废旧轮胎热解及热解产物研究展望

doi:10.16085/j.issn.1000-6613.2020-0559

摘要/Abstract

摘要：

热解作为废旧轮胎处置的重要技术手段，可以有效实现其减量化、无害化和资源化利用。本文综述了废旧轮胎热解的影响因素以及热解产物的研究进展，对废旧轮胎热解的经济、环境和社会效益进行了说明，指出当前工业化热解废旧轮胎存在的问题，并展望了未来节能环保式热解工艺的应用前景。结合现有的工业化热解设备，优化工艺条件和反应器结构型式，进一步分析了热解产物即热解气、热解油及热解炭的成分结构与应用，通过对热解产物改性活化与提质处理，创造更大的经济效益。提出应基于环境法规要求和绿色发展理念，糅合多种处理技术，研制适合废旧轮胎热解的工艺装备，开发集收集/预处理/热解/产物回收与提质于一体的废旧轮胎处置技术，实现废旧轮胎高效清洁转化和高值利用。

关键词: 废旧轮胎, 热解, 处理工艺, 热解产物, 经济, 再利用

Abstract:

Pyrolysis of waste tires, as an important disposal means, could effectively achieve its reduction, harmlessness and resource utilization. This article reviewed the influencing factors of pyrolysis process of waste tires and the progress of pyrolysis products, carried out economics evaluation, and analyzed environmental and societal benefits, pointed out the current problems in industrial pyrolysis process of waste tires, and prospected future application of energy-saving and environmentally friendly pyrolysis process. In combination with the existing industrial pyrolysis equipment, the process conditions and reactor configurations were optimized. Pyrolysis products, i.e. pyrolysis gas, oil and char, were further analyzed for greater values through modification and upgrading techniques. Based on environmental regulations and green development concepts combined various treatment technologies, it was proposed to develop process equipment suitable for pyrolysis of waste tires and waste tires disposal technology that integrated collection/pretreatment/pyrolysis/product recovery and quality improvement to achieve efficient and clean conversion and high value reutilization of waste tires.

Key words: waste tire, pyrolysis, treating and disposal processes, pyrolytic product, economics, reutilization

中图分类号:

X783.3

蒋智慧, 刘洋, 宋永猛, 邓泽宇, 张天昊, 付洁, 敖文雅, 代建军. 废旧轮胎热解及热解产物研究展望[J]. 化工进展, 2021, 40(1): 515-525.

Zhihui JIANG, Yang LIU, Yongmeng SONG, Zeyu DENG, Tianhao ZHANG, Jie FU, Wenya AO, Jianjun DAI. Review of pyrolysis for waste tires and research prospects of pyrolysis products[J]. Chemical Industry and Engineering Progress, 2021, 40(1): 515-525.

