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Ta OiAN2auA TD0xiCi E1110i TH2AE o ieEsuA-0vaE, Delgado HE 280U0a0-y2Aae 120 DD AEO fua 0u30 i UFo iaoDo OD EUAi HAt1 a ola1000÷BA1B0xNEA·“0HA旺TA2uA,上,02、9官AE0 HAleEANv2a;>D0ApA1D0a10和041,EE10AA00BAA×eE±10始aA00°x0距, 1eAAB3 vAHA 1D0210‰±1±f2Eu0Aa,00 B-4AHAxe3E°±f0Table 2 Properties of tested catalysts■ Inert■ DolomiteCatalystsParticle Specific surface Compositiono CalciteNickelAl2O3 SupportSilica-aluminaActivated alumina 3--4Al2O: 99i41 0A2,1-"B" 0 i UEo iaODuA%1019-AiDolomitMgO 12Fig. 1 Effect of catalyst on tar content in outlet gas±i1 Eyooli ExA03。- yAHAxe3Ey°±fAC°,±0800a0 Aae12o DD AEOT HA1ax÷,啊Table 1 Some properties of the"NaturallyEy02A0μAN6。E、№x-1d、N6》AA°ImbNOccurring” catalyst1e和010μANa1D0‰0DAEN%,· c IOlCAn6CompositionParticle SpecificiNE0μ AHuAN6、E10 ANhua10xc,N6ACatalystsCao Mgo co/mm /m?/g calcining Calcineddiameter surface9IWbN。-1e02±036AEAμANaD053.00.641.91.0~2.00. 1 5.4 4 100U101ANVaHA AH NS ii0Magnesite o.747.152.01.0~2.0中国煤化工 Suuberg HE30 ia°6A000i410:E00d36,世0A°x0(A框T880TACNMHGC)>0A0Bx 2A ( IA E1740C)x0 2AlEt, 30iUN,=(UCPIx)/(RPo)Eo iaodHA1019-Ai EUoU 500 mg/m; o OAE- EoEl EEE OAOUN', BHACe iO IA, E1OD: PI=5(爬eoAI)x6"2AIE土,E10U900CE±,1019756eXp(-25M3T);N—1010Dxe·0iEE00,數据AiTuirAi; D--121oioUFEo laoduAAoEc lHEy; cxI96, HAWHAITAluA TD0E3DoEc IA: Ao"3AA￡0USo1aA和A0;P1xe0iA0N1100A±0EEEa。0-1y3101 OI ANYaANExAA￡AUxe0iATa啊9A;PmA0s100U1101uABx"AN%aEUAE, Corella HE[32]ia30AEolax0N1A;R—AAE0;M1x·0iAA和00AEx0:EA;T—TAr= dm/(wdt)=k, exp(- E/RT)CAnOEETEiEoO"30: HtEo laN1AH P.+, 101 ENOD: r-110iAN%aEUAE: m--1101OEAi: CA0÷xe·0μAA0f"AN1050,±a0U10pA036,E110A脏;2—B,ACEA;kEUA10A.0×0A·0243×A.0×0ATBA100ER—iaEy;T—ANTA哐;E100010函ANa印UAE, Serio Hl1a36E0A005ao0IAE2×O±iEIn(1-x)=-kot exp(- E/RT)EE%aE0"11 AN aHAND%i Oy oUoy EO EEACHA10E0D:x-12101×aAE0.c°00×0;t1×,Ec9TE111官 leE HAANv2aEC0096Be010,2h0A6E±a;E了A0;R— Eo iaeE;TND‰A·z0.-E土,10N0,-.°aEB-A啊为1ANa IA爬EoiHA'3"uAi02E0OD'yiv io21 i IA Ix11uc.A2xNs.±±0:Nsa0u36°Ec,1992.2210E÷2A.A°1a1a0N,±4:-Ns1aou36°aEc,19923 0108Aa, By2uEu A',"NSEToE: EToE lENS AM E0302 Ec, 1984.220i Yu L E, Hildemann L M, DaDamio j et al. Characterization of Coal Tar Organics via Gravity Flow Column ChromatographFuel,1998,77:437~4455 Garcia X A. Alarcon N A. Gordon A L. Steam Gasification of Tars Using a CaO Catalyst. Fuel Processing Technology, 199958:1016 Narvaez I, Orio A, Aznar M P et al. Biomass Gasification with Air in an Atmospheric Bubbling Fluidized Bed Effect of SixOperational variables on the Quality of the produGas, Ind Eng Chem Res, 1996, 35: 1157 Seshadri KS, Shamsi A. Effets of Tempeture, Pressure and Carrier Gas on the Cracking of Coal Tar over a Char-DolomiteMixture and Calcined Dolomite in a Fixed-Bed Reactor. Ind Eng Chem Res, 1998,37: 3830--38378 Stiles H N, Kandiyoti R. Secondary Reactions of Flash Pyrolysis Tars Measured in a Fluidized Bed Pyrolysis Reactor withFucl,1989,68:275~28Flash Pyrolysis of Coals Devolatilization of Bituminous Coals in a Small Fluidized Bed Reactor. Fuel, 1980.59: 225o Wornat, Nelson. Effect of lon-Exchanged Calcium on Brown Coal Tar. Energy and Fuels, 1992.6: 136-14211 Li Chunzhu, Bartle K D, Kandiyoti R. Vacuum Pyrolysis of Maceral Concentrates in a Wire-Mesh Reactor. Fuel, 1993, 72:1459~146712 Unger P E, Suuberg E M. Molecular