废轮胎梯级热解中试装置开发与产物特性分析

doi:10.16085/j.issn.1000-6613.2022-0999

化工进展 ›› 2023, Vol. 42 ›› Issue (3): 1240-1247.DOI: 10.16085/j.issn.1000-6613.2022-0999

废轮胎梯级热解中试装置开发与产物特性分析

潘宇涵¹(), 徐俊², 赵光杰³, 林诚乾¹, 金亮³, 薛志亮¹, 周永刚¹, 黄群星¹^,⁴()

^1.浙江大学热能工程研究所，能源清洁利用国家重点实验室，浙江杭州 310027
^2.杭州中策清泉实业有限公司，浙江杭州 311401
^3.中国联合工程有限公司，浙江杭州 310052
^4.浙江省清洁能源与碳中和重点实验室，浙江杭州 310027

收稿日期:2022-05-30 修回日期:2022-07-27 出版日期:2023-03-15 发布日期:2023-04-10
通讯作者: 黄群星
作者简介:潘宇涵（1995—），男，博士研究生，研究方向为固体废弃物资源化利用。E-mail：panyuhan@zju.edu.cn。
基金资助:
浙江省重点研发计划(2020C03084);山东省重点研发计划(2019JZZY020806)

Development of pilot-plant for the step pyrolysis of waste tires and analysis of product characteristics

PAN Yuhan¹(), XU Jun², ZHAO Guangjie³, LIN Chengqian¹, JIN Liang³, XUE Zhiliang¹, ZHOU Yonggang¹, HUANG Qunxing¹^,⁴()

^1.State Key Laboratory of Clean Energy Utilization, Institute for Thermal Power Engineering, Zhejiang University, Hangzhou 310027, Zhejiang, China
^2.Hangzhou Zhongce Qingquan Industrial Corporation Limited, Hangzhou 311401, Zhejiang, China
^3.China United Engineering Corporation Limited, Hangzhou 310052, Zhejiang, China
^4.Key Laboratory of Clean Energy and Carbon Neutrality of Zhejiang Province, Hangzhou 310027, Zhejiang, China

Received:2022-05-30 Revised:2022-07-27 Online:2023-03-15 Published:2023-04-10
Contact: HUANG Qunxing

摘要/Abstract

摘要：

基于固定床管式热解炉对废轮胎热解产物性质进行了详细的研究和分析，根据热解产物特性针对性地提出了产物的改性提质方法，并基于该方法自主设计开发了一套适用于废轮胎高效能源资源化利用的梯级螺旋热解中试装置，以获得高品质热解产物。甲苯抽出物透光率和闪点分别是限制热解炭黑和热解油高效安全应用的瓶颈问题。本文开发的中试热解装置采用梯级热解技术和多级冷凝技术，可有效改善热解产物品质，所得热解炭黑甲苯抽出物透光率达到100%，热解油闪点达到76.5℃，均满足相应标准。同时，中试装置采用热解气循环燃烧供能的方案，可实现装置的热量自维持，显著降低工艺热解能耗。本文基于自主开发的中试梯级热解装置，解决了废轮胎热解产物高值化利用的瓶颈问题，以期为废轮胎热解技术规模化推广应用奠定基础。

关键词: 废轮胎, 中试热解装置, 梯级热解, 多级冷凝, 自热式

Abstract:

In this paper, based on the fixed-bed tubular pyrolysis furnace, the properties of waste tire pyrolysis products were studied and analyzed in detail. A series of modification and upgrading methods were proposed according to the characteristics of the pyrolysis products. Based on the methods, a set of step spiral pilot-scale pyrolysis reactor suitable for efficient energy resource utilization of waste tires was independently designed and developed to obtain pyrolysis products with high-quality. The light transmittance of the toluene extract and the flash point were the bottleneck issues that limited the efficient and safe application of pyrolysis carbon black and pyrolysis oil, respectively. The pilot-scale pyrolysis system developed in this research adopted the step pyrolysis technology and multi-stage condensation technology, which could effectively improve the quality of pyrolysis products. The light transmittance of the toluene extract of the obtained pyrolysis carbon black reached 100% and the flash point of the obtained pyrolysis oil reached 76.5℃, both of which met the corresponding standards. At the same time, the pilot-plant adopted the scheme of circulating pyrolysis gases for energy supply, which could realize the thermal self-sustaining of the system and significantly reduce the energy consumption of the pyrolysis process. In this research, the bottleneck problem of high-value utilization of waste tire pyrolysis products had been solved based on the self-developed pilot-scale step pyrolysis system. This study laid a foundation for the large-scale promotion and application of waste tire pyrolysis technology.