图/表 8

参考文献 68

1	国家统计局. 中华人民共和国国家统计局月度数据报表[R]. 2018.
	National Bureau of Statistics. Monthly data report of the National Bureau of Statistics of the People Republic of China[R]. 2018.
2	中华人民共和国国家商务部. 中国再生资源回收行业发展报告(2018)[R]. 2018.
	Ministry of Commerce of the Peoples Republic of China. China Renewable Resources Recycling Industry Development Report (2018)[R]. 2018.
3	中华人民共和国工业和信息化部. 《废旧轮胎综合利用指导意见》[R]. 2010.
	Ministry of Industry and Information Technology of the People's Republic of China. Guiding Opinions on Comprehensive Utilization of Waste Tires[R]. 2020.
4	中华人民共和国工业和信息化部. 对《废旧轮胎综合利用行业规范条件（修订征求意见稿）》《废旧轮胎综合利用行业规范公告管理暂行办法（修订征求意见稿）》公开征求意见[R]. 2019.
	Ministry of Industry and Information Technology of the People's Republic of China. Public comment on the Regulations for the Comprehensive Utilization of Waste Tire Industry (Revised Draft) and Interim Measures for the Management of the Announcement of the Specification for Comprehensive Utilization of Waste Tire Industry (Revised Draft)[R]. 2019.
5	张峰, 郦亮, 饶绮麟. 废旧轮胎再利用技术[J]. 矿冶, 2011, 20(4): 105-108.
	ZHANG F, LI L, RAO Q L. Waste tire recycling technology[J]. Mining and Metallurgy, 2011, 20(4): 105-108.
6	朱茂电, 王加龙, 赵吕明. 废旧轮胎回收利用技术及其应用前景[J]. 再生资源与循环经济, 2008(8): 32-35.
	ZHU M D, WANG J L, ZHAO L M. Waste tire recycling technology and its application prospects[J]. Recyclable Resources and Circular Economy, 2008(8): 32-35.
7	XU F F, WANG B, YANG D, et al. TG-FTIR and Py-GC/MS study on pyrolysis mechanism and products distribution of waste bicycle tire[J]. Energy Conversion and Management, 2018, 175: 288-297.
8	LI S Q, YAO Q, CHI Y, et al. Pilot-scale pyrolysis of scrap tires in a continuous rotary kiln reactor[J]. Ind. Eng. Chem. Res., 2004, 43: 5133-5145.
9	BOUVIER J M, CHARBEL F, GELUS M. Gas-solid pyrolysis of tire wastes—Kinetics and material balances of batch pyrolysis of used tires[J]. Resources and Conservation, 1987, 3(15): 205-214.
10	AYLÓN E, CALLÉN M S, LÓPEZ J M, et al. Assessment of tire devolatilization kinetics[J]. Journal of Analytical and Applied Pyrolysis, 2005,75(1/2): 259-264.
11	YANG J, TANGUY P A, ROY C. Heat transfer, mass transfer and kinetics study of the vacuum pyrolysis of a large used tire particle[J]. Chemical Engineering Science, 1995, 50(12):1909-1922.
12	AUGUSTINE Quek, RAJASHEKHAR Balasubramanian. An algorithm for the kinetics of tire pyrolysis under different heating rates[J]. Journal of Hazardous Materials, 2009, 166(1): 126-132.
13	TALEB Dzuhairy Ab, HAMID Hamidah Abd, DERIS Raja Razuan Raja, et al. Insights into pyrolysis of waste tire in fixed bed reactor: thermal behavior[J]. Materials Today: Proceedings, 2020, 31: 178-186.
14	Hüseyin AYDIN, Cumali İLKILIÇ. Optimization of fuel production from waste vehicle tires by pyrolysis and resembling to diesel fuel by various desulfurization methods[J]. Fuel, 2012(102): 605-612.
15	崔洪, 杨建丽, 刘振宇. 废旧轮胎热解行为的TG/DTA研究[J]. 化工学报, 1999, 50(6): 826-833.
	CUI H, YANG J L, LIU Z Y. TG/DTA study on pyrolysis behavior of waste tires[J]. CIESC Journal, 1999, 50(6): 826-833.
16	BANAR V, AKYILDIZ A, OZKAN Z, et al. Characterization of pyrolytic oil obtained from pyrolysis of TDF (Tire Derived Fuel)[J]. Energy Conversion and Management, 2012 (62): 22-30.
17	MKHIZE N M, DANON B, GRYP P VAN DER, et al. Kinetic study of the effect of the heating rate on the waste tyre pyrolysis to maximise limonene production[J]. Chemical Engineering Research and Design, 2019, 152: 363-371.
18	WILLIAMS Paul T, BESLER Serpil, TAYLOR David T. The pyrolysis of scrap automotive tyres: the influence of temperature and heating rate on product composition[J]. Fuel, 1990, 69(12): 1474-1482.
19	AYLÓN E, FERNÁNDEZ-COLINO A, MURILLO R, et al. Valorisation of waste tyre by pyrolysis in a moving bed reactor[J]. Waste Management, 2010, 30(7): 1220-1224.
20	POLICELLA Matteo, WANG Zhiwei, BURRA Kiran G, et al. Characteristics of syngas from pyrolysis and CO₂-assisted gasification of waste tires[J]. Applied Energy, 2019(254): 113678.
21	BETANCUR Mariluz, MARTÍNEZ Juan Daniel, MURILLO Ramón. Production of activated carbon by waste tire thermochemical degradation with CO₂[J]. Journal of Hazardous Materials, 2009, 168(2/3): 882-887.
22	KAR Y. Catalytic pyrolysis of car tire waste using expanded perlite[J]. Waste Management, 2011, 31(8): 1772-1782.
23	楚雅杰, 仪垂杰, 陈贺, 等. 催化裂解废旧轮胎的试验研究[J]. 科学技术与工程, 2017, 17(15): 213-217.
