塑料与蜡（重油）催化共热解相互作用研究

doi:10.11949/0438-1157.20190114

摘要/Abstract

摘要：

采用低密度聚乙烯（LDPE）和固体石蜡（WAX）分别作为塑料及重油的模型化合物，以HZSM-5为反应催化剂，通过热重实验进行热解特性及动力学分析，研究了二者在热解行为上的相互作用；并结合固定床反应器对比研究单独热解及不同原料配比下共热解的产物分布，考察了共热解过程相互作用对热解产物的影响规律。结果表明，LDPE与WAX共热解过程二者间相互作用增强，表现为促进反应物的热解失重，降低了原料的特征热分解温度及反应活化能，显著提高了热解油中C_21-轻油馏分及芳烃的选择性，而油中C₂₁₊重油馏分的选择性及固体残渣产率均降低；而且随着共热解原料中WAX比例的增加二者间的相互作用不断增强；基于模型化合物水平初步验证了塑料与裂解重油共热解制备高品质轻质燃油工艺的可行性与技术优势。

关键词: 塑料, 重油, 热解, 相互作用, 催化, 废物处理

Abstract:

Low density polyethylene (LDPE) and paraffin wax (WAX) were used as model compounds for plastics and heavy oils respectively. HZSM-5 was used as the reaction catalyst. The pyrolysis characteristics and kinetic analysis were carried out by thermogravimetric experiments. In product distributions respect, the influence of the co-pyrolysis interaction was discussed by individual pyrolysis of feedstock and co-pyrolysis at different ratios using fixed bed reactor. The results showed that, there was a strong interaction between LDPE and WAX, which accelerated the rate of mass loss and decreased the characteristic degradation temperature and the apparent activation energy. For pyrolysis products, the selectivity of light oil (C_21-) and aromatics were increased, and the selectivity of heavy oil (C₂₁₊) and the yield of solid residues were reduced. Moreover, it was found that the interaction could be enhanced by the increase of WAX content. The results of material balance calculation based on model compounds preliminarily validated that there were practical feasibility and technological advantages to produce high-quality fuel oil by catalytic co-pyrolysis of plastic with its cracking heavy oil.

Key words: plastic, heavy oil, pyrolysis, interaction, catalysis, waste treatment

中图分类号:

X 705

于冬雪, 惠贺龙, 何京东, 李松庚. 塑料与蜡（重油）催化共热解相互作用研究[J]. 化工学报, 2019, 70(8): 2971-2980.

Dongxue YU, Helong HUI, Jingdong HE, Songgeng LI. Study on interaction between plastic with wax (heavy oil) in process of catalytic co-pyrolysis[J]. CIESC Journal, 2019, 70(8): 2971-2980.

图/表 11

图1 塑料与裂解重油催化共热解制燃油工艺流程

Fig.1 Technological process of catalytic co-pyrolysis of plastic and heavy oil to produce fuel oil

图2 固定床热解反应装置

Fig.2 Schematic diagram of fixed-bed reactor

图3 LDPE、WAX及其混合物的TG/DTG曲线

Fig.3 TGA and DTG curves of LDPE, WAX and their mixture

图4 LDPE、WAX共热解ΔW曲线

Fig.4 Variation of ΔW for co-pyrolysis of LDPE and WAX

图5 LDPE、WAX及其混合物的动力学曲线

Fig.5 Kinetic curves of LDPE, WAX and their mixture

表1 LDPE、WAX及其混合物的动力学参数

Table 1 Kinetic parameters of LDPE, WAX and their mixture

Parameter	Catalyst			No-catalyst
Parameter	LDPE	WAX	LDPE/WAX	LDPE	WAX	LDPE/WAX
E _a/(kJ/mol)	88.33	64.22	48.75	96.63	81.18	63.87
R ²	0.98	0.98	0.98	0.97	0.99	0.98

图6 LDPE、WAX及其混合物的热解产物分布

Fig.6 Product distributions for pyrolysis of LDPE, WAX and their mixtures

图7 LDPE、WAX及其混合物的热解气相产物组分分布

Fig.7 Gas product composition distributions for pyrolysis of LDPE, WAX and their mixtures

图8 LDPE、WAX及其混合物的热解油相产物碳数分布

Fig.8 Oil product carbon number distributions for pyrolysis of LDPE, WAX and their mixtures

