废塑料热解—催化改质实验研究
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摘要
本文设计并搭建起一套小型的废塑料热解-催化改质实验装置,在校内实验与理论研究相结合的基础上对废塑料热裂解及其对裂解气催化改质进行了深入研究。本文通过实验证明,PP和LDPE均有自己的热裂解温度特性;研究了各种反应条件,如热解温度,催化剂的种类及其加入量,催化改质温度对PP和LDPE裂解的液体收率、残渣收率、不凝气收率以及汽油馏分、柴油馏分和重油馏分的影响。针对目前废塑料裂解中使用的催化剂昂贵以及种类少的现状,采用造粒、高温烧成工艺与添加造孔剂相结合的方法,制备轻质、球型、多孔粉煤灰陶粒催化剂。
A miniature-testing device with thermal pyrolysis-catalytic reforming of waste plastic was designed and constructed in this work,and based on the test in laboratory and theory,this work made a deep research on the pyrolysis of waste plastic and the catalytic reforming of cracking gas. Experiment demonstrated that PP and LDPE has its own special characteristic of thermal pyrolysis versus temperature. Effects of variety of reaction conditions such as the pyrolysis temperature, the kind of catalyst and the quantityof catalyst, catalytic reforming temperature, on the yields of liquid, carbon residue and gas, and the quantity of gasoline, diesel and heavy oil generated by pyrolysis of PP and LDPE were studied. Facing the fact that the catalyst used in the pyrolysis of waste plastic was costly and few, a light spherical porous biofiltering material was prepared from fly ash used as principal raw material,soil as adhesive agent and organic foaming agent via bailing and high temperature sintering.
A miniature-testing device with thermal pyrolysis-catalytic reforming of waste plastic was designed and constructed in this work,and based on the test in laboratory and theory,this work made a deep research on the pyrolysis of waste plastic and the catalytic reforming of cracking gas. Experiment demonstrated that PP and LDPE has its own special characteristic of thermal pyrolysis versus temperature. Effects of variety of reaction conditions such as the pyrolysis temperature, the kind of catalyst and the quantityof catalyst, catalytic reforming temperature, on the yields of liquid, carbon residue and gas, and the quantity of gasoline, diesel and heavy oil generated by pyrolysis of PP and LDPE were studied. Facing the fact that the catalyst used in the pyrolysis of waste plastic was costly and few, a light spherical porous biofiltering material was prepared from fly ash used as principal raw material,soil as adhesive agent and organic foaming agent via bailing and high temperature sintering.
引文
[1] Audet C, Langlet B. Plastic waste management :Disposal, recycling, and reuse(ed.Mustafa N). Marcel Dekker,1993,141
[2] Carroll W F,Goodman D.Plastics Recycling:Products and Processes(ed.Ehrig R .J).Hanser Publisher,1992,136
[3]村田德治.现代化学.1991,(12):42
[4] Moser M L,Lee D O.A fourteen-year survey of plastics ingestion by western North Atlantic seabirds.Colonial Waterbirds,1992,15(1):83-94
[5] Robard M D.Increasing frequency of plastic particles ingested by seabirds in the Subbartic North pacific.Mar.Pullut.Bull.,1995,30(1):151-157
[6] Arnould J P,Croxall J P.Trends in entanglem of Antarctic Fur Seal(Arctocephalus gazelle) in man-made debris at South Georgia .Mar. Pullut.Bull., 1995 ,30(4):707-712
[7]包永忠,朱慧芳.废塑料的回收利用.2002,20(3):11-14
[8] Wagner J P,El-Ayyoubl M A,Konzen R B. Heavy-metals emissin from controlled combustion of polyvinyl chloride plastics.Polym-plast. Technol.Eng.,1991 ,30(8):827-851
[9] Karasak F W,Viau A G,Guiocbon,G,Gonnord M F.Gas chromalographic mass-spactromatric study on the formation of polychlorinaled dibenzo-para-dioxins and polychlorobenzenes from polyvinyl chloride in a municipal incinerator. J.Chromatogr., 1983,270:227-234
[10] Collegman R T,Carroll W F,Figbbein L. Vinyl industy Response to environmental concern about PVC in Municipal Solid Waste. Energy Progess,1988,8(3):148-153
[11] William F,Carroll W F. PVC and incineration. J. Vinyl.Technol.,1988,10(2):90-94.
