还原法二氧化硫脱除技术师吉辉

师吉辉　曾抗美　尹华强　杨基成(,610065)　　、CaS、、、,。　　　TechniquesforremovalofSO2fromfluegasbyreductionShiJihui　ZengKangmei　YinHuaqiang　YangJicheng(ArchitectureandEnvironmentInstitute,SichuanUniversity,Chengdu610065)Abstract　TheremovalofSO2fromfluegasisveryimportantfortheenvironmentalprotection.TheprogressofSO2removalfromfluegasbyreductionwaywasintroduced,includingcatalyticreduction,CaSreduction,adsorptionreduction,carbonreductionandmicrobereduction.Theirworkingprinciplesandmainstrongpointswerealsore-viewed.Keywords　reduction;fluegasdesulfurization;SO2:2003-06-03;:2003-07-21:(1973～),,,。E-mail:[e-mail]　　SO2。[1],1100。,SO2。,19992.5×106t,,SO2,,。,。,CaSO4,、、、。SO2,。,,SO2,———,。1　1.1　SO2,2030,、H2、CO、NH3CH4。1.1.1　H2还原法,H2SO2,[2]:SO2+2H2※S+2H2OS+H2※H2S2H2S+SO2※3S+2H2O,480℃,H2/SO22.2,FeAl2O3,SO277%,40%。H2/SO23,。300℃,3000L/(kg·h),80%。H2。,,H2S(300℃)SO2,H2,SO2。H2,,,。1.1.2　CO还原法COSO2,CO,,,、,NOx,CO,55Vol.5,No.520045TechniquesandEquipmentforEnvironmentalPollutionControlMay2004,,(400～800℃),。COSO2:SO2+2CO※2CO2+SxCO+Sx※COS2COS+SO2※2CO+Sxx=2～8。COS,SO2,。、Cu、Fe、Ni、Pd/Al2O3Fe/Cr2O3。[3],γ-Al2O3,Fe。La1-xSrxCoO3(x=0.3、0.5、0.60.7),x=0.3,COS。CeO2CuCu-Ce-OSO2CO,450℃CO/SO2=295%,。Ma[4,5],La2O3La2O2S,SO2NOx,95%。1.1.3　合成气法SO2,,。,,,。COH230%SO2,420～550℃,。1.2　,。SO2。Ma[6]CO,SO2。O2,:CO+S※COSO2+S※SO2CO+1/2O2※CO2。,。Fang[7]。,,。,。,,(90%),COSO2NOx。SO2、SO3NOxH2SO3、H2SO4HNOx+1。,,H2SO3、H2SO4、HNOx+1,。SO2NOx96%,98%。,2%10%,。1.3　-。,,,,。,CO,。:CO2CO+1/2O21/2SO2+CO,1/2S+CO2CO+1/2O2※CO2SO2+O2※SO3[8]Fe2O3/γ-Al2O3,,SO2,,SO285%,。。1.4　,。。,,,;,,,;,,H2、COSO2,SO2CO2H2O,。SO2NOx,SO2。765、,。2　CaSCaS[9,10]HongYongSohn、、。CaS,SO2,CaSO4S。CaSO4CaS,。:CaS(s)+2SO2(g)=CaSO4(s)+S2(g)CaS(s)+1/2SO2(g)=CaO(s)+3/4S2(g)CaS(s)+3CaSO4(s)=4CaO(s)+4SO2(g)3/2CaS(s)+1/2CaSO4(s)=2CaO(s)+S2(g)CaSO4(s)=CaO(s)+SO3(g)CaSO4(s)=CaO(s)+SO2(g)+1/2O2(g)(2)～(6)1000K,ΔG0。CaS:CaSO4(s)+4H2(g)=CaS(s)+4H2O(g),1153K,SO225.8kPa,20min75%CaSCaSO4。SO2S。,Ni,1123K,86.1kPa,20min,95%CaSO4CaS。10,CaSO4CaS。,X,CaSO4CaS,。,。3　3.1　Na2S　　,SO2,,,,SO2、,。[11][12]FGD,Na2S--Na2S。Na2S,SO2H2S,Claus,Na2SNa2SO3。:5SO2+5H2O※5H2SO33H2SO3+3Na2S※3Na2SO3+3H2SH2S+Na2S※2NaHS2H2S+SO2※3S+2H2O3S+3Na2SO3※3Na2S2O32NaHS+2H2SO3※2NaHSO3+2H2S:6SO2+4Na2S+3H2O※3Na2S2O3+NaHSO3+2H2S,Na2SSO2,,Na2SSO2Na2S2O3NaH-SO3H2S。,SO21%～50%,Na2S,。:pH2.0～3.0,Na2S0.4mol/L,SO2300～600mL/min,,,SO299.8%。,pH,2.0～3.0,,。3.2　Na2CO3　　Na2CO3[13,14],。Na2CO3/γ-Al2O3、。,、、/。、。HongshanShang[15]Na2CO3(0.28mm)。:Na2CO3/+SO280～100℃Na2SO3/+CO2Na2SO3/S+Na2CO3+H2O,80%(W/W)Na2CO3/Na2CO3/γ-Al2O35.4,80.6%。70～300℃,,,,Na2CO3。4　4.1　　　SO2,775::C+SO2※S+CO2。