图9 LDPE、WAX及其混合物的热解油相产物组成分布

Fig.9 Oil product composition distributions for pyrolysis of LDPE, WAX and their mixtures

图10 LDPE、WAX催化共热解制燃油系统物料平衡计算

Fig.10 Material balance calculations in catalytic co-pyrolysis systems for production of fuel oil by LDPE and its derived heavy oil

参考文献 35

1	全球塑料垃圾达49亿吨热解处理技术成突破口[J].塑料科技, 2018, 46(8): 23.
	Global plastic waste reaches 4.9 billion tons, and pyrolysis technology becomes a breakthrough[J]. Plast. Sci. Technol., 2018, 46(8): 23.
2	Zhang X S , Lei H W . Synthesis of high-density jet fuel from plastics via catalytically integral processes[J]. RSC Adv., 2016, 6(8): 6154-6163.
3	刘博洋, 周华兰, 夏峰峰, 等 . 废塑料制油技术研究及产业化进展[J]. 化工进展, 2017, 36: 416-426.
	Liu B Y , Zhou H L , Xia F F , et al . Technology research and commercialization review for waste plastics to fuel[J], Chem. Ind. Eng. Prog., 2017, 36: 416-426.
4	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(11): 6650-6659.
5	Marcilla A , García N N , Hernndez M R . Thermal degradation of LDPE-vacuum gas oil mixtures for plastic wastes valorization[J]. Energy & Fuels, 2007, 21(2): 870-880.
6	Vicente G , Aguado J , Serrano D P , et al . HDPE chemical recycling promoted by phenol solvent[J]. J. Anal. Appl. Pyrolysis, 2009, 85(1/2): 366-371.
7	Serrano D P , Aguado J , Vicente G , et al . Effects of hydrogen-donating solvents on the thermal degradation of HDPE[J]. J. Anal. Appl. Pyrolysis, 2007, 78(1): 194-199.
8	Passamonti F J , Sedran U . Recycling of waste plastics into fuels. LDPE conversion in FCC[J]. Appl. Catal. B Environ., 2012, 125: 499-506.
9	Uçar S , Özkan A R , Karagöz S , et al . Co-pyrolysis of waste polyolefins with waste motor oil[J]. J. Anal. Appl. Pyrolysis, 2016, 119: 233-241.
10	周华兰, 魏跃, 宋金文,等 . 混合废塑料与焦化蜡油共催化裂解制取燃料油[J]. 工业催化, 2018, 26(3): 80-84.
	Zhou H L , Wei Y , Song J W , et al . Study on catalytic cracking of mixed waste plastics and coker gas oil to fuel oil[J]. Ind. Catal., 2018, 26(3): 80-84.
11	Miskolczi N , Ateş F . Thermo-catalytic co-pyrolysis of recovered heavy oil and municipal plastic wastes[J]. J. Anal. Appl. Pyrolysis, 2016, 117: 273-281.
12	景晓东 . “热裂化-过热水蒸汽直接加热裂解” 两步法回收废聚烯烃的研究[D]. 北京: 中国科学院大学, 2015.
	Jing X D . Study on waste polyolefin recovery: a two-step method of “thermal cracking-pyrolysis directly heated by superheaded steam”[D]. Beijing: University of Chinese Academy of Sciences, 2015.
13	闫国荀 . 聚烯烃热裂解及裂解产物作低碳烯烃生产原料的研究[D]. 青岛: 青岛科技大学, 2015.
	Yan G X . The study on thermal cracking polyolefins and production of steam pyrolysis feedstocks[D]. Qingdao: Qingdao University of Science & Technology, 2015.
14	袁兴中, 陈志勇, 陈晓青, 等 . 聚丙烯与重油混合裂解特性的研究[J]. 应用基础与工程科学学报, 2002, 10(2): 150-155.
	Yuan X Z , Chen Z Y , Chen X Q , et al . A study of manufacture fuel oil from polypropylene and heavy oil by cracking[J]. Journal of Basic Science and Engineering, 2002, 10(2): 150-155.
15	Arabiourrutia M , Elordi G , Lopez G , et al . Characterization of the waxes obtained by the pyrolysis of polyolefin plastics in a conical spouted bed reactor[J]. J. Anal. Appl. Pyrolysis, 2012, 94: 230-237.
16	张建平 . 塑料盐浴热解制取燃料油的研究[D]. 天津: 天津大学, 2007.
	Zhang J P . Study on salt-bath pyrolysis of plastic for recovery of fuel oil[D]. Tianjin: Tianjin University, 2007.
17	Elordi G , Olazar M , Lopez G , et al . Catalytic pyrolysis of HDPE in continuous mode over zeolite catalysts in a conical spouted bed reactor[J]. J. Anal. Appl. Pyrolysis, 2009, 85(1/2): 345-351.
