Technology research and commercialization review for waste plastics to fuel

doi:10.16085/j.issn.1000-6613.2016-2282

Abstract

Abstract: Since increasing amount of waste plastics is becoming a severe global environmental threat, recovering waste plastics and converting it to usable resources has attracted a lot of attention in the world. This review has summarized the current R&D and commercialization status for various technologies including thermal cracking, catalytic cracking which convert waste plastics to fuel around the world. After thorough comparison, we believe that catalytic cracking has the best potential to become the future commercial technology for converting waste plastics to fuel efficiently, environment-friendly, and without secondly pollution. It also describes the impact of temperature, residence time, waste plastics composition, catalyst, and reactor configuration on cracking reactions. Suggestions and recommendations are provided regarding how to improve technology commercialization, especially dechlorination of mixed waste plastics, increasing the yield of liquid products and improving the stability of oil products.

Key words: waste treatment, fuel, catalyst, catalytic cracking, reactors, industrialization

摘要： 废塑料造成的环境污染日趋严重，废塑料的回收和绿色资源化利用已成为全球关注的问题。本文详细介绍了热裂解和催化裂解等废塑料裂解制油工艺技术的研发和产业化现状，分析比较了它们各自的优缺点，认为催化裂解是一种潜力巨大的废塑料回收利用方法，具有高效、环保、无二次污染和产物油品质量高等优点，是未来废塑料制油技术的发展方向。本文还重点阐述了裂解过程中的温度、停留时间、原料组成、催化剂种类和反应器类型对裂解反应的影响，并针对废塑料制油技术产业化发展现状和存在的问题提出了建议：应重点关注混合废塑料脱氯工艺、提高液态产物产率和提高油品稳定性。

关键词: 废物处理, 燃料, 催化剂, 催化裂解, 反应器, 产业化

CLC Number:

TQ032.4

LIU Boyang, ZHOU Hualan, XIA Fengfeng, SONG Jinwen, YU Gengzhi, WANG Ming. Technology research and commercialization review for waste plastics to fuel[J]. Chemical Industry and Engineering Progress, 2017, 36(S1): 416-427.

刘博洋, 周华兰, 夏峰峰, 宋金文, 禹耕之, 王鸣. 废塑料制油技术研究及产业化进展[J]. 化工进展, 2017, 36(S1): 416-427.