,,,,。Cesar[16]———、Blackwood、Stein-er,。,,700～800℃。,,,。4.2　[17]　　1966,,,。,NOx,,。、,。,。SO2。15%SO2,,。,1990。4.3　-,。[18],3/4(3/4λ),。,,SO2(SO2+C=CO2+S),SO2CO2。,---SO2。、SO2。:,,CO2,。,,,,,。5　1864,Barton[19]。5.1　　　SO2、;,(SRB)、;,。2,SO2[20～22]。5.1.1　吸收SO2的工作原理,,SO2,、。、pH、,。:SO2(g)SO2(l)SO2(l)+H2OHSO-3+H+HSO-3SO2-3+H+2SO2-3+O※2SO2-4,SO2H+。,H+,。5.1.2　含硫吸收液生物脱硫的工作原理,:SO2-4+4H2※HS-+OH-+3H2O,:2HS-+O2※2S0+2OH-,,pH,。5.2　Bio-FGD,Bio-FGD。1992HTSEW&EPaques(Bio-FGD),。Bio-FGD12SO2。SO2785。,S,1。1　Bio-FGDFig.1　FlowdiagramofBio-FGD　　,。,,;SO2、pH。(TC),(SRB),,。。,S。,pH,SO2pH。,,。。,92%。,675%SO2,25%。6,6.0kgSO2/h,SO2。,。,。5.3　Bio-FGDBio-FGD3,、。,,。,Marc[23]2。,,。SO2,,,SO2-3SO2-4。SO2-3SO2-4,S。,CO2,,pH。,SO2300～1000mg/L,6sSO2100%,SO280%。NOx,5%～20%。。5.4　/(LSFO)30%,98%,、,、。Bio-FGD(,);();。6　(1),795:,,,。。(2),,,;,,,,。(3)、CaS-,,,。(4),,Bio-FGD,、、、,Bio-FGD。[1],..:,2001[2]PaikS.C.,KimH.,ChungJ.S.CatalyticreductionofSO2toelementalsulfurwithH2orCO.CatalysisToday,1997,38(2):193～198[3],,,.SO2.,2001,29(6):499～503[4]MaJ.,FangM.,LauN.T.ActivationofLa2O3forthecatalyticreductionofSO2byCO.JournalofCatalysis,1996,163(2):271～278[5]M.Fang,J.Ma.Catalyticremovalofsulfurdioxidefromfluegas,USPatent5,1998,853;684[6]MaJ.,FangM.,LauN.T.ThecatalyticreductionofSO2byCOoverlanthanumoxysulphide.Appl.Catal.,1997,150(2):253～268[7]FangM.,MaJ.,LauN.T.,etal.Applicationofcoalgasifi-cationtechnologyasafluegaspre-conditioningstepforthecatalyticreductionofacidgases.ChemicalEngineeringJour-nal,2002,87(3):395～402[8],,,.-SO2.,1998,26(5):395～399[9]HongYongSohn,Byung-SuKim.Anovelcyclicreactionsys-teminvolvingCaSandCaSO4forconvertingsulfurdioxidetoel-ementalsulfurwithoutgeneratingsecondarypollutants.1.Deter-minationofprocessfeasibility.Ind.Eng.Chem.Res.,2002,41(13):3081～3086[10]HongYongSohn,Byung-SuKim.AnewprocessforconvertingSO2tosulfurwithoutgeneratingsecondarypollutantsthroughreactionsinvolvingCaSandCaSO4.Enviro.Sci.Technol.,2002,36(13):3020～3024[11],,.———.(),1997,(2):6～8[12],,DondaldW.Kirk..,1997,20(2):158～161[13]XuG.,LuoG.,AkamatsuH.,etal.Adaptivesorbentforthecombineddesulfurization/denitrationprocessusingapowder-particlefluidizedbed.Ind.Eng.Chem.Res.,2000,39(7):2190～2198[14]Cig∨demGǜldǜr,GǜlsenDog∨u,TimurDog∨u.Kineticsoftronasulfurdioxidereaction.Chem.Eng.Proc.,2001,40(1):13～18[15]HongshanShang,TiOuyang,FanYang,etal.Abiomass-sup-portedNa2CO3sorbentforfluegasdesulfurization.Environ.Sci.Technol.,2003,37(11):2596～2599[16]CesarA.,Bejarano,CharlesQ.Jia.AStudyoncarbothermalreductionofsulfurdioxidetoelementalsulfurusingoilsandsfluidcoke.Enviro