Key words: waste tires, pilot pyrolysis plant, step pyrolysis, multistage condensing, self-heated

中图分类号:

TE992.3

潘宇涵, 徐俊, 赵光杰, 林诚乾, 金亮, 薛志亮, 周永刚, 黄群星. 废轮胎梯级热解中试装置开发与产物特性分析[J]. 化工进展, 2023, 42(3): 1240-1247.

PAN Yuhan, XU Jun, ZHAO Guangjie, LIN Chengqian, JIN Liang, XUE Zhiliang, ZHOU Yonggang, HUANG Qunxing. Development of pilot-plant for the step pyrolysis of waste tires and analysis of product characteristics[J]. Chemical Industry and Engineering Progress, 2023, 42(3): 1240-1247.

图/表 12

参考文献 35

1	康永. 废橡胶热裂解技术现状及发展方向[J]. 橡塑技术与装备, 2021, 47(1): 30-37.
	KANG Yong. Current status and development direction of waste rubber pyrolysis technology[J]. China Rubber/Plastics Technology and Equipment, 2021, 47(1): 30-37.
2	季炫宇, 林伟坚, 周雄, 等. 废轮胎热裂解技术研究现状与进展[J]. 化工进展, 2022, 41(8): 4498-4512.
	JI Xuanyu, LIN Weijian, ZHOU Xiong, et al. Research status and progress of waste tire pyrolysis technology[J]. Chemical Industry and Engineering Progress, 2022, 41(8): 4498-4512.
3	PAN Yuhan, SIMA Jingyuan, WANG Xinwen, et al. BTEX recovery from waste rubbers by catalytic pyrolysis over Zn loaded tire derived char[J]. Waste Management, 2021, 131: 214-225.
4	MARTÍNEZ Juan Daniel, Neus PUY, MURILLO Ramón, et al. Waste tyre pyrolysis—A review[J]. Renewable and Sustainable Energy Reviews, 2013, 23: 179-213.
5	WILLIAMS Paul T. Pyrolysis of waste tyres: a review[J]. Waste Management, 2013, 33(8): 1714-1728.
6	KAMINSKY W. Thermal recycling of polymers[J]. Journal of Analytical and Applied Pyrolysis, 1985, 8: 439-448.
7	KAMINSKY Walter. Pyrolysis of plastic waste and scrap tyres in a fluid bed reactor[J]. Resource Recovery and Conservation, 1980, 5(3): 205-216.
8	QUEK Augustine, BALASUBRAMANIAN Rajasekhar. Liquefaction of waste tires by pyrolysis for oil and chemicals—A review[J]. Journal of Analytical and Applied Pyrolysis, 2013, 101: 1-16.
9	HITA Idoia, ARABIOURRUTIA Miriam, OLAZAR Martin, et al. Opportunities and barriers for producing high quality fuels from the pyrolysis of scrap tires[J]. Renewable and Sustainable Energy Reviews, 2016, 56: 745-759.
10	ARABIOURRUTIA M, LOPEZ G, ARTETXE M, et al. Waste tyre valorization by catalytic pyrolysis—A review[J]. Renewable & Sustainable Energy Reviews, 2020, 129: 109932.
11	XU Junqing, YU Jiaxue, HE Wenzhi, et al. Wet compounding with pyrolytic carbon black from waste tyre for manufacture of new tyre—A mini review[J]. Waste Manag Res, 2021, 39(12): 1440-1450.
12	SHEN Boxiong, WU Chunfei, GUO Binbin, et al. Pyrolysis of waste tyres with zeolite USY and ZSM-5 catalysts[J]. Applied Catalysis B: Environmental, 2007, 73(1/2): 150-157.
13	WANG Kai, XU Yuping, DUAN Peigao, et al. Thermo-chemical conversion of scrap tire waste to produce gasoline fuel[J]. Waste Management, 2019, 86: 1-12.
14	Dina CZAJCZYŃSKA, Renata KRZYŻYŃSKA, JOUHARA Hussam, et al. Use of pyrolytic gas from waste tire as a fuel: a review[J]. Energy, 2017, 134: 1121-1131.
15	路明, 张红霞, 和富金, 等. 炭黑表面能与甲苯抽出物透光率的关系[J]. 橡胶工业, 2020, 67(9): 709-712.
	LU Ming, ZHANG Hongxia, HE Fujin, et al. Relationship between surface free energy of carbon black and light transmittance of toluene extract[J]. China Rubber Industry, 2020, 67(9): 709-712.
16	张雪. 废轮胎热解残渣升级为商业炭黑的研究[D]. 太原: 太原理工大学, 2018.
	ZHANG Xue. Study on upgrading pyrolytic residue from waste tires to commercial carbon black[D]. Taiyuan: Taiyuan University of Technology, 2018.
17	Cezary DĘBEK. Modification of pyrolytic oil from waste tyres as a promising method for light fuel production[J]. Materials, 2019, 12(6): 880.
