典型杂质掺混对废塑料热解油特性的影响

doi:10.16085/j.issn.1000-6613.2020-1468

摘要/Abstract

摘要：

以从4个典型的废弃物处理场取得的与废塑料掺混的杂质样品作为纯塑料热解过程中的添加剂，研究不可回收废塑料中掺混的杂质组分对塑料热解油品质的影响。研究内容包括4种杂质（I₁～I₄）对聚乙烯、聚丙烯、聚苯乙烯及混合塑料热解的影响以及杂质中的无机和有机组分在热解中分别起到的作用。结果表明，杂质的添加将塑料热解油中主要组分的富集度由65.5%提升到79.2%～90.3%；其中来源于废旧自行车拆解厂的杂质I₄对热解油组成的影响最为显著。I₄使得聚乙烯及聚丙烯热解油中的烯烃含量分别提高了25.0%及21.1%，但对聚苯乙烯的热解没有显著影响。I₄对塑料热解的影响可分为三个方面：无机灰分作为热载体起到的作用、特定活性灰分组分的催化作用以及杂质中有机组分参与热解的影响。灰分作为热载体促进了聚合物分子链的裂解；活性灰分组分能够催化加氢及氢转移等反应；而I₄中有机组分热解提高了油相产物中芳烃和烯烃的含量。该研究将为废塑料规模化热解过程中原料的预处理及热解油品质调控提供指导。

关键词: 热解, 废物处理, 聚合物, 塑料, 杂质, 油

Abstract:

Fine impurity particles were separated from the waste plastics at four waste disposal sites and used as additives in the pyrolysis of pure plastics in order to study the effect of impurities on the oil quality during the pyrolysis of non-recyclable waste plastics. The effects of four types of impurities (I₁—I₄) on polyethylene, polypropylene, polystyrene and their mixture were investigated, as well as the role of organics and inorganics in the impurities. The additives increased the concentration of primary components in oil from 65.5% to 79.2%—90.3%. The highest concentration was obtained with impurity sample I₄, collected at a bicycle dismantling plant. I₄ also increased the alkenes in the polyethylene/polypropylene pyrolysis oil by 25.0% and 21.1%, but had no significant effect on polystyrene pyrolysis. The I₄ had 3 effects on the pyrolysis of plastics: inorganic ash acting as a heat carrier, the catalytic effect of specific active ash components and the effect of organics in the impurities. Ash as a heat carrier promoted the cleavage of polymer chains. Active ash components catalyzed hydrogenation and hydrogen transfer reaction. Pyrolysis of the organic components in I₄ produced additional aromatics and alkenes. The study would provide guidance for the pretreatment and oil quality control in the large-scale waste plastic pyrolysis process.

Key words: pyrolysis, waste treatment, polymer, plastic, impurity, oil

中图分类号:

X705

孙锴, 王琬丽, 黄群星. 典型杂质掺混对废塑料热解油特性的影响[J]. 化工进展, 2021, 40(6): 3499-3506.

SUN Kai, WANG Wanli, HUANG Qunxing. Effect of typical impurities on the pyrolysis oil of waste plastics[J]. Chemical Industry and Engineering Progress, 2021, 40(6): 3499-3506.

