结合TG-TDLAS的煤热解反应毒性的评估

孟星星; 康文运; 王庚乾; 李琳; 田亚莉; 郭古青; 刘强; 邱选兵; 李传亮

doi:10.37188/CO.2024-0128

结合TG-TDLAS的煤热解反应毒性的评估

doi: 10.37188/CO.2024-0128

cstr: 32171.14.CO.2024-0128

1.
太原科技大学应用科学学院, 山西省精密测量与在线检测装备工程研究中心, 山西省光场调控与融合应用技术创新中心, 太原 030024
2.
北京跟踪与通信技术研究所, 北京 100089
3.
中国科学院合肥物质科学研究院安徽光学精密机械研究所, 中国科学院大气光学重点实验室, 安徽合肥 230031

基金项目: 国家重点研发计划（No. 2023YFF0718100）；国家自然科学基金（No. 62475182，No. 52076145 & No. 12304403）；山西省科技创新人才团队专项资助（No. 202304051001034）；山西省重点研发计划（No. 202302150101017）；山西省留学人员科技活动项目（No. 20230031）；山西省省筹资金资助回国留学人员科研资助项目（No. 2023-151）；山西省基础研究计划（No. 202303021221147，No. 202203021222204 & No. 202303021212224）；山西省科技合作交流专项（No. 202304041101022）；江淮前沿技术协同创新中心追梦基金课题（No. 2023-ZM01C002）；太原科技大学科研启动基金（No. 20222121 & No. 20232033）；山西省科研实践创新类项目（No. 2023KY667）

详细信息

作者简介:
孟星星（1998—），男，山西朔州人，硕士研究生，2021年于太原科技大学获得学士学位,现于太原科技大学就读硕士，主要从事TDLAS气体检测。E-mail：1977382035@qq.com

邱选兵（1980—），男，四川资中人，博士，教授，2003年在重庆大学获得学士学位，2006年在太原理工大学获得硕士学位，2013年在太原科技大学获得博士学位，主要从事光电微机接口技术、嵌入式系统等方面的研究。E-mail：qiuxb@tyust.edu.cn

中图分类号: TP394.1;TH691.9
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出版历程
- 网络出版日期: 2024-11-11

Assessment of the toxicity of coal pyrolysis reaction in combination with TG-TDLAS

1.
Shanxi Province Engineering Research Center of Precision Measurement and Online Detection Equipment, Shanxi Center of Technology Innovation for Light Manipulations and Applications, School of Applied Science, Taiyuan University of Science and Technology, Taiyuan 030024, China
2.
Beijing Institute of Tracking and Telecommunications Technology, Beijing 100089, China
3.
Key Laboratory of Atmospheric Optics, Anhui Institute of Optics and Fine Mechanics, Hefei Institutes of Physical Science, HFIPS, Chinese Academy of Sciences, Anhui Hefei 230031, China

Funds: National Key R&D Program of China (No. 2023YFF0718100); National Natural Science Foundation of China (No. 62475182, No. 52076145 & No. 12304403); Special Funding for Shanxi Provincial Science and Technology Innovation Talent Team (No. 202304051001034); Key R&D Program of Shanxi Province (No. 202302150101017); Science and Technology Activities Project for Overseas Students in Shanxi Province (No. 20230031); Shanxi Provincial Fund-raising Funding Project for Returning Overseas Students (2023-151); Basic Research Program of Shanxi Province (No. 202303021221147, No. 202203021222204 & No. 202303021212224); Shanxi Provincial Science and Technology Cooperation and Exchange Project (No. 202304041101022); JAC Frontier Technology Collaborative Innovation Center Dream Fund Project (No. 2023-ZM01C002); Taiyuan University of Science and Technology Research Start-up Fund (No. 20222121 & No. 20232033); Shanxi Provincial Scientific Research Practice Innovation Project (No. 2023KY667)

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Corresponding author: qiuxb@tyust.edu.cn