18	HOOSHMAND AHOOR Amir, Navid ZANDI-ATASHBAR. Fuel production based on catalytic pyrolysis of waste tires as an optimized model[J]. Energy Conversion and Management, 2014, 87: 653-669.
19	MARTÍNEZ Juan Daniel, LAPUERTA Magín, Reyes GARCÍA-CONTRERAS, et al. Fuel properties of tire pyrolysis liquid and its blends with diesel fuel[J]. Energy & Fuels, 2013, 27(6): 3296-3305.
20	国家质量监督检验检疫总局, 中国国家标准化管理委员会. 化学品分类和标签规范第7部分：易燃液体: [S]. 北京: 中国标准出版社, 2014.
	General Administration of Quality Supervision, Inspection and Quarantine of the People’s Republic of China, Standardization Administration of the People’s Republic of China. Rules for classification and labelling of chemicals—Part 7: Flammable liquids: [S]. Beijing: Standards Press of China, 2014.
21	SENNECA O, SALATINO P, CHIRONE R. A fast heating-rate thermogravimetric study of the pyrolysis of scrap tyres[J]. Fuel, 1999, 78(13): 1575-1581.
22	PAN Yuhan, YANG Diancai, SUN Kai, et al. Pyrolytic transformation behavior of hydrocarbons and heteroatom compounds of scrap tire volatiles[J]. Fuel, 2020, 276: 118095.
23	杨渺, 孙媛媛, 王伟勇. 根据单一气体物理特性计算焦炉煤气低热值[J]. 山东化工, 2014, 43(6): 133-134.
	YANG Miao, SUN Yuanyuan, WANG Weiyong. According to the physical properties of single gas of coke oven gas with low calorific value calculation[J]. Shandong Chemical Industry, 2014, 43(6): 133-134.
24	SALEH Tawfik A, GUPTA Vinod Kumar. Processing methods, characteristics and adsorption behavior of tire derived carbons: a review[J]. Advances in Colloid and Interface Science, 2014, 211: 93-101.
25	孟德营, 陈晓燕, 王贝贝, 等. 不同废旧轮胎裂解炭黑的性能研究[J]. 橡胶科技, 2021, 19(12): 591-594.
	MENG Deying, CHEN Xiaoyan, WANG Beibei, et al. Properties of pyrolysis carbon black from different waste tires[J]. Rubber Science and Technology, 2021, 19(12): 591-594.
26	闫大海. 废轮胎回转窑中试热解产物应用及热解机理和动力学模型研究[D]. 杭州: 浙江大学, 2006.
	YAN Dahai. Study on the utilization of pyrolytic products from pyrolysis of used tyre in a pilot-scale rotary kiln and the mechanism and kinetic model of rubber pyrolysis[D]. Hangzhou: Zhejiang University, 2006.
27	DANON B, P van der GRYP, SCHWARZ C E, et al. A review of dipentene (dl-limonene) production from waste tire pyrolysis[J]. Journal of Analytical and Applied Pyrolysis, 2015, 112: 1-13.
28	JANUSZEWICZ K, KAZIMIERSKI P, KOSAKOWSKI W, et al. Waste tyres pyrolysis for obtaining limonene[J]. Materials (Basel, Switzerland), 2020, 13(6): 1359.
29	FARZAD Somayeh, MANDEGARI Mohsen, GÖRGENS Johann F. A novel approach for valorization of waste tires into chemical and fuel (limonene and diesel) through pyrolysis: process development and techno economic analysis[J]. Fuel Processing Technology, 2021, 224: 107006.
30	WILLIAMS Paul T, TAYLOR David T. Aromatization of tyre pyrolysis oil to yield polycyclic aromatic hydrocarbons[J]. Fuel, 1993, 72(11): 1469-1474.
31	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.
32	LARESGOITI M F, CABALLERO B M, DE MARCO I, et al. Characterization of the liquid products obtained in tyre pyrolysis[J]. Journal of Analytical and Applied Pyrolysis, 2004, 71(2): 917-934.
33	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.
34	CHEUNG Kwok Yuen, LEE King Lung, LAM Ka Leung, et al. Operation strategy for multi-stage pyrolysis[J]. Journal of Analytical and Applied Pyrolysis, 2011, 91(1): 165-182.
35	徐文胜, 蒋旭光, 严大海, 等. 废轮胎中试回转窑热解气特性及能耗分析[J]. 能源工程, 2005(2): 30-34.
	XU Wensheng, JIANG Xuguang, YAN Dahai, et al. Chromatographic analysis and calorific value calculation of gave from scrap tyres pyrolysed in a pilot-scale rotary kiln[J]. Energy Engineering, 2005(2): 30-34.