18	任晓红, 赵雄燕, 姜志绘, 等 . 废旧塑料回收技术及设备的研究进展[J]. 应用化工, 2018, 47(4): 813-816.
	Ren X H , Zhao X Y , Jiang Z H , et al . Research progress of recycling technology and equipments for waste plastics[J]. Appl. Chem. Ind., 2018, 47(4): 813-816.
19	Zhang X , Lei H , Yadavalli G , et al . Gasoline-range hydrocarbons produced from microwave-induced pyrolysis of low-density polyethylene over ZSM-5[J]. Fuel, 2015, 144: 33-42.
20	Sharuddin S D A , Abnisa F , Daud W M A W , et al . A review on pyrolysis of plastic wastes[J]. Energy Convers. Manag., 2016, 115: 308-326.
21	王刚, 李爱民, 全翠 . 生物质与聚乳酸塑料共热解特性[J]. 化工学报, 2009, 60(7): 1787-1792.
	Wang G , Li A M , Quan C . Thermal decomposition of biomass/polylactic acid during co-pyrolysis [J]. CIESC Journal, 2009, 60(7): 1787-1792.
22	徐艺, 陈宇, 华德润, 等 . 固定床反应器中生物质/废塑料共热解制备燃料油[J]. 化工进展, 2013, 32(3): 563-569.
	Xu Y , Chen Y , Hua D R , et al . Co-pyrolysis of biomass and waste plastic for biofuel in fixed-bed reactor[J]. Chem. Ind. Eng. Prog., 2013, 32(3): 563-569.
23	Wang Z , Shen D , Wu C , et al . Thermal behavior and kinetic study for catalytic co-pyrolysis of biomass with plastics[J]. Bioresour. Technol., 2016, 220: 233-238.
24	李文, 田福军, 李保庆 . 塑料与煤低温共焦化的液体产物性质分析[J]. 化工学报, 2000, 51(4): 501-505.
	Li W , Tian F J , Li B Q . Analysis of tars from low-temperature co-carbonization of plastics and coal[J]. Journal of Chemical Industry and Engineering(China), 2000, 51(4): 501-505.
25	惠贺龙, 李松庚, 宋文立 . 生物质与废塑料催化热解制芳烃(Ⅰ): 协同作用的强化[J]. 化工学报, 2017, 68(10): 3832-3840.
	Hui H L , Li S G , Song W L . Aromatic hydrocarbon from catalytic pyrolysis of biomass and plastic wastes (Ⅰ): Enhancing synergistic effect[J]. CIESC Journal, 2017, 68(10): 3832-3840.
26	Gunasee S D , Carrier M , Gorgens J F , et al . Journal of analytical and applied pyrolysis and combustion of municipal solid wastes: evaluation of synergistic effects using TGA-MS[J]. J. Anal. Appl. Pyrolysis, 2016, 121: 50-61.
27	Fan H , Gu J , Wang Y , et al . Study on co-pyrolysis characteristics of biomass components and polyethylene by TG-MS[J]. Chinese J. Eng. Sci., 2018, 20(3): 102.
28	Marcilla A , Beltrán M I , Navarro R . Thermal and catalytic pyrolysis of polyethylene over HZSM5 and HUSY zeolites in a batch reactor under dynamic conditions[J]. Appl. Catal. B Environ., 2009, 86(1/2): 78-86.
29	何奕工, 舒兴田, 龙军 . 正碳离子何相关的反应机理[J]. 石油学报(石油加工), 2007, 23(4): 1-7.
	He Y G , Shu X T , Long J . Carbenium ions and relative reaction mechanism[J]. Acta Petrolei Sinica (Petroleum Processing Section), 2007, 23(4): 1-7.
30	Ahmad I , Khan M I , Khan H , et al . Pyrolysis study of polypropylene and polyethylene into premium oil products[J]. Int. J. Green Energy, 2015, 12(7): 663-671.
31	Lin X , Zhang Z , Tan S , et al . In line wood plastic composite pyrolyses and HZSM-5 conversion of the pyrolysis vapors[J]. Energy Convers. Manag., 2017, 141: 206-215.
32	Zhang X S , Lei H W . Synthesis of high-density jet fuel from plastics via catalytically integral processes[J]. RSC Adv., 2016, 6: 6154-6163.
33	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: 233-248.
34	Serrano D P , Aguado J , Vicente G , et al . Effects of hydrogen-donating solvents on the thermal degradation of HDPE[J]. J. Anal. Appl. Pyrolysis, 2007, 78(1): 194-199.
35	Liu S , Xie Q , Zhang B , et al . Fast microwave-assisted catalytic co-pyrolysis of corn stover and scum for bio-oil production with CaO and HZSM-5 as the catalyst[J]. Bioresour. Technolo., 2016, 204: 164-170.