图/表 8

参考文献 29

1	PLASTICSEUROPE, Plastics—The facts 2019. An analysis of European plastics production, demand and waste data[R]. Brussels: Plastics Europe, 2019.
2	张君涛, 刘健康, 梁生荣, 等. 废塑料化学转化制燃料的催化剂研究进展[J]. 化工进展, 2014, 33(10): 2644-2649.
	ZHANG J T, LIU J K, LIANG S R, et al. Recent developments in catalyst for waste plastic to fuels via chemical conversion process[J]. Chemical Industry and Engineering Progress, 2014, 33(10): 2644-2649.
3	KUNWAR B, CHENG H N, CHANDRASHEKARAN S R, et al. Plastics to fuel: a review[J]. Renewable and Sustainable Energy Reviews, 2016, 54: 421-428.
4	Commission European. A European strategy for plastics in a circular economy[R]. Brussels: European Commission, 2018.
5	AL-SALEM S M, ANTELAVA A, CONSTANTINOU A, et al. A review on thermal and catalytic pyrolysis of plastic solid waste (PSW)[J]. Journal of Environmental Management, 2017, 197: 177-198.
6	LOPEZ G, ARTETXE M, AMUTIO M, et al. Thermochemical routes for the valorization of waste polyolefinic plastics to produce fuels and chemicals: a review[J]. Renewable and Sustainable Energy Reviews, 2017, 73: 346-368.
7	WU C, WILLIAMS P T. Pyrolysis-gasification of plastics, mixed plastics and real-world plastic waste with and without Ni-Mg-Al catalyst[J]. Fuel, 2010, 89(10): 3022-3032.
8	BHASKAR T, UDDIN M A, MURAI K, et al. Comparison of thermal degradation products from real municipal waste plastic and model mixed plastics[J]. Journal of Analytical and Applied Pyrolysis, 2003, 70(2): 579-587.
9	CANOPOLI L, FIDALGO B, COULON F, et al. Physico-chemical properties of excavated plastic from landfill mining and current recycling routes[J]. Waste Management, 2018, 76: 55-67.
10	ROTLIWALA Y C, PARIKH P A. Thermal co-processing of high density polyethylene with coal, fly ashes, and biomass: characterization of liquid products[J]. Energy Sources, A: Recovery, Utilization, and Environmental Effects, 2012, 34(11): 1055-1066.
11	宋学君, 于雅洁, 武士威, 等. 煤渣催化聚苯乙烯泡沫塑料热解的研究[J]. 中国塑料, 2009, 23(4): 85-87.
	SONG X J, YU Y J, WU S W, et al. Study on thermal cracking of wasted expanded polystyrene catalyzed by cinder[J]. China Plastics, 2009, 23(4): 85-87.
12	赵磊, 王中慧, 陈德珍, 等. 杂质对废塑料裂解产物及污染物排放的影响[J]. 环境科学, 2012, 33(1): 329-336.
	ZHAO L, WANG Z H, CHEN D Z, et al. Influence of impurities on waste plastics pyrolysis: products and emissions[J]. Environmental Science, 2012, 33(1): 329-336.
13	CARROLL W F, GOODMAN D. Plastics recycling : products and processes[M]. Munich: Hanser Publisher, 1992: 136.
14	MUKHERJEE S, BORTHAKUR P C. Effect of leaching high sulphur subbituminous coal by potassium hydroxide and acid on removal of mineral matter and sulphur[J]. Fuel, 2003, 82(7): 783-788.
15	HU G, FAN H, LIU Y. Experimental studies on pyrolysis of Datong coal with solid heat carrier in a fixed bed[J]. Fuel Processing Technology, 2001, 69(3): 221-228.
16	黄雷, 张玉明, 张亮, 等. 页岩灰和FCC催化剂调控油页岩热解产物二次反应特性[J]. 化工学报, 2017, 68(10): 3770-3778.
	HUANG L, ZHANG Y M, ZHANG L, et al. Effects of shale ash and FCC catalyst on adjusting secondary reaction of volatiles in oil shale pyrolysis[J]. CIESC Journal, 2017, 68(10): 3770-3778.
17	周茜, 郑丽, 王玉忠. 热化学循环法回收聚苯乙烯的研究进展[J]. 石油化工, 2003, 32(11): 1003-1006.
	ZHOU Q, ZHENG L, WANG Y Z. Research progress on the recovery of polystyrene by thermochemical recycling[J]. Petrochemical Technology, 2003, 32(11): 1003-1006.
18	RANA M, TAKI G, ISLAM M N, et al. Effects of temperature and salt catalysts on depolymerization of kraft lignin to aromatic phenolic compounds[J]. Energy & Fuels, 2019, 33(7): 6390-6404.
19	ZHANG T, WANG W. Catalytic pyrolysis of rice husks for syngas production over Fe-based catalyst in a fixed-bed reactor[J]. Energy Sources A: Recovery, Utilization, and Environmental Effects, 2016, 38(15): 2190-2196.
20	冀星, 钱家麟. 聚乙烯聚丙烯树脂及废料的热解[J]. 环境科学, 1999, 20(5): 82-85.
	JI X, QIAN J L. The pyrolysis of polyethylene polypropene and its wastes[J]. Environmental Science, 1999, 20(5): 82-85.
21	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.
	LIU Z M, JIANG X, LIU Y P. Production of styrene monomer by cracking of recycled polystyrene[J]. Petrochemical Technology, 2003, 32(10): 885-891.
22	CHENG S, TAKAHASHI F, GAO N, et al. Evaluation of oil sludge ash as a solid heat carrier in the pyrolysis process of oil sludge for oil production[J]. Energy & Fuels, 2016, 30(7): 5970-5979.
23	YU Y, YU J, SUN B, et al. Influence of catalyst types on the microwave-induced pyrolysis of sewage sludge[J]. Journal of Analytical and Applied Pyrolysis, 2014, 106: 86-91.
24	GAO Z, HONG Y, HU Z, et al. Transfer hydrogenation of cinnamaldehyde with 2-propanol on Al₂O₃ and SiO₂-Al₂O₃ catalysts: role of Lewis and Brønsted acidic sites[J]. Catalysis Science & Technology, 2017, 7(19): 4511-4519.
25	NIU H, LU J, SONG J, et al. Iron oxide as a catalyst for nitroarene hydrogenation: important role of oxygen vacancies[J]. Industrial & Engineering Chemistry Research, 2016, 55(31): 8527-8533.
26	KIJENSKI J, GLINSKI M, CZARNECKI J. Reduction of alkyl alkyl, aryl alkyl and cyclic ketones by catalytic hydrogen transfer over magnesium oxide[J]. Journal of the Chemical Society, 1991, 2(11): 1695-1698.
27	YOUNG Z D, DAVIS R J. Hydrogen transfer reactions relevant to Guerbet coupling of alcohols over hydroxyapatite and magnesium oxide catalysts[J]. Catalysis Science & Technology, 2018, 8(6): 1722-1729.
28	WOO O S, AYALA N, BROADBELT L J. Mechanistic interpretation of base-catalyzed depolymerization of polystyrene[J]. Catalysis Today, 2000, 55(1-2): 161-171.
29	袁剑, 张波, 汤明慧, 等. ZrO₂/MCM-41催化的苯乙酮氢转移反应[J]. 高校化学工程学报, 2013, 27(5): 818-824.
	YUAN J, ZHANG B, TANG M H, et al. Hydrogen-transfer reaction of acetophenone over ZrO₂/MCM-41[J]. Journal of Chemical Engineering of Chinese Universities, 2013, 27(5): 818-824.

