矿化垃圾衍生燃料热解过程HCl与H<sub>2</sub>S析出规律

林均衡; 杨文申; 阴秀丽; 吴创之

矿化垃圾衍生燃料热解过程HCl与H₂S析出规律

林均衡^{1, 2},
杨文申^1, ,,
阴秀丽¹,
吴创之¹

1.
中国科学院广州能源研究所中国科学院可再生能源重点实验室, 广东省新能源和可再生能源重点实验室, 广东广州 510640
2.
中国科学院大学, 北京 100049

基金项目:

国家重点研发计划 2016YFE0203300

广东省自然科学基金 2017B030308002

广州市科技计划项目 201707010242

详细信息

中图分类号: X705
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- 被引次数: 0
出版历程
- 收稿日期: 2017-11-19
- 修回日期: 2018-01-09
- 网络出版日期: 2021-01-23
- 刊出日期: 2018-02-10

Release of HCl and H₂S during pyrolysis of aged refuse derived-fuels

1.
Key Laboratory of Renewable Energy, CAS, Guangdong Provincial Key Laboratory of New and Renewable Energy Research and Development, Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640, China
2.
University of Chinese Academy of Sciences, Beijing 100049, China

Funds:

the National Key R&D Program of China 2016YFE0203300

the Guangdong Natural Science Foundation 2017B030308002

the Science and Technology Program of Guangzhou 201707010242

More Information

Corresponding author: YANG Wen-shen, E-mail: yangws@ms.giec.ac.cn

摘要

摘要: 采用热重红外质谱联用法（TG-FTIR-MS）和水平管式热解炉/化学吸收法，对比研究了矿化垃圾（ARDF）和常规垃圾（NRDF）衍生燃料热解过程腐蚀性气体（HCl和H₂S）的析出特性，分析了热解温度及热解类型对析出行为的影响并对热解固相产物腐蚀性元素的赋存特点进行了考察。结果表明，慢速热解过程，两者腐蚀性气体的析出特征温度区间相似，均分为两段，HCl析出区间为200-400和420-500 ℃，H₂S析出区间为230-370和380-670 ℃，而ARDF表现为较低的HCl和H₂S析出率；快速热解过程，两者腐蚀性气体的析出受热解温度影响较大，且规律有所差别：随热解温度的升高，HCl析出率呈S型变化（先高后低再高），而H₂S析出率呈正相关，均在850 ℃达到峰值，其中，HCl析出率分别为48.8%（ARDF）和29.4%（NRDF），H₂S析出率分别为6.8%（ARDF）和44.6%（NRDF）。因腐蚀性气体差异性的析出规律，两类垃圾热解固相产物腐蚀性元素的赋存与热解温度相关，ARDF的Cl和S元素最高赋存率分别可达59.4%（450 ℃）和84.3%（750 ℃），而NRDF的Cl和S元素最高赋存率分别仅为36.7%（850 ℃）和15.2%（650 ℃）。说明在合适的热解条件下，相比NRDF，ARDF腐蚀性元素不易释放，倾向于固相赋存，此为不同垃圾衍生燃料的热利用提供了一定依据和参考。
- 氯化氢 /
- 硫化氢 /
- 矿化垃圾衍生燃料 /
- 常规垃圾衍生燃料 /
- 热解
Abstract: Based on the horizontal tubular reactor-chemical absorption together with TG-FTIR-MS methods, release characteristics of corrosive gases, viz., HCl and H₂S, during pyrolysis of refuse derived-fuels were investigated. The effects of pyrolysis temperature and pyrolysis type on their release behaviors for the aged (ARDF) and normal (NRDF) categories were compared. Meanwhile, the occurrence properties of corrosive elements (Cl and S) in solid products were also explored. The results indicate that the release of each corrosive gas has similar characteristic temperature range for slow pyrolysis of two categories. The release of HCl occurs at 200-400 and 420-500℃, respectively, while the emission of H₂S is observed at 230-370 and 380-670℃, respectively. In addition, ARDF has a lower emission amounts of both HCl and H₂S compared to NRDF under this condition. With regard to fast pyrolysis, the release of corrosive gases show different regularities, which largely depends on pyrolysis temperature. With increasing temperature, the emission of HCl and H₂S present a nonlinear and an increasing trends, respectively, reaching peak values at 850℃; It is 48.8% (ARDF) and 29.4% (NRDF) for HCl, 6.8% (ARDF) and 44.6% (NRDF) for H₂S. Subsequently, due to the distinctive release characteristics of corrosive gases, the occurrence of corrosive elements in solid phase relating to temperature differs in two categories. The retained amounts of Cl and S reach to 59.4% (450℃) and 84.3% (750℃) for ARDF, respectively. But for NRDF, that is 36.7% (850℃) and 15.2% (650℃), repetitively. It can be inferred that ARDF has the more stable corrosive elements difficult to be released into gases, which could provide some guidelines on thermal utilization of refuse derived-fuels.
- HCl /
- H₂S /
- aged refuse derived-fuels /
- normal refuse derived-fuels /
- pyrolysis