[12] Akira M.Chemical recycling polymer.1997,46(6):406-410
[13]森本尚夫.复合材料废弃物的再资源化技术.高分子加工,1997,46(2):88-93
[14] Scott D S, Czernik SR. Fast pyrolysis of plastic wastes. Energy and fuels.1990,4(4):407-411
[15]周继承.废旧聚苯乙烯泡沫塑料的回收利用.化学世界,1995,(2):63-67
[16] Scott D S,Majerski P,Piskorz J.Production of liquid fuels from waste plastics. Canadian Journal of Chemical Engineering, 1999,77(5):1021-1027
[17] Ciocco M V,Cugini A V,Wildman D J,et al.Rheology of coal/waste coprocessing mixtures.Powder Technology,1997,94(3):207-210
[18] Collin G,Bujnowska B,Polaczek J.Co-coking of coal with pitches and waste plastics.Fuel Processing Technology,1997,50(2-3):179-184
[19] Feng Z,Zhao J,Rockwell J,et al.Direct liquefaction of waste plastics and coliquefation of coal-plastic mixtures. Fuel Processing Technology ,1996,49(1-3):17-30
[20]戴星,王剑秋.我国废塑料油化技术的应用现状与前景.化工环保,2000,20(6):18-22
[21] Walendziewskj J, Steininger M. Thermal and catalytic conversion of waste polyolefines. Catalysis Today,2001,65(2-4):323-330
[22] Mcintosh M J, Arzoumanidis G G, Brockmeier F E.Recovery of fuels and chemicals through catalytic pyrolysis of plastic wastes.Enviromental Progress,1998,17(1):19-23
[23] Sakata Y,Uddin A,Muto A, Koizumi K,et al.Thermal and catalytic degradation of municipal waste plastics into fuel oil. Polymer Recycling, 1996,2(4):309-315
[24] Songip A R,Masuda T,Kuwanhara H,et al. Production of High-Quality Gasoline by Catalytic Cracking over Rare-Earth Metal Exchanged Y-type Zeolite of Heavy Oil from Waste Plastics.Energy and Fuels,1994,18(1):136-140
[25] Songip A R, Masuda T,Kuwanhara H, et al. Kinetic Studies for Catalytic Cracking of Heavy Oil over REY Zeolite.Energy and Fuels,1994,18(1):131-135
[26] Masuda T, Kuwahara H, Mukai S R, Hashimoto K. Production of high quality gasoline from waste polysthylene derived heavy oil over Ni-REY catalyst in steam atmosphere. Chem.Eng. Sci., 1998,54(13):2773-2779
[27]登蜀平,张健民,王洋.我国废塑料回收利用技术的发展.化工环保,1995,15(6):338-342
[28]曹志荣.流化床在废塑料回收生产中的应用.化学世界,1999,(8):444-446
[29]刘以荣.废聚苯乙烯的化学回收方法.化工环保,1999,18(6):332-337
[30] Veba P G.Apparatus for recovery of fuel oils from waste from plastics treatment.Umwelt,1993,23(5):301-302
[31] Botom P G. System of thermal decomposition of waste plastics for oil manufacture. Chemical Week, July21,1993
[32] Ono T,Tabele G,Kobayashi A, Matsuda A.Manufacture of aromatic hydrocarbon oils by pyrolysis of waste polyolefinic plastics.JP 04 180995,1991