工业分析质量分数/%					元素分析质量分数/%
M_ad	A_ad	V_ad	FC_ad		C_ad	H_ad	O_ad^①	N_ad	S_ad
1.21	8.01	62.27	28.51		74.77	7.24	5.87	0.69	2.21

工业分析质量分数/%					元素分析质量分数/%
M_ad	A_ad	V_ad	FC_ad		C_ad	H_ad	O_ad^①	N_ad	S_ad
1.21	8.01	62.27	28.51		74.77	7.24	5.87	0.69	2.21

热解产物	固定床小试装置	移动床中试装置
热解炭	39.3±0.1	38.3±1.0
一级热解油	—	37.8±2.0
二级热解油	—	12.7±1.0
总热解油	45.5±0.4	50.5±3.0
热解气	15.2±0.5	10.7±0.1

热解产物	固定床小试装置	移动床中试装置
热解炭	39.3±0.1	38.3±1.0
一级热解油	—	37.8±2.0
二级热解油	—	12.7±1.0
总热解油	45.5±0.4	50.5±3.0
热解气	15.2±0.5	10.7±0.1

项目	固定床热解炭黑	移动床热解炭黑	目标值
甲苯抽出物透光率/%	36.1±0.3	100.0±0	≥80
吸碘值/g·kg^-1	115.2±3.9	163.3±2.2	≥90
吸油值/10^-5 m³·kg^-1	106.4±3.8	79.8±0.2	≥60
加热减量/%	1.5±0.1	0.6±0.1	≤2

废轮胎梯级热解中试装置开发与产物特性分析

Development of pilot-plant for the step pyrolysis of waste tires and analysis of product characteristics

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 12

参考文献 35

相关文章 8

编辑推荐

Metrics

本文评价

类别	闪点/℃
固定床热解油	26.5±0.5
移动床一级冷凝热解油	76.5±1.0
移动床二级冷凝热解油	15.0±1.0

指标	值/kJ·kg^-1	百分比/%
热解气供能	4668.5	95.30
天然气供能	230.3	4.70
输入热量	4898.8	100.00
热解能耗	1014.1	20.70
排烟热损失	2999.1	61.22
散热损失	885.6	18.08
输出热量	4898.8	100.00

[1]	王家庆, 宋广伟, 李强, 郭帅成, DAI Qingli. 橡胶混凝土界面改性方法及性能提升路径[J]. 化工进展, 2023, 42(S1): 328-343.
[2]	季炫宇, 林伟坚, 周雄, 柏继松, 杨宇, 孔杰, 廖重阳. 废轮胎热裂解技术研究现状与进展[J]. 化工进展, 2022, 41(8): 4498-4512.
[3]	吕全伟, 林顺洪, 柏继松, 李长江, 江辽, 李伟. 热重-红外联用(TG-FTIR)分析含油污泥-废轮胎混合热解特性[J]. 化工进展, 2017, 36(12): 4692-4699.
[4]	高新源, 徐庆, 李占勇, 田玮, 张建国. 生物质快速热解装置研究进展[J]. 化工进展, 2016, 35(10): 3032-3041.
[5]	苏亚欣，邓文义，姜凡，沈恒根. 废轮胎的燃料特性及用于燃煤锅炉再燃脱硝 [J]. 化工进展, 2011, 30(3): 642-.
[6]	王慧，邹滢，余锋，翁惠新. 废轮胎热解油的化学组成分布 [J]. 化工进展, 2011, 30(3): 656-.
[7]	刘霞1，邓德敏1，廖洪强2，张振国2. 废轮胎与煤共焦化焦油分析 [J]. 化工进展, 2010, 29(8): 1571-.
[8]	陆王琳；金余其；池涌；严建华；岑可法. 废轮胎热解制油技术及油品应用前景 [J]. 化工进展, 2007, 26(1): 13-.

类别	热值/MJ·m^-3
固定床热解气	42.96
移动床热解气	47.73

类别	热值/MJ·m^-3
固定床热解气	42.96
移动床热解气	47.73