废轮胎热解油气喷水急冷特性

doi:10.16085/j.issn.1000-6613.2024-0319

化工进展 ›› 2025, Vol. 44 ›› Issue (3): 1263-1274.DOI: 10.16085/j.issn.1000-6613.2024-0319

废轮胎热解油气喷水急冷特性

毛宇炜¹(), 薛志亮¹(), 洪钦², 付鑫³, 金建龙¹, 周永刚¹, 黄群星¹

^1.浙江大学热能工程研究所，能源高效清洁利用全国重点实验室，浙江杭州 310027
^2.桐乡泰爱斯环保能源有限公司，浙江嘉兴 314500
^3.浙江物产环保能源股份有限公司，浙江杭州 310003

收稿日期:2024-02-26 修回日期:2024-06-01 出版日期:2025-03-25 发布日期:2025-04-16
通讯作者: 薛志亮
作者简介:毛宇炜（1999—），男，硕士研究生，研究方向为废轮胎热解气污染物脱除。E-mail：22327125@zju.edu.cn。
基金资助:
浙江省领雁计划(2022C03082)

Study on water spray quenching characteristics of waste tire pyrolysis oil-gas

MAO Yuwei¹(), XUE Zhiliang¹(), HONG Qin², FU Xin³, JIN Jianlong¹, ZHOU Yonggang¹, HUANG Qunxing¹

^1.State Key Laboratory of Clean Energy Utilization, Institute for Thermal Power Engineering, Zhejiang University, Hangzhou 310027, Zhejiang, China
^2.Tongxiang Taiaisi Environmental Protection Energy Corporation Limited, Jiaxing 314500, Zhejiang, China
^3.Zhejiang Materials Industry Environmental Energy Corporation Limited, Hangzhou 310003, Zhejiang, China

Received:2024-02-26 Revised:2024-06-01 Online:2025-03-25 Published:2025-04-16
Contact: XUE Zhiliang

摘要/Abstract

摘要：

常规间接换热冷凝得到的废轮胎热解油存在闪点偏低的问题。为解决此问题，本文提出了一种用于热解油气冷凝的喷水急冷技术。基于闭杯闪点实验与气相色谱-质谱联用（GC-MS）技术分析了喷水急冷条件下热解油的闪点和组分，得到了废轮胎热解油气的喷水急冷特性。实验结果表明，油气喷水急冷可以快速冷凝油气，降低油气分压，从而显著降低热解油中低闪点组分的含量，提高热解油的闪点。GC-MS分析结果表明，油气喷水急冷技术降低了热解油中低碳数组分的含量，提高了高碳数组分的含量，导致热解油组分的碳数分布由低碳向高碳转变。同时，油气喷水急冷降低了热解油中脂肪烃、单环芳烃（MAHs）以及杂原子化合物的含量，提高了多环芳烃（PAHs）的含量，高附加值产物BTEX（苯、甲苯、乙苯和二甲苯）和D-柠檬烯的含量有所下降。此外，油气喷水急冷还降低了热解油中含氮/含硫组分的总含量，其中含氮组分和含氮含硫组分的含量下降，而含硫组分的含量略有上升。本文为废轮胎热解油的提质改性研究提供了参考。

关键词: 废轮胎, 热解油, 喷水急冷, 闪点, 组分分布

Abstract:

The flash point of waste tire pyrolysis oil obtained by conventional indirect heat transfer condensation is low. A water spray quenching technology for the condensation of pyrolytic oil and gas was proposed in this paper to solve the problem. The flash point and composition of pyrolysis oil were analyzed by closed cup flash test and GC-MS technique, and the water spray quenching characteristics of waste tire pyrolysis oil-gas were obtained. The results showed that water spray quenching technology condensed the oil-gas rapidly and reduced its partial pressure, thereby reducing the content of low flash point components in the pyrolysis oil significantly and increasing the flash point of the pyrolysis oil. The results of GC-MS analysis showed that the water spray quenching process reduced the content of low carbon components and increased the content of high carbon components in the pyrolysis oil, resulting in a shift in the carbon number distribution of pyrolysis oil components from low carbon to high carbon. Water spray quenching reduced the content of aliphatic hydrocarbons, monocyclic aromatic hydrocarbons (MAHs) and heteroatomic compounds in the pyrolysis oil while the content of polycyclic aromatic hydrocarbons (PAHs) was increased. The content of BTEX and D-limonene as high value-added products was also decreased. In addition, water spray quenching reduced the total content of components containing nitrogen or sulfur in the pyrolysis oil, wherein the content of nitrogen compounds and nitrogen-sulfur compounds decreased, while the content of sulfur compounds increased slightly. This study provided a reference for the research on the quality improvement and modification of waste tire pyrolysis oil.