References

[1] Plastics Europe,lastics-the Facts 2016[EB/OL].[2016-10-20]. http://www.plasticseurope.org/Document/plastics-the-facts-2016-15787.aspx?Page=SEARCH&FolID=2.
[2] 商务部流通业发展司,中国再生资源回收行业发展报告2016[EB/OL].[2016-05-25]. http://ltfzs.mofcom.gov.cn/article/ztzzn/an/201605/20160501325666.shtml.
[3] 汤桂兰,胡彪,康在龙,等. 废旧塑料回收利用现状及问题[J]. 再生资源与循环经济,2013, 6(1):31-35. TANG G L,HU B,KANG Z L,et al. Current status and problems on waste plastic recycling[J]. Recy. Res. Circu. Econ.,2013,6(1):31-35.
[4] KUNWAR B,CHENG H N,CHANDRASHEKARAN S R,et al. Plastics to fuel:a review[J]. Renew Sust. Energ. Rev.,2016,54:421-428.
[5] PANDA A K,SINGH R K,MISHRA D K. Thermolysis of waste plastics to liquid fuel:a suitable method for plastic waste management and manufacture of value added products——A world prospective[J]. Renew Sust. Energ. Rev., 2010,14(1):233-248.
[6] AL-SALEM S M,LETTIERI P,BAEYENS J. Recycling and recovery routes of plastic solid waste (PSW):a review[J]. Waste Manag.,2009,29(10):2625-2643.
[7] 杨基和,姚致远,严明亮,等. 废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. YANG J H,YAO Zh Y,YAN M L,et al. Study on the process of preparing fuel oil using waste plastics by method of thermal cracking and catalytic racking[J]. J. Jiangsu Inst. Petrochem. Technol., 2002,14(3):12-14.
[8] 李晓祥,石炎福,余华瑞. 废塑料催化裂解制燃料油[J]. 化工环保,2002,22(2):90-94. LI X X,SHI Y F,YU H R. Preparation of fuel oil from plastic waste by catalytic cracking[J]. Environ. Prot. Chem. Ind.,2002,22(2):90-94.
[9] 伍艳辉,吴高胜,刘春燕,等. 废塑料裂解催化剂研究进展[J]. 工业催化,2014,22(8):569-575. WU Y H,WU G S,LIU C Y,et al. Progress in the catalysts for cracking of waste plastics[J]. Ind. Catal.,2014,22(8):569-575.
[10] SAKATA Y,UDDIN M A,KOIZUMI K,et al. Thermal degradation of polyethylene mixed with poly(vinyl chloride) and poly(ethyleneterephthalate)[J]. Polym. Degrad. Stab.,1996,53:111-117.
[11] DEMIRBAS A. Pyrolysis of municipal plastic wastes for recovery of gasoline-range hydrocarbons[J]. J. Anal. Appl. Pyrol.,2004,72:97-102.
[12] TRÖGER N, RICHTER D, STAHL R. Effect of feedstock composition on product yields and energy recovery rates of fast pyrolysis products from different straw types[J]. J. Anal. Appl. Pyrol.,2013,100:158-165.
[13] KUNWAR B,CHENG H N,CHANDRASHEKARAN S R,et al. Plastics to fuel:a review[J]. Renew Sust. Energ. Rev.,2016,54:421-428.
[14] MISKOLCZI N,ANGYAL A,BARTHA L,et al. Fuel by pyrolysis of waste plastics from agricultural and packaging sectors in a pilot scale reactor[J]. Fuel Process. Technol.,2009,90:1032-1040.
[15] AGUADO J,SERRANO D P,ESCOLA J M. Fuels from waste plastics by thermal and catalytic processes:a review[J]. Ind. Eng. Chem. Res., 2008,47(21):7982-7992.
[16] MARCILLA A,GARCIA A N,HERNANDEZ M R. Thermal degradation of LDPE-Vacuum gas oil mixtures for plastic wastes valorization[J]. Energy Fuels,2007,21(2):870-880.
[17] SERRANO D P,AGUADO J,ESCOLA J M,et al. Performance of a continuous screw kiln reactor for the thermal and catalytic conversion of polyethylene-lubricating oil mixtures[J]. Appl. Catal. B.,2003,44(2):95-105.