	CHU Y J, YI C J, CHEN Y, et al. Experimental study on catalytic pyrolysis of waste tires[J]. Science Technology and Engineering, 2017, 17(15): 213-217.
24	Nguy&#x DŨNG100166;n Anh, KLAEWKLA Raweewan, WONGKASEMJIT Sujitra,et al. Light olefins and light oil production from catalytic pyrolysis of waste tire[J]. Journal of Analytical and Applied Pyrolysis,2009, 86(2): 281-286.
25	SHEN B X, WU C F, LIANG C, et al. Pyrolysis of waste tires: the influence of USY catalyst/tire ratio on products[J]. Journal of Analytical and Applied Pyrolysis, 2007, 2(78): 243-249.
26	王文选, 仲兆平, 陈晓平，等. 催化剂在轮胎裂解中作用的研究[J]. 东南大学学报, 1999(S1): 47-50.
	WANG W X, ZHONG Z P, CHEN X P, et al. Research on catalysts in the pyrolysis of waste tires[J]. Journal of Southeast University, 1999(S1): 47-50.
27	WILLIAMS P T, BRINDLE A J. Catalytic pyrolysis of tires: inﬂuence of catalyst temperature[J]. Fuel, 2002, 81: 2425-2434.
28	MIANDAD R, BARAKAT M A. Effect of advanced catalysts on tire waste pyrolysis oil[J]. Process Safety and Environmental Protection, 2018(116): 542-552.
29	LI W, HUANG C F, LI D P, et al. Derived oil production by catalytic pyrolysis of scrap tires[J]. Chinese Journal of Catalysis, 2016, 37(4): 526-532.
30	HE Z Z, JIAO Q Z. Light olefin production from catalytic pyrolysis of waste tires using nano-HZSM-5/γ-Al₂O₃ catalysts[J]. Journal of Analytical and Applied Pyrolysis, 2018(129): 66-71.
31	DUNG N A, KLAEWKLA R, WONGKASEMJIT S, et al. Light olefins and light oil production from catalytic pyrolysis of waste tire[J]. Journal of Analytical and Applied Pyrolysis, 2009，86: 281-286.
32	HIJAZI Ayman, BOYADJIAN Cassia. Solar pyrolysis of waste rubber tires using photoactive catalysts[J]. Waste Management, 2018, 77: 10-21.
33	张兴华, 常杰, 王铁军, 等. 真空条件下金属氧化物催化废轮胎热解研究[J]. 能源工程, 2006(1): 41-45.
	ZHANG X H, CHANG J, WANG T J, et al. A study on metal-oxide catalyzed pyrolysis of waste tires under vacuum conditions[J]. Energy Engineering, 2006(1): 41-45.
34	DAI X W, YIN X L, WU C Z, et al. Pyrolysis of waste tires in a circulating fluidized-bed reactor[J]. Energy, 2001, 26(4): 385-399.
35	UCAR Suat, KARAGOZ Selhan, OZKAN Ahmet R, et al. Evaluation of two different scrap tires as hydrocarbon source by pyrolysis[J]. Fuel, 2005 84(14/15): 1884-1892.
36	SINGH R K, MONDAL S, RUJ B, et al. Interaction of three categories of tyre waste during co-pyrolysis: effect on product yield and quality[J]. Journal of Analytical and Applied Pyrolysis, 2019, 141: 104618.
37	WANG M Y, ZHANG L, LI A M, et al. Comparative pyrolysis behaviors of tire tread and side wall from waste tire and characterization of the resulting chars[J]. Journal of Environmental Management, 2019， 232: 364-371.
38	YAZDANI Esmaeil, HASHEMABADI Seyed Hassan, TAGHIZADEH Afshin. Study of waste tire pyrolysis in a rotary kiln reactor in a wide range of pyrolysis temperature[J]. Waste Management, 2019, 85(15): 195-201.
39	RYMS M, JANUSZEWICZ K, LEWANDOWSKI W M, et al. Pyrolysis process of whole waste tires as a biomass energy recycling[J]. Ecol. Chem. Eng., 2013(20): 93-107.
40	LOPEZ G, ALVAREZ J. Waste truck-tire processing by flash pyrolysis in a conical spouted bed reactor[J]. Energy Conversion and Management, 2017， 142: 523-532.
41	CUNLIFFE Adrian M, WILLIAMS Paul T. Composition of oils derived from the batch pyrolysis of tires[J]. Journal of Analytical and Applied Pyrolysis, 1998, 2(44): 131-152.
42	ZHANG Y Z, BIAN T T, ZHANG Y, et al. High-efficiency green microwave pyrolysis waste tire method[J]. Journal of Zhejiang University-Science A(Applied Physics & Engineering), 2018,19(12): 951-960.
43	MKHIZE N M, DANON B, GRYP P VAN DER, et al. Condensation of the hot volatiles from waste tyre pyrolysis by quenching[J]. Journal of Analytical and Applied Pyrolysis, 2017, 124: 180-185.
44	ELBABA Ibrahim F, WILLIAMS Paul T. Two stage pyrolysis-catalytic gasification of waste tyres: influence of process parameters[J]. Applied Catalysis B: Environmental, 2012, 125: 136-143.
45	SONG Z L, YANG Y Q, SUN J, et al. Effect of power level on the microwave pyrolysis of tire powder[J]. Energy, 2017, 127: 571-580.
46	WILLIAMS P T, BOTTRILL R P, CUNLIFFE A M. Combustion of tyre pyrolysis oil[J]. Process Safety and Environmental Protection, 1998, 76(4): 291-301.
