalsolidwastesincinera2tors[J]1EnergyTechnology,1994,(4):242281)[8]1[P]1:ZL2376579,20002052031(LINWei2gang1Double2diplegcirculatingfluidizedbedincineratorformunicipalsolidwastes[P]1Chinese:ZL2376579,20002052031)[9],,,1TG2DSC[J]1,2002,53(7):75927641(LIJi,ZHANGZheng,YANGXue2min,etal1TG2DSCstudyonpyrolysischaracteristicsofmunicipalsolidwastes[J]1JournalofChemicalIndustryandEngineering,2002,53(7):75927641)THERMODYNAMICSEQUILIBRIUMANALYSISOFMUNICIPALSOLIDWASTESINCINERATIONSYSTEMLIJi,YANGXue2min,LINWei2gang(Multiple2phaseReactionLaboratory,InstituteofProcessEngineering,ChineseAcademyofSciences,Beijing100080,China)Abstract:Incinerationhasbeenwidelyappliedoverthepastdecadefordisposalofmunicipalsolidwastes(MSWs)inChina1However,highchlorinecontentinMSWresultsintwomajorproblems:hightemperaturecorrosionandtheemissionofdioxins1Inthispaper,thermodynamicequilibriumcalculationswereperformedtorevealtheformationandtransformationofchlorine2containingcompoundsduringthermalconversionprocessofPVCandMSWsunderdifferentconditions1CalculationswerealsoappliedtothereactionsbetweenCa2basedsorbentsandchlorine2containingcom2pounds1TheresultsshowedthatHClwasthemainchlorinecontainingproductforPVC1ForMSWs,organicandinor2ganicchlorinecantransformintoHClgascompletelywhentemperaturewasover6001Ca2basedsorbentswaseffec2tiveontheHClremovalforPVCbutineffectiveforMSWsatthetemperatureofnormalincinerationconditions1There2fore,anewchlorine2removalprocesswasproposed,whichcanremovechlorineandrestraindioxinemissionsimulta2neously1Keywords:municipalsolidwastes;thermodynamicsequilibriumanalysis;HCl;Ca2basedsorbentsAuthorintroduction:LIJi(19732),male,DoctorcandidateofChemicalTechnology1E2mail:jli@home1ipe1ac1cn88531