样品	工业分析/%			元素分析/%					灰成分分析/%							高位发热量 /kJ	废塑料中的占比 /%
样品	A_d	V_d	FC_d	C_d	H_d	N_d	S_d	O_d	SiO₂	Al₂O₃	Fe₂O₃	CaO	MgO	K₂O	Na₂O	高位发热量 /kJ	废塑料中的占比 /%
I₁	63.5	33.1	3.4	17.6	1	1.1	0.2	16.6	47.3	8.7	8.6	23.2	7.2	2.1	2.9	5333	11.4
I₂	66.7	31.8	1.5	14.6	1.1	0.4	0.2	17	49.5	10.2	4.3	23.3	9.9	1.3	1.5	3978	14.6
I₃	68.3	31.0	0.7	19.9	2.2	0.7	0.6	8.3	34.5	11.1	29.6	8.2	13.6	1.1	1.9	6787	24.7
I₄	62.9	36.6	0.5	22.5	2.3	0.8	0.8	10.7	35.2	9.2	36.3	9.3	7.3	1.0	1.7	5220	21.9

样品	工业分析/%			元素分析/%					灰成分分析/%							高位发热量 /kJ	废塑料中的占比 /%
样品	A_d	V_d	FC_d	C_d	H_d	N_d	S_d	O_d	SiO₂	Al₂O₃	Fe₂O₃	CaO	MgO	K₂O	Na₂O	高位发热量 /kJ	废塑料中的占比 /%
I₁	63.5	33.1	3.4	17.6	1	1.1	0.2	16.6	47.3	8.7	8.6	23.2	7.2	2.1	2.9	5333	11.4
I₂	66.7	31.8	1.5	14.6	1.1	0.4	0.2	17	49.5	10.2	4.3	23.3	9.9	1.3	1.5	3978	14.6
I₃	68.3	31.0	0.7	19.9	2.2	0.7	0.6	8.3	34.5	11.1	29.6	8.2	13.6	1.1	1.9	6787	24.7
I₄	62.9	36.6	0.5	22.5	2.3	0.8	0.8	10.7	35.2	9.2	36.3	9.3	7.3	1.0	1.7	5220	21.9

组分	烷烃/%			烯烃/%					芳烃/%
组分	C₅~C₁₁	C₁₂~C₂₀	C₂₁~C₃₆	C₅~C₁₁	C₁₂~C₂₀	C₂₁~C₃₆	双烯	四烯	苯乙烯	其他单环芳烃	双环芳烃
热裂解	0	4.3	0	4.0	14.0	13.4	3.3	0	15.5	6.5	4.5
I₁	0	2.7	1.6	4.9	27.2	22.7	4.9	0	9.4	10.0	3.0
I₂	0	2.9	1.9	3.8	18.8	25.0	6.8	0	10.2	6.2	3.7
I₃	0	2.5	0	3.9	23.5	24.7	8.2	1.2	9.7	6.4	2.6
I₄	0.7	2.0	0	3.0	27.9	30.8	4.9	0	11.3	4.6	5.1