HTML全文

图 1 ARDF(a)和NRDF(b)样品的照片

Figure 1 Pictures of ARDF(a) and NRDF(b)

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图 2 快速热解实验装置示意图

Figure 2 Schematic diagram of rapid pyrolysis system

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图 3 ARDF(a)和NRDF(b)的TG和DTG曲线

Figure 3 TG and DTG curves of ARDF(a) and NRDF(b)

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图 4 ARDF(a)和NRDF(b)慢速热解过程中HCl随温度的析出曲线

Figure 4 Evolution profiles of HCl throughout ARDF (a) and NRDF (b) pyrolysis

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图 5 ARDF(a)、NRDF(b)慢速热过程中H₂S随温度的析出曲线

Figure 5 Evolution profiles of H₂S throughout ARDF (a) and NRDF (b) pyrolysis

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图 6 ARDF(a)、NRDF(b)在快速热解过程中HCl析出率和固相中Cl含量随热解温度的变化

Figure 6 Conversion of HCl-Cl and solid-Cl from ARDF (a) and NRDF (b) during rapid pyrolysis process at different temperatures

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图 7 ARDF(a)、NRDF(b)在快速热解过程中H₂S析出率和固相中S含量随热解温度的变化

Figure 7 Conversion of H₂S-S (a) and Solid-S (b) from ARDF and NRDF during rapid pyrolysis process at different temperatures

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表 1 ARDF和NRDF的元素分析与工业分析

Table 1 Ultimate and proximate analysis of ARDF and NRDF

Sample	Ultimate analysis w_db^*/%								Proximate analysis w_db^*/%
Sample	C	H	N	O^**	total S	inorganic S	total Cl	inorganic Cl	A	V	FC
ARDF	35.95	2.56	0.85	18.29	0.65	0.103	0.95	0.46	41.68	40.75	17.57
NRDF	57.26	6.23	0.87	22.64	0.15	0.007	1.37	0.14	11.48	75.96	12.56
^: dried basis；^*: calculated by difference

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表 2 ARDF和NRDF的HCl红外吸收峰峰面积及HCl相对析出率计算值R_HCl

Table 2 Absorbance area of HCl and R_HCl of HCl from ARDF and NRDF

Sample	Area of peak A	Area of peak B	Result of R_HCl
ARDF	0.6632	0.4344	115.5
NRDF	2.973	0.7283	270.2

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表 3 ARDF及NRDF的H₂S离子吸收峰峰面积及H₂S相对析出率计算值R_H₂S值

Table 3 Ion current area of H₂S and R_H₂S of ARDF and NRDF

Sample	Area of peak A / 1×10^-11	Area of peak B / 1×10^-11	Result of R_H₂S / 1×10^-9
ARDF	0.861	0.316	1.811
NRDF	1.276	1.792	20.453

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