[33] Ono T,Hirota T.Manufacture of low-boiling hydrocarbon oils.JP 0386790,1991
[34] Gotanda B S. Waste plastic treatment accompanied with no environmental pollution and thermal decomposition apparatus. Waste Manage Res, 1993,11(4):319-332
[35] Yamaguchi T.Apparatus for oil production from pyrolysis of waste plastics. JP 0450 292,1992
[36] Kurata H.Light oils from pyrolysis waste plastics.JP 05 279 673,1994
[37] Kurata H.Apparatus for production of heavy fuel oils from waste plastics.JP 05279 672,1994
[38] Kaminsky W,Menzel J,Sinn H. Method for aromatic hydrocarbon recovery from waste plastics.Cons.Rec.,1976,1
[39] Potts J E.In paper presented before the division of water,air and waste chemistry.ACS,Chicafo,1970
[40] Nishioka J. Apparatus for oil recovery from pyrolysis of waste plastics.JP 08 188 788,1996
[41] Takahashi T,Tanimoto Y.Thermal decomposition of plastic wastes using catalysis.EP 555 833,1993
[42] Kastner H,Kaminsky W.Recycle plastics into Feedstocks.Hydrocabon process,1995,74(5):109-112
[43]杨震,张惠珍.CN 1164542A,1997
[44]孙原恒,牧原洋.CN 1157296A,1996
[45]唐敖庆.高分子反应统计动力学.北京:科学出版社, 1985:366
[46]戴星,王剑秋,钱家戴.等温相继气相色谱法研究聚丙烯的热裂解.石油化工,1999,28(2):82-86
[47]戴星,王剑秋,钱家戴.等温相继气相色谱法研究聚丙烯高密度聚乙烯的热裂解.中国环境科学,1999,19(4):301-305
[48] Wu C H,Chang C Y,Hor J L,et al.On the thermal treatment of plastic mixtures of MSW:Pyrolysis kinetics.Waste management(N.Y),1993,13(3):221-235
[49] Willems P A,Freoment G F. Kinetics modeling of the thermal cracking of hydrocarbons,2 Calculation of Activation Energies.Ind Eng Chem Res,1988,(27):1966-1971
[50]角仕云,余建川,M衣库拉.液体废塑料热裂化转换过程动力学的研究与模型化.四川化工与腐蚀控制,1999,2(2):28-31
[51] Weekman V W.Kinetic and dynamics of catalytic cracking selectivity in fixed-bed reactors.Ind.Eng.Chem.,Process Des.Dev.,1969,8(3):385-391
[52] Oliverra L L,et al.Catalytic kinetic models:Parameter estimation and model evaluation.Ind.Eng.Chem.Res.,1989,28(3):264-271
[53] Leidner J.Plastic waster.Recycling of economic value.Marcel Dekker,1981,64
[54] Allen N S.Degradation and stabilizationg of polyolefines.Applied Science Publishers.1983
[55]芊振明,高忠爱,吴天宝.固体废物的处理与处置(修改版).北京:高等教育出版社,1993:209-228
[56] Zhou J.Zhang X.Co-processing of waste polyethylene with vacuum residue in delayed coking process.Preprints,1998,43(1):194-198
[57]戴星,王剑秋,钱家戴.聚乙烯聚丙烯树脂及废料的裂解.环境科学,1999,20(5):82-85
[58]杨震,江勇,王世明,等.废聚苯乙烯热降解回收苯乙烯单体的研究.环境科学,1997,18(2):43-45