Key words: waste tires, pyrolysis oil, water spray quenching, flash point, component distribution

中图分类号:

TE992.3

毛宇炜, 薛志亮, 洪钦, 付鑫, 金建龙, 周永刚, 黄群星. 废轮胎热解油气喷水急冷特性[J]. 化工进展, 2025, 44(3): 1263-1274.

MAO Yuwei, XUE Zhiliang, HONG Qin, FU Xin, JIN Jianlong, ZHOU Yonggang, HUANG Qunxing. Study on water spray quenching characteristics of waste tire pyrolysis oil-gas[J]. Chemical Industry and Engineering Progress, 2025, 44(3): 1263-1274.

图/表 18

参考文献 37

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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
1.03	7.81	61.70	29.46	80.76	6.81	0.39	0.39	2.84

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
1.03	7.81	61.70	29.46	80.76	6.81	0.39	0.39	2.84

测量参数	测量次数	计算方法	u_A
油气冷凝温度	120	贝塞尔法	0.182℃
油气冷凝压力	120	贝塞尔法	1.526Pa
热解油闪点	3	极差法	1.264℃
热解油组分相对含量	3	极差法	0.0465%

测量参数	测量次数	计算方法	u_A
油气冷凝温度	120	贝塞尔法	0.182℃
油气冷凝压力	120	贝塞尔法	1.526Pa
热解油闪点	3	极差法	1.264℃
热解油组分相对含量	3	极差法	0.0465%

传感器名称	型号	精度	u_B
K型铠装热电偶	WRNK-131	±0.5%	0.508℃
智能差压传感器	3151DP3B22TM7B3i	±0.1% FS	0.577Pa
单通道K型热电偶	HY-101	±0.1%（±0.4℃）	0.272℃
载气流量检测器	AFC-2030	±5%	0.232%

废轮胎热解油气喷水急冷特性

Study on water spray quenching characteristics of waste tire pyrolysis oil-gas

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参考文献 37

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工况	序号	热解油闪点/℃	冷凝温度/℃	热解油产率/%
未采用喷水急冷	1	78	205.1	17.27
未采用喷水急冷	2	62	170.0	17.52
采用喷水急冷	3	78	176.7	18.72
采用喷水急冷	4	62	146.2	21.23

组分类别	碳数区间	未采用喷水急冷组分物质的量占比/%		采用喷水急冷组分物质的量占比/%
组分类别	碳数区间	147℃	176℃	147℃	176℃
MAHs	C₇~C₁₀	74.19	67.41	65.73	60.98
	C₁₁~C₁₈	25.81	32.59	32.50	35.04
	C₁₉~C₃₂	0	0	1.77	3.97
杂原子化合物	C₇~C₁₀	29.27	14.69	17.56	10.41
杂原子化合物	C₁₁~C₁₈	70.73	85.31	82.43	89.59
脂肪烃	C₁₁~C₁₈	62.49	23.97	29.86	21.59
脂肪烃	C₁₉~C₃₂	37.51	76.03	70.14	78.41

组分	CAS号	组分名称	分子式	类别
含氮组分	1198-37-4	2,4-二甲基喹啉	C₁₁H₁₁N	喹啉类
	629-79-8	十六腈	C₁₆H₃₁N	腈类
	5399-02-0	十七腈	C₁₇H₃₃N	腈类
	101-54-2	对氨基二苯胺	C₁₂H₁₂N₂	二苯胺
	793-24-8	4-[(4-甲基-2-戊基) 氨基]二苯胺	C₁₈H₂₄N₂	二苯胺
含硫组分	18428-05-2	2-乙基-5,7- 二甲基苯并[b]噻吩	C₁₂H₁₄S	噻吩衍生物
同时含氮含硫组分	95-16-9	苯并噻唑	C₇H₅NS	苯并噻唑
同时含氮含硫组分	883-93-2	2-苯基苯并噻唑	C₁₃H₉NS	苯并噻唑衍生物

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冷凝温度/℃	闪点/℃
188	67
177	63
177	62
175	61
150	47
145	46

冷凝温度/℃	闪点/℃
188	67
177	63
177	62
175	61
150	47
145	46