废轮胎热解气燃烧NO x 和SO2生成及控制

doi:10.16085/j.issn.1000-6613.2023-2027

化工进展 ›› 2024, Vol. 43 ›› Issue (12): 7059-7066.DOI: 10.16085/j.issn.1000-6613.2023-2027

• 资源与环境化工 • 上一篇

废轮胎热解气燃烧NO _x 和SO₂生成及控制

代权晨¹(), 薛志亮¹, 周永刚¹, 洪钦², 冯宏², 金亮³, 黄群星¹()

^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.桐乡泰爱斯环保能源有限公司，浙江嘉兴 314500
^3.中国联合工程有限公司，浙江杭州 310052

收稿日期:2023-11-20 修回日期:2023-12-12 出版日期:2024-12-15 发布日期:2025-01-11
通讯作者: 黄群星
作者简介:代权晨（1998—），男，硕士研究生。研究方向为废轮胎热解气燃烧。E-mail：22160491@zju.edu.cn。
基金资助:
浙江省科技计划(2022C03082)

Research on the generation and control of NO _x and SO₂ during the combustion of pyrolysis gas from waste tires

DAI Quanchen¹(), XUE Zhiliang¹, ZHOU Yonggang¹, HONG Qin², FENG Hong², JIN Liang³, 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.China United Engineering Corporation Limited, Hangzhou 310052, Zhejiang, China

Received:2023-11-20 Revised:2023-12-12 Online:2024-12-15 Published:2025-01-11
Contact: HUANG Qunxing

摘要/Abstract

摘要：

废轮胎热解不凝气的稳定清洁燃烧是热解系统稳定运行的关键，但由于不凝气组分复杂，其污染物控制一直是行业的难点。本文基于废轮胎一级热解-二级燃烧的两段式实验系统，研究了废轮胎热解气的组分含量及净化工艺。结果表明废轮胎热解气主要由CH₄、H₂和少量其他小分子碳氢化合物（C₂~C₄）组成，其热值为46.49MJ/m³（标准状况）；热解气中还含有多种含氮含硫化合物，主要是含量为96.43mg/m³（标准状况）的HCN和含量为308.44mg/m³（标准状况）的H₂S；热解气在过量空气气氛下800℃时直接燃烧产生的NO _x 和SO₂平均排放浓度分别为206.65mg/m³（标准状况）和706.01mg/m³（标准状况），且NO _x 主要为燃料型NO。采用分别装有200mL碱性溶液和有机溶剂（如乙二醇、乳酸、甘油和柴油）的洗气瓶对热解气进行清洗可以有效控制燃烧产生的NO _x 和SO₂，其中pH=13.7的NaOH溶液搭配甘油对热解气清洗的控制效果最好，可使NO _x 和SO₂的平均排放浓度分别降低至27.72mg/m³（标准状况）和48.86mg/m³（标准状况），脱除效果分别达到86.58%和93.08%。本文可为废轮胎热解技术规模化推广应用提供有效方法。

关键词: 废轮胎, 热解气, 氮氧化物, 二氧化硫, 清洁燃烧

Abstract:

The stable and clean combustion of pyrolysis gas from waste tires is a key factor for the stable operation of the pyrolysis system. However, due to the complexity of gas composition, controlling pollutants has always been a challenge in the industry. Based on a two-stage experimental system of primary pyrolysis and secondary combustion, the composition of the pyrolysis gas and its purification process were studied in this paper. The results showed that the pyrolysis gas was mainly composed of CH₄, H₂, and small amounts of other hydrocarbons (C₂—C₄), with a calorific value of 46.49MJ/m³ (standard state). The pyrolysis gas also contained a variety of N- and S-containing compounds, mainly including 96.43mg/m³ (standard state) of HCN and 308.44mg/m³ (standard state) of H₂S. When the pyrolysis gas was directly combusted at 800℃ in an excess air atmosphere, the average emission concentrations of NO _x and SO₂ were 206.65mg/m³ (standard state) and 706.01mg/m³ (standard state), respectively, with NO _x mainly in the form of fuel NO. Washing the pyrolysis gas with a wash bottle containing 200mL of alkaline solution and organic solvents (such as ethylene glycol, lactic acid, glycerol, and diesel) could effectively control the NO _x and SO₂. Specifically, using a NaOH solution with a pH=13.7 combined with glycerol for washing the pyrolysis gas shows the best control effect, reducing the average emission concentrations of NO _x and SO₂ to 27.72mg/m³ (standard state) and 48.86mg/m³ (standard state) respectively, achieving removal efficiencies of 86.58% and 93.08%. This study could provide an effective method for the large-scale application and promotion of waste tire pyrolysis technology.

Key words: waste tires, pyrolysis gas, nitrogen oxides, sulfur dioxide, clean combustion

中图分类号:

TE992.3

代权晨, 薛志亮, 周永刚, 洪钦, 冯宏, 金亮, 黄群星. 废轮胎热解气燃烧NO _x 和SO₂生成及控制[J]. 化工进展, 2024, 43(12): 7059-7066.

DAI Quanchen, XUE Zhiliang, ZHOU Yonggang, HONG Qin, FENG Hong, JIN Liang, HUANG Qunxing. Research on the generation and control of NO _x and SO₂ during the combustion of pyrolysis gas from waste tires[J]. Chemical Industry and Engineering Progress, 2024, 43(12): 7059-7066.

图/表 9

表1 废轮胎胶粒工业分析和元素分析（质量分数）

材料	工业分析/%				元素分析/%
材料	M_ad	A_ad	V_ad	FC_ad	C_ad	H_ad	O_ad^①	N_ad	S_ad
废轮胎胶粒	0.76	8.52	61.65	29.07	79.01	6.50	3.53	0.66	1.02

图1 废轮胎一级燃烧-二级热解两段式利用实验系统

表2 废轮胎热解气中含氮含硫化合物种类及含量

种类	含量/mg·m^-3（标准状况）
氰化氢	96.43
氰酸	1.59
氨气	34.62
硫氰酸	33.35
硫化氢	308.44
羰基硫	9.98
甲硫醇	16.00
乙硫醇	3.14
甲硫醚	0.12
二硫化碳	0.57
2-丙硫醇	0.51
2-甲基-2-丙硫醇	0.06
1-丙硫醇	0.21
噻吩	0.11

图2 废轮胎热解气二段燃烧尾气排放物浓度

图3 热解温度对二段燃烧NO x 排放的影响

图4 碱液浓度对NO x 和SO2排放的影响

图5 碱液种类对NO x 和SO2排放的影响

图6 稀硫酸洗气对NO x 和SO2排放的影响

图7 有机溶液洗气对NO x 和SO2排放的影响

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废轮胎热解气燃烧NO _x 和SO₂生成及控制

Research on the generation and control of NO _x and SO₂ during the combustion of pyrolysis gas from waste tires

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