[18] 郑典模,卢钱峰,刘明,等. 废塑料与废机油共催化裂解制取燃料油的研究[J]. 现代化工,2011,31(8):47-49. ZHENG D M,LU Q F,LIU M,et al. Study on the catalytic cracking of waste plastics and waste lubricatingoil for producing fuel oil[J]. Mod. Chem. Ind.,2011,31(8):47-49.
[19] 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.
[20] 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.
[21] LÓPEZ A,DE MARCO I,CABALLERO B M,et al. Dechlorination of fuels in pyrolysis of PVC containing plastic wastes[J]. Fuel Process. Technol.,2011,92:253-260.
[22] LOPEZ-URIONABARRENECHEA A,DE MARCO I,CABALLERO B M,et al. Catalytic stepwise pyrolysis of packaging plastic waste[J]. J. Anal. Appl. Pyrol.,2012,96:54-62.
[23] ALI M F,SIDDIQUI M N. Thermal and catalytic decomposition behavior of PVC mixed plastic waste with petroleum residue[J]. J. Anal. Appl. Pyrol.,2004,74(1/2):282-289.
[24] MIO H,SAEKI S,KANO J,et al. Estimation of mechanochemical dechlorination rate of poly(vinylchloride)[J]. Environ. Sci. Technol., 2002,36(6):1344-1348.
[25] 李法鸿,袁兴中,陈晓青. 废塑料混合物分段热裂解的研究[J]. 石油炼制与化工,2001,32(5):51-54. LI F H,YUAN X Z,CHEN X Q. Study on staged pyrolysis of waste plastic mixture[J]. Petrol Process Petrochem.,2001,32(5):51-54.
[26] ONWUDILI J A,INSURA N,WILLIAMS P T. Composition of products from the pyrolysis of polyethylene and polystyrene in a closed batch reactor:effects of temperature and residence time[J]. J. Anal. Appl. Pyrol.,2009,86:293-303.
[27] MASTRAL F J,ESPERANZA E,GARCIA P,et al. Pyrolysis of high-density polyethylene in a fluidized bed reactor:Influence of the temperature and residence time[J]. J. Anal. Appl. Pyrol.,2002,63:1-15.
[28] 冀星,钱家麟,王剑秋. 聚丙烯油化催化剂的研制与性能[J]. 石油化工,1999,28(10):681-686. JI X,QIAN J L,WANG J Q. Preparation and properties of catalysts for the treatment of polypropylene waste[J]. Petrochem Technol.,1999,28(10):681-686.
[29] 冀星,钱家麟,王剑秋.聚乙烯及其废料油化技术中催化剂的研制与性能研究[J]. 环境化学,1999,18(5):437-444. JI X,QIAN J L,WANG J Q. The preparation and study on the property of the catalyst for the reformation of the pyrolysis product of polyethylene waste[J]. Environ Chem.,1999,18(5):437-444.
[30] SCOTT D S,CZERNIK S R,PISKORZ J,et al. Fast pyrolysis of plastic wastes[J]. Energ Fuel.,1990,4(4):407-411.
[31] KUMAGAI S,HASEGAWA I,GRAUSE G,et al. Thermal decomposition of individual and mixed plastics in the presence of CaO or Ca(OH)₂[J]. J. Anal. Appl. Pyrol.,2015,113:584-590.
[32] SEO Y H,LEE K H,SHIN D H. Investigation of catalytic degradation of high density, polyethylene by hydrocarbon group type analysis[J]. J. Anal. Appl. Pyrol.,2003,70:383-398.
[33] HERNÁNDEZ M D R,GÓMEZ A,GARCÓA Á N,et al. Effect of the temperature in the nature and extension of the primary and secondary reactions in the thermal and HZSM-5 catalytic pyrolysis of HDPE[J]. Appl. Catal. A:Gen.,2007,317:183-194.
[34] MARCILLA A,BELTRÁN M I,NAVARRO R. Thermal and catalytic pyrolysis of polyethylene over HZSM5 and HUSY zeolites in a batch reactor under dynamic condition[J]. Appl. Catal. B:Environ.,2009,86:78-86.
[35] WILLIAMS P T,WILLIAMS E A. Fluidised bed pyrolysis of low density polyethylene to produce petrochemical feedstock[J]. J. Anal. Appl. Pyrol.,1998,51:107-126.
