混合塑料热裂解和催化裂解的工艺研究
|
摘要
对混合塑料[m(聚乙烯)∶m(聚丙烯)∶m(聚苯乙烯)为13∶6∶6]分别进行热裂解与催化裂解,考察了裂解温度和催化剂用量(占混合塑料的质量分数)对产物分布及汽油和柴油收率的影响,并采用色谱模拟蒸馏技术测定液相产物的馏程。结果表明:在裂解温度为420~460℃时,混合塑料热裂解得到的汽油、柴油收率估算值分别为38.6%~44.5%,14.8%~19.3%,催化裂解得到的两者收率估算值分别为39.8%~54.8%,14.9%~15.7%;在相同的裂解温度下,催化裂解得到的汽油收率略高于热裂解的;在最佳裂解温度(460℃)下,当催化剂用量为5%~20%时,液相产物收率为60.0%~77.9%,汽油、柴油收率估算值分别为39.3%~62.4%,15.6%~28.9%;催化剂用量以20%为宜;在催化剂用量为5%时,采用再生催化裂化(FCC)催化剂裂解得到的产物品质与采用新鲜FCC催化剂的相近。
The mixed plastics [m( polyethylene) ∶m( polypropylene) ∶ m( polystyrene) 13 ∶ 6 ∶ 6]were processed by thermal cracking and catalytic cracking respectively,the effects of cracking temperature and catalyst amount( mass fraction of mixed plastics) on distribution and gasoline and diesel yields were investigated,and the distillation range was determined by the gas chromatography simulation distillation technology. The results showed that when the cracking temperature was 420-460 ℃,the estimated yields of gasoline and diesel processed by thermal cracking were 38. 6%-44. 5%,14. 8%-19. 3%respectively,those processed by catalytic cracking were 39. 8%-54. 8%,14. 9%-15. 7% in turn;under the condition of the same cracking temperature,the gasoline yield by catalytic cracking was higher than that by thermal cracking; under the condition of optimum cracking temperature( 460 ℃),the catalyst amount( 5%-20%),the yields of liquid product were 60. 0%-77. 9%,the estimated yields of gasoline and diesel were 39. 3%-62. 4%,15. 6%-28. 9% respectively; the optimum catalyst amount was 20%; when the catalyst amount was5%,the properties of product obtained by regenerated fluid catalytic catalyst were similar with those of fresh FCC catalyst.
The mixed plastics [m( polyethylene) ∶m( polypropylene) ∶ m( polystyrene) 13 ∶ 6 ∶ 6]were processed by thermal cracking and catalytic cracking respectively,the effects of cracking temperature and catalyst amount( mass fraction of mixed plastics) on distribution and gasoline and diesel yields were investigated,and the distillation range was determined by the gas chromatography simulation distillation technology. The results showed that when the cracking temperature was 420-460 ℃,the estimated yields of gasoline and diesel processed by thermal cracking were 38. 6%-44. 5%,14. 8%-19. 3%respectively,those processed by catalytic cracking were 39. 8%-54. 8%,14. 9%-15. 7% in turn;under the condition of the same cracking temperature,the gasoline yield by catalytic cracking was higher than that by thermal cracking; under the condition of optimum cracking temperature( 460 ℃),the catalyst amount( 5%-20%),the yields of liquid product were 60. 0%-77. 9%,the estimated yields of gasoline and diesel were 39. 3%-62. 4%,15. 6%-28. 9% respectively; the optimum catalyst amount was 20%; when the catalyst amount was5%,the properties of product obtained by regenerated fluid catalytic catalyst were similar with those of fresh FCC catalyst.
引文
[1]王雷,罗国华,李强.塑料裂解技术进展[J].化工进展,2003,22(2):130-134.
[2]柴国梁.探讨塑料的市场现状与发展趋势(上)[J].上海化工,2008,33(1):39-41.
[3]Carroll W F,Goodman D.Plastics recycling:Products and processes[M].Munich:Hanser Publisher,1992:136.
[4]王永耀.聚乙烯、聚丙烯塑料回收利用进展[J].石油化工,2003,32(8):718-723.
[5]刘博洋,周华兰,夏峰峰,等.塑料制油技术研究及其产业化进展[J].化工进展,2017,36(Z 1):416-427.
[6]刘贤响.一种催化裂解塑料制燃料油的催化剂:中国,101024776[P].2007-08-29.
[7]刘治猛,蒋欣,刘煜平.利用回收聚苯乙烯裂解制苯乙烯单体[J].石油化工,2003,32(10):885-891.
[8]Wu Shikui,Xu Kaixiong,Jiang Lusen,et al.The co-cracking experiment and application route of waste plastics and heavy oil[J].AASRI Procedia,2014(7):231.
[9]Kunwar B,Cheng H N,Chandrashekaran S R,et al.Plastics to fuel:A review[J].Renew Sust Energ Rev,2016(54):421-428.
[10]杨基和,姚致远,严明亮,等.塑料制备燃料油热裂解与催化裂解工艺研究比较[J].江苏石油化工学院学报,2002,14(3):12-14.
[11]李晓祥,石炎福,余华瑞.塑料催化裂解制燃料油[J].化工环保,2002,22(2):90-94.
[12]Demirbas A.Pyrolysis of municipal plastic wastes for recovery of gasoline-range hydrocarbons[J].J Anal Appl Pyrol,2004(72):97-102.