[59] Ohkita H, Nishiyama R,Tochihara Y,et al.Acid Properties of silica-alumina catalysts.Bull. Chem.Soc.Jpn.,1983,56(9):2768-2773
[60] Songip A R,Masuda T,Kuwahara et al. K.Test to screen catalysts for reforming heavy oil from waste plastics.Appl.Catal.B.Environ.,1993,(2):153-164
[61] Songip A R,Masuda T,Kuwahara et al. Production for producing hydracabon catalytic cracking over REY zeolites of heavy oil from waste plastics.Energy and Fuels,1994,8(1):136-140
[62]杨震,乔维川,张晋华,等.聚烯烃类废塑料分解技术中催化剂的选择和机理初探.环境科学,1998,19(5):48-51
[63] Uemichi Y, Kashiwaya T, Tsukidate M, et al. Priduct distribution of polypropylene over silica-alumina and CaX zeolite catalysts.Bull. Chem. Soc.Jpn.,1983,56(9):2768-2773
[64]李稳宏,李逸红.废塑料降解工艺过程催化剂的应用研究.石油化工,2000,29(5):344-346
[65]戴星,王剑秋,钱家戴.聚丙烯油化催化剂的研制与性能.石油化工,1999,28(10):681-685
[66] Arandes J M,Abajo I,Valerio D L,et al.,Thermodynamic simulation pyrolysis of plastics at elevated temperatures.Ind. Eng.Res.,1997,36(11):4523-4529
[67]席国喜,梁蕊,汤清虎,等.废聚苯乙烯裂解催化剂的筛选及工艺条件的优化.环境科学研究,1999,12(3):60-61
[68]毕明树,王淑兰,丁信伟.废塑料油化技术综述.节能,2000,(3):40-41
[69]许翩翩,张藩贤.废旧塑料催化裂解制取汽油.1998,18(1):20-24
[2] Carroll W F,Goodman D.Plastics Recycling:Products and Processes(ed.Ehrig R .J).Hanser Publisher,1992,136
[3]村田德治.现代化学.1991,(12):42
[4] Moser M L,Lee D O.A fourteen-year survey of plastics ingestion by western North Atlantic seabirds.Colonial Waterbirds,1992,15(1):83-94
[5] Robard M D.Increasing frequency of plastic particles ingested by seabirds in the Subbartic North pacific.Mar.Pullut.Bull.,1995,30(1):151-157
[6] Arnould J P,Croxall J P.Trends in entanglem of Antarctic Fur Seal(Arctocephalus gazelle) in man-made debris at South Georgia .Mar. Pullut.Bull., 1995 ,30(4):707-712
[7]包永忠,朱慧芳.废塑料的回收利用.2002,20(3):11-14
[8] Wagner J P,El-Ayyoubl M A,Konzen R B. Heavy-metals emissin from controlled combustion of polyvinyl chloride plastics.Polym-plast. Technol.Eng.,1991 ,30(8):827-851
[9] Karasak F W,Viau A G,Guiocbon,G,Gonnord M F.Gas chromalographic mass-spactromatric study on the formation of polychlorinaled dibenzo-para-dioxins and polychlorobenzenes from polyvinyl chloride in a municipal incinerator. J.Chromatogr., 1983,270:227-234
[10] Collegman R T,Carroll W F,Figbbein L. Vinyl industy Response to environmental concern about PVC in Municipal Solid Waste. Energy Progess,1988,8(3):148-153
[11] William F,Carroll W F. PVC and incineration. J. Vinyl.Technol.,1988,10(2):90-94.