[36] 李稳宏,李迓红. 废塑料降解工艺过程催化剂的应用研究[J]. 石油化工,2000,29(5):344-347. LI W H,LI Y H. Application research on catalysts for the degradation of waste plastics[J]. Petrochem Technol.,2000,29(5):344-347.
[37] LÓPEZ A,MARCO D I,CABALLERO B M,et al. Pyrolysis of municipal plastic waste Ⅱ:Influence of raw material composition under catalytic conditions[J]. Waste Manag.,2011,31:1973-1983.
[38] MASTRAL F J,ESPERANZA E,BERRUECO C,et al. Fluidized bed thermal degradation products of HDPE in an inert atmosphere and in airnitrogen mixtures[J]. J. Anal. Appl. Pyrol.,2003,70:1-17.
[39] 姚凌岷. 废弃塑料的回收再利用技术[J]. 化工新型材料,1996(5):20-24. YAO L M. Recycling technology of waste plastics[J]. New Chem. Mater.,1996(5):20-24.
[40] 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.
[41] SYAMSIRO M,SAPTOADI H,NORSUJIANTO T,et al. Fuel oil production from Municipal plastic wastes in sequential pyrolysis and catalytic reforming reactors[J]. Energ. Procedia.,2014,47:180-188.
[42] LUDLOW-PALAFOX C,CHASE H A. Microwave-induced pyrolysis of plastic waste[J]. Ind. Eng. Chem. Res.,2001,40:4749-4756.
[43] 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.
[44] 龚新怀,陈婷婷,康晓燕. 废聚苯乙烯泡沫塑料的催化裂解[J]. 化工环保,2014,34(2):150-154. GONG X H,CHEN T T,TANG X Y. Catalytic Cracking of Waste Expanded Polystyrene[J]. Environ. Protect. Chem. Ind.,2014,34(2):150-154.
[45] 宋学君,曹晓慧,潘文浩. 粉煤灰共混废弃聚苯乙烯塑料裂解的研究[J]. 山东化工,2015,44(19):144-146. SONG X J,CAO X H,PAN W H. The study on cracking of wasted expaned polysterene blended by fly ash[J].Shandong chem Ind, 2015,44(19):144-146.
[46] 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.
[47] KYONG H L,NAM S N,DAE H S,et al. Comparison of plastic types for catalytic degradation of waste plastics into liquid product with spent FCC catalyst[J]. Polym. Degrad. Stab.,2002,78:539-544.
[48] MISKOLCZI N,ANGYAL A, BARTHA L,et al. Fuels by pyrolysis of waste plastics from agricultural and packaging sectors in a pilot scale reactor[J]. Fuel Process Technol.,2009,90(7/8):1032-1040.
[49] 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. XIA H A,YANG L,WANG C,et al. Catalytic pyrolysis of low-density polyolefins on micropore zeolite catalysts and its reaction mechanism[J]. China. Sci. Pap.,2013,8(9):869-873.
[50] 安杰,朱向学,李秀杰,等. 废塑料在改性ZSM-5上裂解转化生产车用液体燃料[J]. 化工进展,2012,31(s1):448-452. AN J,ZHU X X,LI X J,et al. Waste plastics cracking and transforming into liquid fuel for production vehicle on modified ZSM-5[J]. Chemical Industry and Engineering Progress,2012, 31(s1):448-452.
[51] 梅丽伟,纵秋云. 废塑料化学转化制燃料催化剂的相关研究[J]. 化工管理,2016(18):64. MEI L W,ZONG Q Y. Study on the catalysts for chemical conversion of waste plastics to fuel[J]. Chem. Enterprise Manage,2016(18):64.
[52] SAKATA Y,UDDIN M A,MUTO A,et al. Catalytic degradation of polyethylene into fuel oil over mesoporous silica (KFS-16) catalyst[J]. J. Anal. Appl. Pyrol.,1997,43:15-25.
[53] UEMICHI Y,NAKAMURA J,ITOH T,et al. Conversion of polyethylene into gasoline-range fuels by two-stage catalytic degradation using silica-alumina and HZSM-5 zeolite[J]. Ind. Eng. Chem. Res.,1998,38(2):385-390.