[13]Kaminsky W,Schlesselmann B,Simon C M.Thermal degradation of mixed plastic waste to aromatics and gas[J].Polym Degrad Stab,1996(53):189-197.
[14]Grause G,Matsumoto S,Kameda T,et al.Pyrolysis of mixed plastics in a fluidized bed of hard burnt lime[J].Ind Eng Chem Res,2011(50):5459-5466.
[15]Olazar M,Lopez G,Amutio M,et al.Influence of FCC catalyst steaming on HDPE pyrolysis product distribution[J].J Anal Appl Pyrol,2009(85):359-365.
[16]伍艳辉,吴高胜,刘春燕,等.塑料裂解催化剂研究进展[J].工业催化,2014,22(8):569-575.
[17]夏海岸,杨莉,王晨,等.低密度聚烯烃在微孔分子筛上的催化裂解及其机理研究[J].中国科技论文,2013,8(9):869-873.
[18]Luo G,Suto T,Yasu S,et al.Catalytic degradation of high density polyethylene and polypropylene into liquid fuel in a powder-particle fluidized bed[J].Polym Degrad Stab,2000,70(1):97-102.
[19]Marcilly C R.Where and how shape selectivity of molecular sieves operates in refining and petrochemistry catalytic processes[J].Top Catal,2000(13):357-366.
[20]Kumagai S,Hasegawa I,Grause G,et al.Thermal decomposition of individual and mixed plastics in the presence of Ca O or Ca(OH)2[J].J Anal Appl Pyrol,2015(113):584-590.
[21]石油化工科学研究院.石油馏分沸程分布测定法(气相色谱法)[S].北京:石油化工出版社,2004.
[22]周华兰,魏跃,刘博洋,等.混合塑料裂解液相产物的分析[J].工业催化,2017,25(11):48-51.
[2]柴国梁.探讨塑料的市场现状与发展趋势(上)[J].上海化工,2008,33(1):39-41.
[3]Carroll W F,Goodman D.Plastics recycling:Products and processes[M].Munich:Hanser Publisher,1992:136.
[4]王永耀.聚乙烯、聚丙烯塑料回收利用进展[J].石油化工,2003,32(8):718-723.
[5]刘博洋,周华兰,夏峰峰,等.塑料制油技术研究及其产业化进展[J].化工进展,2017,36(Z 1):416-427.
[6]刘贤响.一种催化裂解塑料制燃料油的催化剂:中国,101024776[P].2007-08-29.
[7]刘治猛,蒋欣,刘煜平.利用回收聚苯乙烯裂解制苯乙烯单体[J].石油化工,2003,32(10):885-891.
[8]Wu Shikui,Xu Kaixiong,Jiang Lusen,et al.The co-cracking experiment and application route of waste plastics and heavy oil[J].AASRI Procedia,2014(7):231.
[9]Kunwar B,Cheng H N,Chandrashekaran S R,et al.Plastics to fuel:A review[J].Renew Sust Energ Rev,2016(54):421-428.
[10]杨基和,姚致远,严明亮,等.塑料制备燃料油热裂解与催化裂解工艺研究比较[J].江苏石油化工学院学报,2002,14(3):12-14.
[11]李晓祥,石炎福,余华瑞.塑料催化裂解制燃料油[J].化工环保,2002,22(2):90-94.
[12]Demirbas A.Pyrolysis of municipal plastic wastes for recovery of gasoline-range hydrocarbons[J].J Anal Appl Pyrol,2004(72):97-102.
[13]Kaminsky W,Schlesselmann B,Simon C M.Thermal degradation of mixed plastic waste to aromatics and gas[J].Polym Degrad Stab,1996(53):189-197.
[14]Grause G,Matsumoto S,Kameda T,et al.Pyrolysis of mixed plastics in a fluidized bed of hard burnt lime[J].Ind Eng Chem Res,2011(50):5459-5466.
[15]Olazar M,Lopez G,Amutio M,et al.Influence of FCC catalyst steaming on HDPE pyrolysis product distribution[J].J Anal Appl Pyrol,2009(85):359-365.
[16]伍艳辉,吴高胜,刘春燕,等.塑料裂解催化剂研究进展[J].工业催化,2014,22(8):569-575.
[17]夏海岸,杨莉,王晨,等.低密度聚烯烃在微孔分子筛上的催化裂解及其机理研究[J].中国科技论文,2013,8(9):869-873.
[18]Luo G,Suto T,Yasu S,et al.Catalytic degradation of high density polyethylene and polypropylene into liquid fuel in a powder-particle fluidized bed[J].Polym Degrad Stab,2000,70(1):97-102.
[19]Marcilly C R.Where and how shape selectivity of molecular sieves operates in refining and petrochemistry catalytic processes[J].Top Catal,2000(13):357-366.
[20]Kumagai S,Hasegawa I,Grause G,et al.Thermal decomposition of individual and mixed plastics in the presence of Ca O or Ca(OH)2[J].J Anal Appl Pyrol,2015(113):584-590.
[21]石油化工科学研究院.石油馏分沸程分布测定法(气相色谱法)[S].北京:石油化工出版社,2004.
[22]周华兰,魏跃,刘博洋,等.混合塑料裂解液相产物的分析[J].工业催化,2017,25(11):48-51.