Weight Distributions of Tars Produced by Flash Pyrolysis of Coals, Fuel,1984,63: 60613 Suuberg E M, Unger P E, Lilly W D. Experimental Study on Mass Transfer from Pyrolysing Coal Particles. Fuel, 1985,6414 Messenbock R C, Dugwell D R, Kandiyoti R. COz and Stesm Gasification in a High-Pressure Wire-Mesh Reactor: TheReactivity of Daw Mill Coal and Combustion Reactivity of its Chars. Fuel. 1999.78:79215 Unger P E. Suuberg E M. Molecular Weight Distributions of Tar Produced by Flash Pyrolysis of Coals. Fuel, 1984.63: 61016 Sathe C. Pang Yanyuan, Li Chunzhu. Effects of Heating Rate and lon-Exchangeable Cations on the Pyrolysis Yields from aVictorian Brown Coal. Energy and Fuels, 1999,13: 748--75517 Katheklakis L. E, Iu Shilin, Bartle K D ef al. Effect of Freeboard Residence Time on the Molecular Mass Distributions ofFluidized Bed Pyrolysis Tars, Fuel,1990.69: 172-176中国煤化工18 Williams P T. Besler S, Taylor D T. The Pyrolysis of Scrap AutCNMHG7I-I48119 Bruinsma OS L, Geertsma R S, Bank P et al. Gas Phase pyrolysed Aromatic Compounds in a Coiled TubeFlow Reactor, Fuel. 1988. 67: 32920 Simell P A, Hepola J O, Krause A O. Effects of Gasification Gas Components on Tar and Ammonia Decomposition over HeGas Cleanup Catalysts, Fuel21A万方数掘N。,El0IA010:09xe0pB-ANa.a,a"0NsNs±“(x0 EniENS a),197,37(2):6~1022FH D, Peters WA, Howard J B. Mineral Matter Effects on the Rapid Pyrolysis and Hydropyrolysis of a Bituminou62000AeCoal 1: Effects on Yields of Char, Tar and Light Gaseous Volatiles, Fuel, 1982, 61: 155-16023 Khan M R, Seshadri K. Cpmpositional Changes in the Mild Gasification Liquids Produced in the Presence of Calcium240U.N6,E啊A2AAEy310°AN死:[NTA0TA.1-:01EN091÷AL”NNE,1999Corella J, Orio A, Toledo J M. Biomass Gasification with Air in a Fluidized Bed: Exhaustive Tar Elimination withmmercial Steam Reforming Catalysts, Energy and Fuels, 1999, 13: 702-726 Corella J, Orio A, Annar P. Biomass Gasification with Air in a Fluidized Bed: Reforming of The Gas CompoCommercial Steam Reforming Catalysts. Ind Eng Chem Res, 1998.37: 4617--4624ci0死,A+-B-AN。,p2°,±:ib101a36°a8 Delgado J, Aznar M P, Corella J, Calcined Dolomite, Magnesite, Calcite for Cleaning Hot Gas from a Fluidized Bed BiomassGasifier with Steam: Life and Usefulness. Ind Eng Chem Res, 1996.35,3637--364329 Simell P A, son Bredenberg B J. Catalytic Purification of Tarry Fuel Gas. Fuel.1990. 69: 1219-122530 Suuberg E M. Unger P E. Lilly W D. Experimental Study on Mass Transfer from Pyrolysing Coal Particles. Fuel,1985.6431 Serio M A, Peters W A, Howard T B. Kinetics of vapor-Phase Secondary Reactions of Prompt Coal Pyrolysis Tars. Ind EngChem res,1987,26:183432 Corella J, Aznar M P, Delgada J et al. Steam Gasification of Cellulosic Wastes in a Fluidized Bed with Downstream VesselsInd Eng Chem Res, 1991, 30: 2260STUDY ON TAR CRACKING IN PYROLYSIS ORGASIFICATION PROCESSJia Yongbin Zhang Shouyu Cheng Zhonghu Huang Jie jie and Wang Yang(Institute of Coal Chemistry, Chinese Acade2o01rV山中国煤化工ABSTRACT Tar cracking in pyrolysis or galCNMHGiewed. Effects oftemperature, pressure, atmosphere, residence time and heating rate on tar cracking arediscussed. Effects of the catalyst of Cao on tar cracking are also discussed and activities ofdifferent catalysts are compairedK数帮 rds tar crackin, pyrolysis,gtn