47	BUTLER Eoin, DEVLIN Ger, MEIER Dietrich, et al. A review of recent laboratory research and commercial developments in fast pyrolysis and upgrading[J]. Renewable and Sustainable Energy Reviews, 2011, 15(8): 4171-4186.
48	ALVAREZ J, LOPEZ G, AMUTIO M, et al. Evaluation of the properties of tyre pyrolysis oils obtained in a conical spouted bed reactor[J]. Energy, 2017, 128: 463-474.
49	KAMINSKY W, MENNERICH C, ZHANG Z. Feedstock recycling of synthetic and natural rubber by pyrolysis in a ﬂuidized bed[J]. Journal of Analytical and Applied Pyrolysis, 2009, 85: 334-337.
50	MARTÍNEZ Juan Daniel, MURILLO Ramón, Tomás GARCÍA, et al. Demonstration of the waste tire pyrolysis process on pilot scale in a continuous auger reactor[J]. Journal of Hazardous Materials, 2013, 261: 637-645.
51	BLACK J W, RROWN D B. Development of a continuous ablative reactor for fast pyrolysis[C]//Advances in Thermochemical Biomass Conversion, 1992.
52	MARTÍNEZ Juan D, VESES Alberto, MASTRAL Ana M, et al. Co-pyrolysis of biomass with waste tires: upgrading of liquid bio-fuel[J]. Fuel Processing Technology, 2014, 119: 263-271.
53	唐兰, 黄海涛, 吴创之，等. 等离子体热解处理废轮胎实验研究[J]. 环境科学与技术, 2004, 27(6): 82-83， 99.
	TANG L, HUANG H T, WU C Z，et al. Experimental research on plasma pyrolysis treatment of waste tires[J]. Environmental Science and Technology, 2004, 27(6): 82-83, 99.
54	ZHANG X, WANG T, MA L. et al. Vacuum pyrolysis of waste tires with basic additives[J]. Waste Management, 2005, 28(11): 2301-2310.
55	梁著文. 烟气余热回收装置的利用[J]. 沿海企业与科技, 2010(10): 111-113.
	LIANG Z W. Utilization of flue gas waste heat recovery device[J]. Coastal Enterprises and Technology, 2010(10): 111-113.
56	徐宗平, 郭庆民. 废轮胎热解回收中的废气综合利用[J]. 中国轮胎资源综合利用, 2018(11):36-39.
	XU Z P, GUO Q M. The comprehensive utilization of waste gas in waste tire pyrolysis recycling[J]. China Tire Resources Recycling, 2018(11): 36-39.
57	Mustafa KARAGÖZ, AĞBULUTÜmit, SARIDEMIR Suat. Waste to energy: production of waste tire pyrolysis oil and comprehensive analysis of its usability in diesel engines[J]. Fuel, 2020, 275: 117844.
58	ZHANG Y L, JI G Z, LI C J, et al. Templating synthesis of hierarchical porous carbon from heavy residue of tire pyrolysis oil for methylene blue removal[J]. Chemical Engineering Journal, 2020, 390: 124398.
59	郭豪, 梁鹏, 郭庆民. 废轮胎热解回收的产业现状与创新技术[J]. 再生资源与循环经济, 2013, 6(8): 22-26.
	GUO H, LIANG P, GUO Q M. Industry status and innovative technology of waste tire pyrolysis and recycling[J]. Renewable Resources and Circular Economy, 2013, 6(8): 22-26.
60	ZHOU J, WAN G G J D, REN X H, et al. Surface modification of pyrolytic carbon black from waste tires and its use as pigment for offset printing ink[J]. Chinese Journal of Chemical Engineering, 2006, 14(5): 654-659.
61	Rubén GÓMEZ-HERNÁNDEZ, Yesmin PANECATL-BERNAL, MÉNDEZ-ROJAS Miguel Ángel. High yield and simple one-step production of carbon black nanoparticles from waste tires[J]. Heliyon, 2019, 5(7): 102139.
62	肖国良, 彭小芹, 盖国胜. 废轮胎裂解炭黑的超细粉碎和表面改性及在NR中的应用[J]. 橡胶工业, 2004(2): 78-82.
	XIAO G L, PENG X Q, GAI G S. Superfine crushing and surface modification of waste tire pyrolysis carbon black and its application in NR[J]. Rubber Industry, 2004(2): 78-82.
63	SAGAR M, NIBEDITA K, MANOHAR N, et al. A potential utilization of end-of-life tyres as recycled carbon black in EPDM rubber[J]. Waste Management, 2018, 74: 110-122.
64	FENG Z G, RAO W Y, CHEN C, et al. Performance evaluation of bitumen modified with pyrolysis carbon black made from waste tyres[J]. Construction and Building Materials, 2016, 111: 495-501.
65	HERAS F, JIMENEZ-CORDERO D, GILARRANZ M A, et al. Activation of waste tire char by cyclic liquid-phase oxidation[J]. Fuel Processing Technology, 2014, 127: 157-162.
66	BHAUMIK Madhumita, RAJU Kumar, ARUNACHELLAN Iviwe, et al. High-performance supercapacitors based on S-doped polyaniline nanotubes decorated with Ni(OH)₂ nanosponge and onion-like carbons derived from used car tyres[J]. Electrochimica Acta, 2020, 342: 136111.
67	李成, 张斌, 任泽, 等. 废轮胎裂解技术能耗经济分析及建议[J].中国轮胎资源综合利用, 2018(7):36-41.
	LI C, ZHANG B, REN Z, et al. Economic analysis and suggestions on energy consumption of waste tire cracking technology[J]. China Tire Resources Recycling, 2018(7): 36-41.
68	李德治, 姜莉莉, 周鑫. 高效环保型废旧轮胎裂解设备[J]. 橡胶工业, 2013, 60(8): 493-496.
	LI D Z, JIANG L L, ZHOU X. Efficient and environment-friendly waste tire cracking equipment[J]. China Rubber Industry, 2013, 60(8): 493-496.