[1]	程业品, 胡达清, 徐奕莎, 刘华彦, 卢晗锋, 崔国凯. 离子液体基低共熔溶剂在转化CO₂中的应用[J]. 化工学报, 2023, 74(9): 3640-3653.
[2]	陈杰, 林永胜, 肖恺, 杨臣, 邱挺. 胆碱基碱性离子液体催化合成仲丁醇性能研究[J]. 化工学报, 2023, 74(9): 3716-3730.
[3]	范孝雄, 郝丽芳, 范垂钢, 李松庚. LaMnO₃/生物炭催化剂低温NH₃-SCR催化脱硝性能研究[J]. 化工学报, 2023, 74(9): 3821-3830.
[4]	李艺彤, 郭航, 陈浩, 叶芳. 催化剂非均匀分布的质子交换膜燃料电池操作条件研究[J]. 化工学报, 2023, 74(9): 3831-3840.
[5]	杨学金, 杨金涛, 宁平, 王访, 宋晓双, 贾丽娟, 冯嘉予. 剧毒气体PH₃的干法净化技术研究进展[J]. 化工学报, 2023, 74(9): 3742-3755.
[6]	吴雷, 刘姣, 李长聪, 周军, 叶干, 刘田田, 朱瑞玉, 张秋利, 宋永辉. 低阶粉煤催化微波热解制备含碳纳米管的高附加值改性兰炭末[J]. 化工学报, 2023, 74(9): 3956-3967.
[7]	杨欣, 彭啸, 薛凯茹, 苏梦威, 吴燕. 分子印迹-TiO₂光电催化降解增溶PHE废水性能研究[J]. 化工学报, 2023, 74(8): 3564-3571.
[8]	张曼铮, 肖猛, 闫沛伟, 苗政, 徐进良, 纪献兵. 危废焚烧处理耦合有机朗肯循环系统工质筛选与热力学优化[J]. 化工学报, 2023, 74(8): 3502-3512.
[9]	韩晨, 司徒友珉, 朱斌, 许建良, 郭晓镭, 刘海峰. 协同处理废液的多喷嘴粉煤气化炉内反应流动研究[J]. 化工学报, 2023, 74(8): 3266-3278.
[10]	杨菲菲, 赵世熙, 周维, 倪中海. Sn掺杂的In₂O₃催化CO₂选择性加氢制甲醇[J]. 化工学报, 2023, 74(8): 3366-3374.
[11]	李凯旋, 谭伟, 张曼玉, 徐志豪, 王旭裕, 纪红兵. 富含零价钴活性位点的钴氮碳/活性炭设计及甲醛催化氧化应用研究[J]. 化工学报, 2023, 74(8): 3342-3352.
[12]	屈园浩, 邓文义, 谢晓丹, 苏亚欣. 活性炭/石墨辅助污泥电渗脱水研究[J]. 化工学报, 2023, 74(7): 3038-3050.
[13]	李盼, 马俊洋, 陈志豪, 王丽, 郭耘. Ru/α-MnO₂催化剂形貌对NH₃-SCO反应性能的影响[J]. 化工学报, 2023, 74(7): 2908-2918.
[14]	涂玉明, 邵高燕, 陈健杰, 刘凤, 田世超, 周智勇, 任钟旗. 钙基催化剂的设计合成及应用研究进展[J]. 化工学报, 2023, 74(7): 2717-2734.
[15]	张琦钰, 高利军, 苏宇航, 马晓博, 王翊丞, 张亚婷, 胡超. 碳基催化材料在电化学还原二氧化碳中的研究进展[J]. 化工学报, 2023, 74(7): 2753-2772.