[12] Akira M.Chemical recycling polymer.1997,46(6):406-410
[13]森本尚夫.复合材料废弃物的再资源化技术.高分子加工,1997,46(2):88-93
[14] Scott D S, Czernik SR. Fast pyrolysis of plastic wastes. Energy and fuels.1990,4(4):407-411
[15]周继承.废旧聚苯乙烯泡沫塑料的回收利用.化学世界,1995,(2):63-67
[16] Scott D S,Majerski P,Piskorz J.Production of liquid fuels from waste plastics. Canadian Journal of Chemical Engineering, 1999,77(5):1021-1027
[17] Ciocco M V,Cugini A V,Wildman D J,et al.Rheology of coal/waste coprocessing mixtures.Powder Technology,1997,94(3):207-210
[18] Collin G,Bujnowska B,Polaczek J.Co-coking of coal with pitches and waste plastics.Fuel Processing Technology,1997,50(2-3):179-184
[19] Feng Z,Zhao J,Rockwell J,et al.Direct liquefaction of waste plastics and coliquefation of coal-plastic mixtures. Fuel Processing Technology ,1996,49(1-3):17-30
[20]戴星,王剑秋.我国废塑料油化技术的应用现状与前景.化工环保,2000,20(6):18-22
[21] Walendziewskj J, Steininger M. Thermal and catalytic conversion of waste polyolefines. Catalysis Today,2001,65(2-4):323-330
[22] Mcintosh M J, Arzoumanidis G G, Brockmeier F E.Recovery of fuels and chemicals through catalytic pyrolysis of plastic wastes.Enviromental Progress,1998,17(1):19-23
[23] Sakata Y,Uddin A,Muto A, Koizumi K,et al.Thermal and catalytic degradation of municipal waste plastics into fuel oil. Polymer Recycling, 1996,2(4):309-315
[24] Songip A R,Masuda T,Kuwanhara H,et al. Production of High-Quality Gasoline by Catalytic Cracking over Rare-Earth Metal Exchanged Y-type Zeolite of Heavy Oil from Waste Plastics.Energy and Fuels,1994,18(1):136-140
[25] Songip A R, Masuda T,Kuwanhara H, et al. Kinetic Studies for Catalytic Cracking of Heavy Oil over REY Zeolite.Energy and Fuels,1994,18(1):131-135
[26] Masuda T, Kuwahara H, Mukai S R, Hashimoto K. Production of high quality gasoline from waste polysthylene derived heavy oil over Ni-REY catalyst in steam atmosphere. Chem.Eng. Sci., 1998,54(13):2773-2779
[27]登蜀平,张健民,王洋.我国废塑料回收利用技术的发展.化工环保,1995,15(6):338-342
[28]曹志荣.流化床在废塑料回收生产中的应用.化学世界,1999,(8):444-446
[29]刘以荣.废聚苯乙烯的化学回收方法.化工环保,1999,18(6):332-337
[30] Veba P G.Apparatus for recovery of fuel oils from waste from plastics treatment.Umwelt,1993,23(5):301-302
[31] Botom P G. System of thermal decomposition of waste plastics for oil manufacture. Chemical Week, July21,1993
[32] Ono T,Tabele G,Kobayashi A, Matsuda A.Manufacture of aromatic hydrocarbon oils by pyrolysis of waste polyolefinic plastics.JP 04 180995,1991
[33] Ono T,Hirota T.Manufacture of low-boiling hydrocarbon oils.JP 0386790,1991
[34] Gotanda B S. Waste plastic treatment accompanied with no environmental pollution and thermal decomposition apparatus. Waste Manage Res, 1993,11(4):319-332
[35] Yamaguchi T.Apparatus for oil production from pyrolysis of waste plastics. JP 0450 292,1992
[36] Kurata H.Light oils from pyrolysis waste plastics.JP 05 279 673,1994
[37] Kurata H.Apparatus for production of heavy fuel oils from waste plastics.JP 05279 672,1994