技术	主要内容	特点
重建
原形利用	防护堤坝、游乐玩具等	处理量低，<总量1%
翻新	翻新轮胎寿命等同新轮胎寿命60%～90%	翻新率低；硫化过程中产生危害性有机物
材料回收
再生橡胶	加工制备成能重新使用的橡胶	二次污染严重、再生手段不够成熟，推广度低
生产胶粉	用于制备离子交换剂等	工艺不够成熟，造成二次污染
能量回收
焚烧	直接焚烧，部分能量得以回收	二次污染，产生二英、VOC、颗粒物等
气化	采用气化法处理废轮胎制取可燃气体	产品较少，与热解相比，经济性低
热解	无氧热分解，生产富含烃的热解气、油和热解炭	减量化、无害化，资源化综合利用好

技术	主要内容	特点
重建
原形利用	防护堤坝、游乐玩具等	处理量低，<总量1%
翻新	翻新轮胎寿命等同新轮胎寿命60%～90%	翻新率低；硫化过程中产生危害性有机物
材料回收
再生橡胶	加工制备成能重新使用的橡胶	二次污染严重、再生手段不够成熟，推广度低
生产胶粉	用于制备离子交换剂等	工艺不够成熟，造成二次污染
能量回收
焚烧	直接焚烧，部分能量得以回收	二次污染，产生二英、VOC、颗粒物等
气化	采用气化法处理废轮胎制取可燃气体	产品较少，与热解相比，经济性低
热解	无氧热分解，生产富含烃的热解气、油和热解炭	减量化、无害化，资源化综合利用好