[54] 刘光宇,栾健,马晓波,等. 垃圾废塑料裂解工艺和反应器[J]. 环境工程,2009,27:383-388. LIU G Y,LUAN J,MA X B,et al. Pyrolysis of MSW plastics:technologies and their reactors[J].Environ. Eng.,2009,27:383-388.
[55] 吴鹏锋. 一种废塑料炼油裂解釜:201010532487.X[P]. 2014-02-23. WU P F. A kind of waste plastics refining cracking kettle:201010532487. X[P]. 2014-02-23.
[56] 刘贤响,尹笃林. 废塑料裂解制燃料的研究进展[J]. 化工进展,2008,34(3):348-351. LIU X X,YIN D L. The research progress of waste plastic crackingsystem[J]. Chemical Industry and Engineering Progress,2015,34(3):348-351.
[57] 丁亚峰,黄秀玲,王志伟,等. 一种新型废塑料裂解反应釜的研究与设计[J]. 机械设计与制造,2013(1):20-22. DING Y F,HUANG X L,WANG Z W,et al. The research and design of a new type of waste plastic cracking reactor[J]. Mach. Des. Manu.,2013(1):20-22.
[58] ELORDI G,OLAZAR M,LOPEZ G,et al. Product yields and compositions in the continuous pyrolysis of high-density polyethylene in a conical spouted bed reactor[J]. Ind. Eng. Chem. Res.,2011,50:6650-6659.
[59] PREDEL M,KAMINSKY W. Pyrolysis of mixed polyolefins in a fluidised-bed reactor and on a pyro-GC/MS to yield aliphatic waxes[J]. Polym. Degrad. Stab.,2000,70:373-385.
[60] HALL W J,WILLIAMS P T. Pyrolysis of brominated feedstock plastic in a fluidised bed reactor[J]. J. Anal. Appl. Pyrol.,2006,77:75-82.
[61] 张郑磊. 废塑料热解-催化改质实验研究[D]. 保定:华北电力大学,2014. ZHANG Z L. Waste plastics pyrolysis,catalytic reforming experimentalresearch[D]. Baoding:North China Electric Power University,2014.
[62] Ocean recovery alliance. 2015 Plastics-to-fuel project developer's guide[EB/OL].http://www.oceanrecov.org/assets/files/Valuing_Plastic/2015-PTF-Project-Developers-Guide.pdf.
[63] 我国废塑料炼油技术首次达到国家标准并实现产业化[J]. 品牌与标准化,2014(18):9. China's waste plastics refining technology meet the national standards for the first time and realize industrialization[J]. Brand Standard,2014(18):9.
[64] 废塑料裂解制油清洁技术产业化[J]. 工程塑料应用,2015,41(2):116. Industrialization of clean technology for waste plastics cracking to fuel[J]. Eng. Plast Application, 2015,41(2):116.
[65] 任冬梅,齐美荣. 废塑料裂解制取燃料油的新型工业装置[J]. 齐鲁石油化工, 2005, 33(3);173-177. REN D M, QI M R. Novel industrial device for producing fuel oil by cracking waste plastics[J]. QILU Petrochemical Tech., 2005, 33(3);173-177.
[66] 刘公召, 陈尔霆. 废塑料催化裂解生成汽柴油中试工艺的研究[J]. 环境科学与技术, 2001, 24(6):9-10. LIU G Z, CHEN E T. Catalytic cracking of scrap plastics into gasoline and diesel oil by a pilot experiment unit[J]. Environmental Science & Technology, 2001, 24(6):9-10.
[67] 刘海波,杜亚威,王永国. 间歇法工艺炼废塑料生产燃料油的工业生产改进[J]. 甘肃石油和化工,2007(1):28-31. LIU H B, DU Y W,WANG Y G. Industrial improvement of batch process for producing fuel oil from waste plastics[J]. Gansu Petrochem Technol, 2007(1):28-31.
[68] 胡玉莹, 陈海峰, 钟转转,等. 聚乙烯废塑料流化床裂解炉的设计[J]. 环境工程,2013,31(4):80-84. HU Y Y, CHEN H F, ZHONG Z Z, et al. Design of fluidized bed reactor to crack waste PE plastics[J]. Environmental Engineering, 2013,31(4):80-84.
[69] 王晓毅, 汪心想. 废塑料催化裂解烟气中污染物分析与解决方案[J]. 工业安全与环保,2011, 37(9):29-30. WANG X Y, WANG X X. The analyses and settlements of the pollutants in the flue gas from the catalytic cracking of the wasted plastic[J]. Industrial Safety and Environmental Protection, 2011, 37(9):29-30.