[38] Kaminsky W,Menzel J,Sinn H. Method for aromatic hydrocarbon recovery from waste plastics.Cons.Rec.,1976,1
[39] Potts J E.In paper presented before the division of water,air and waste chemistry.ACS,Chicafo,1970
[40] Nishioka J. Apparatus for oil recovery from pyrolysis of waste plastics.JP 08 188 788,1996
[41] Takahashi T,Tanimoto Y.Thermal decomposition of plastic wastes using catalysis.EP 555 833,1993
[42] Kastner H,Kaminsky W.Recycle plastics into Feedstocks.Hydrocabon process,1995,74(5):109-112
[43]杨震,张惠珍.CN 1164542A,1997
[44]孙原恒,牧原洋.CN 1157296A,1996
[45]唐敖庆.高分子反应统计动力学.北京:科学出版社, 1985:366
[46]戴星,王剑秋,钱家戴.等温相继气相色谱法研究聚丙烯的热裂解.石油化工,1999,28(2):82-86
[47]戴星,王剑秋,钱家戴.等温相继气相色谱法研究聚丙烯高密度聚乙烯的热裂解.中国环境科学,1999,19(4):301-305
[48] Wu C H,Chang C Y,Hor J L,et al.On the thermal treatment of plastic mixtures of MSW:Pyrolysis kinetics.Waste management(N.Y),1993,13(3):221-235
[49] Willems P A,Freoment G F. Kinetics modeling of the thermal cracking of hydrocarbons,2 Calculation of Activation Energies.Ind Eng Chem Res,1988,(27):1966-1971
[50]角仕云,余建川,M衣库拉.液体废塑料热裂化转换过程动力学的研究与模型化.四川化工与腐蚀控制,1999,2(2):28-31
[51] Weekman V W.Kinetic and dynamics of catalytic cracking selectivity in fixed-bed reactors.Ind.Eng.Chem.,Process Des.Dev.,1969,8(3):385-391
[52] Oliverra L L,et al.Catalytic kinetic models:Parameter estimation and model evaluation.Ind.Eng.Chem.Res.,1989,28(3):264-271
[53] Leidner J.Plastic waster.Recycling of economic value.Marcel Dekker,1981,64
[54] Allen N S.Degradation and stabilizationg of polyolefines.Applied Science Publishers.1983
[55]芊振明,高忠爱,吴天宝.固体废物的处理与处置(修改版).北京:高等教育出版社,1993:209-228
[56] Zhou J.Zhang X.Co-processing of waste polyethylene with vacuum residue in delayed coking process.Preprints,1998,43(1):194-198
[57]戴星,王剑秋,钱家戴.聚乙烯聚丙烯树脂及废料的裂解.环境科学,1999,20(5):82-85
[58]杨震,江勇,王世明,等.废聚苯乙烯热降解回收苯乙烯单体的研究.环境科学,1997,18(2):43-45
[59] Ohkita H, Nishiyama R,Tochihara Y,et al.Acid Properties of silica-alumina catalysts.Bull. Chem.Soc.Jpn.,1983,56(9):2768-2773
[60] Songip A R,Masuda T,Kuwahara et al. K.Test to screen catalysts for reforming heavy oil from waste plastics.Appl.Catal.B.Environ.,1993,(2):153-164
[61] Songip A R,Masuda T,Kuwahara et al. Production for producing hydracabon catalytic cracking over REY zeolites of heavy oil from waste plastics.Energy and Fuels,1994,8(1):136-140
[62]杨震,乔维川,张晋华,等.聚烯烃类废塑料分解技术中催化剂的选择和机理初探.环境科学,1998,19(5):48-51
[63] Uemichi Y, Kashiwaya T, Tsukidate M, et al. Priduct distribution of polypropylene over silica-alumina and CaX zeolite catalysts.Bull. Chem. Soc.Jpn.,1983,56(9):2768-2773
[64]李稳宏,李逸红.废塑料降解工艺过程催化剂的应用研究.石油化工,2000,29(5):344-346
[65]戴星,王剑秋,钱家戴.聚丙烯油化催化剂的研制与性能.石油化工,1999,28(10):681-685
[66] Arandes J M,Abajo I,Valerio D L,et al.,Thermodynamic simulation pyrolysis of plastics at elevated temperatures.Ind. Eng.Res.,1997,36(11):4523-4529
[67]席国喜,梁蕊,汤清虎,等.废聚苯乙烯裂解催化剂的筛选及工艺条件的优化.环境科学研究,1999,12(3):60-61
[68]毕明树,王淑兰,丁信伟.废塑料油化技术综述.节能,2000,(3):40-41
[69]许翩翩,张藩贤.废旧塑料催化裂解制取汽油.1998,18(1):20-24