组分	烷烃/%			烯烃/%					芳烃/%
组分	C₅~C₁₁	C₁₂~C₂₀	C₂₁~C₃₆	C₅~C₁₁	C₁₂~C₂₀	C₂₁~C₃₆	双烯	四烯	苯乙烯	其他单环芳烃	双环芳烃
热裂解	0	4.3	0	4.0	14.0	13.4	3.3	0	15.5	6.5	4.5
I₁	0	2.7	1.6	4.9	27.2	22.7	4.9	0	9.4	10.0	3.0
I₂	0	2.9	1.9	3.8	18.8	25.0	6.8	0	10.2	6.2	3.7
I₃	0	2.5	0	3.9	23.5	24.7	8.2	1.2	9.7	6.4	2.6
I₄	0.7	2.0	0	3.0	27.9	30.8	4.9	0	11.3	4.6	5.1

[1]	邵博识, 谭宏博. 锯齿波纹板对挥发性有机物低温脱除过程强化模拟分析[J]. 化工进展, 2023, 42(S1): 84-93.
[2]	贺美晋. 分子管理在炼油领域分离技术中的应用和发展趋势[J]. 化工进展, 2023, 42(S1): 260-266.
[3]	许友好, 王维, 鲁波娜, 徐惠, 何鸣元. 中国炼油创新技术MIP的开发策略及启示[J]. 化工进展, 2023, 42(9): 4465-4470.
[4]	罗成, 范晓勇, 朱永红, 田丰, 崔楼伟, 杜崇鹏, 王飞利, 李冬, 郑化安. 中低温煤焦油加氢反应器不同分配器中液体分布的CFD模拟[J]. 化工进展, 2023, 42(9): 4538-4549.
[5]	廖志新, 罗涛, 王红, 孔佳骏, 申海平, 管翠诗, 王翠红, 佘玉成. 溶剂脱沥青技术应用与进展[J]. 化工进展, 2023, 42(9): 4573-4586.
[6]	程涛, 崔瑞利, 宋俊男, 张天琪, 张耘赫, 梁世杰, 朴实. 渣油加氢装置杂质沉积规律与压降升高机理分析[J]. 化工进展, 2023, 42(9): 4616-4627.
[7]	林晓鹏, 肖友华, 管奕琛, 鲁晓东, 宗文杰, 傅深渊. 离子聚合物-金属复合材料（IPMC）柔性电极的研究进展[J]. 化工进展, 2023, 42(9): 4770-4782.
[8]	邵志国, 任雯, 许世佩, 聂凡, 许毓, 刘龙杰, 谢水祥, 李兴春, 王庆吉, 谢加才. 终温对油基钻屑热解产物分布和特性影响[J]. 化工进展, 2023, 42(9): 4929-4938.
[9]	朱传强, 茹晋波, 孙亭亭, 谢兴旺, 李长明, 高士秋. 固体高分子脱硝剂选择性非催化还原NO _x 特性[J]. 化工进展, 2023, 42(9): 4939-4946.
[10]	李志远, 黄亚继, 赵佳琪, 于梦竹, 朱志成, 程好强, 时浩, 王圣. 污泥与聚氯乙烯共热解重金属特性[J]. 化工进展, 2023, 42(9): 4947-4956.
[11]	杨莹, 侯豪杰, 黄瑞, 崔煜, 王兵, 刘健, 鲍卫仁, 常丽萍, 王建成, 韩丽娜. 利用煤焦油中酚类物质Stöber法制备碳纳米球用于CO₂吸附[J]. 化工进展, 2023, 42(9): 5011-5018.
[12]	李伯耿, 罗英武, 刘平伟. 聚合物产品工程研究内容与方法的思考[J]. 化工进展, 2023, 42(8): 3905-3909.
[13]	王报英, 王皝莹, 闫军营, 汪耀明, 徐铜文. 聚合物包覆膜在金属分离回收中的研究进展[J]. 化工进展, 2023, 42(8): 3990-4004.
[14]	高聪, 陈城虎, 陈修来, 刘立明. 代谢工程改造微生物合成生物基单体的进展与挑战[J]. 化工进展, 2023, 42(8): 4123-4135.
[15]	王晓晗, 周亚松, 于志庆, 魏强, 孙劲晓, 姜鹏. 不同晶粒尺寸Y分子筛的合成及其加氢裂化反应性能[J]. 化工进展, 2023, 42(8): 4283-4295.