过程	热解温度/℃	反应
初级反应	＜200	水分蒸发
	＞200	油类助剂、增塑剂等有机助剂分解
	200~300	天然橡胶分解
	250~500	合成橡胶分解
二次反应	500～900	Diels-Alder聚合反应及二次炭化反应

过程	热解温度/℃	反应
初级反应	＜200	水分蒸发
	＞200	油类助剂、增塑剂等有机助剂分解
	200~300	天然橡胶分解
	250~500	合成橡胶分解
二次反应	500～900	Diels-Alder聚合反应及二次炭化反应

催化剂	轮胎种类（粒径）	热解温度/℃	实验结论	参考文献
ZSM-5	汽车（1.0～1.4mm）	430	苯和二甲苯等芳烃产率提高	[27]
Al₂O₃	混合轮胎粉末（2.0～3.5mm）	450	热解油中芳香族化合物含量为84.6%	[28]
Ca(OH)₂		450	热解油产率最高，其中芳香族化合物降低至60.9%	[28]
天然沸石		450	热解油中芳香族化合物含量为71.0%	[28]
Si∶Al=3∶7	汽车（0.01～0.09mm）	500	热解油产率最高为55.7%，且芳香族化合物最高	[29]
Nano HZSM-5/γ-Al₂O₃	汽车（0.5～2.0mm）	400	对轻质烯烃的选择性更高	[30]
Ru/MCM-41	汽车（8～18目）	470	轻质烯烃产率提高	[31]
NaOH（35%）	汽车（20～100目）	550	热解油产率最高	[23]
Fe粉（35%）		550	热解炭产物分布影响最大	[23]
高炉渣（35%）		550	热解气产物产率最高	[23]
TiO₂	汽车（2.0mm）	550	热解气产率提高	[32]
CaO（2.5%）	汽车轮胎小块（100mm×120mm）	500	液相产率提高到48.0%	[33]
ZnO（2.5%）		530	液相产率提高到48.0%	[33]
CaO，ZnO，TiO₂		600	热解油和热解炭黑产率大幅度下降，热解气产率上升	[33]