摘要

摘要:
成功构建了一套基于热重-可调谐半导体激光吸收光谱技术（TG-TDLAS）的煤热解HCN气体浓度检测系统，并结合波长调制技术进一步提高了系统的稳定性和灵敏度。利用HCN在波长1531 nm处具有较高吸收强度且受烟气中常见气体干扰较小的特性，通过二次谐波信号处理获取HCN浓度信息。采用高精度的流量控制器，利用99％标准氮气稀释配比得到5×10^-6 mol/mol到20×10^-6 mol/mol的HCN，最后对测量数据进行校准。实验结果表明，HCN的线性相关系数R²为0.9978。基于该实验装置，深入探讨了不同煤种、升温速率和煤粒径大小对热解的影响，以及煤样失重率与HCN浓度释放量的关系。分析了三种不同煤化程度煤种的挥发分中HCN的释放特性和非等温热解动力学。通过划分热解温度阶段，建立了热解动力学模型，并计算不同煤种在不同升温速率下的活化能和频率因子。结果表明，HCN释放量与煤种煤化程度及含氮量密切相关，煤化程度越低，含氮量越高，其HCN释放量越多。在固定的热解终温下，升温速率的增加会导致HCN释放量的增多。随着煤样粒径的减小，热解反应释放HCN的时间会相对滞后，且HCN浓度有所减少。不同热解阶段HCN浓度释放量与煤样失重率之间存在不同的对应关系，热解反应越剧烈，HCN浓度释放量与煤样失重率的比重越大。本研究为进一步评估煤热解反应过程中HCN的毒性提供了重要的实验基础。
- TG-TDLAS /
- 煤热解 /
- 波长调制 /
- 热解动力学
Abstract:
In this paper, a coal pyrolysis HCN gas concentration detection system based on thermogravimetry-tunable diode laser absorption spectroscopy (TG-TDLAS) was successfully constructed, and the stability and sensitivity of the system were further improved by combining wavelength modulation technology. Taking advantage of the characteristics of HCN with high absorption intensity at wavelength 1531 nm and less interference by common gases in the atmosphere, the HCN concentration information was obtained by second harmonic signal processing. A high-precision flow controller is used to obtain HCN from 5×10^-6 mol/mol to 20×10^-6 mol/mol using a 99% standard nitrogen dilution ratio, and the measurement data is calibrated. The experimental results show that the linear correlation coefficient R2 of HCN reaches 0.9978. Then, the effects of different coal types, heating rate, and coal particle size on pyrolysis were discussed, as well as the relationship between the coal samples’ weight loss rate and the amount of HCN concentration released. The release characteristics of HCN and the nonisothermal pyrolysis kinetics in the volatile matter of three coal types with different coalification degrees were analyzed. A pyrolysis kinetic model was established by dividing the pyrolysis temperature stages, and the activation energy and frequency factors of varying coal types at different heating rates were calculated. The results show that the HCN emission is closely related to the degree of coalification and nitrogen content of coal types. The lower the degree of coalification, the higher the nitrogen content and the more HCN emitted. Under the fixed pyrolysis final temperature, an increase in the heating rate will increase the amount of HCN released. With the decrease in coal particle size, the time of HCN release from the pyrolysis reaction will be delayed, and the HCN concentration will decrease. There was a different correspondence between the release of HCN concentration and the coal samples’ weight loss rate in different pyrolysis stages. The more intense the pyrolysis reaction, the greater the proportion of HCN concentration released to the coal samples’ weight loss rate. This study provides an important experimental basis for further evaluation of the toxicity of HCN during coal pyrolysis reactions.
- TG-TDLAS /
- coal pyrolysis /
- wavelength modulation /
- pyrolysis kinetics

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图 1 煤热解HCN检测系统(a)系统原理图；(b)系统实物图

Figure 1. Coal pyrolysis HCN detection system (a) Schematic diagram of the system (b) Physical diagram of the system

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图 2 HCN在1531.154 nm附近的吸收谱线

Figure 2. Absorption line of HCN around 1531.154 nm

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图 3 (a) 在5-20×10⁻⁶ mol/mol范围HCN的光谱吸收曲线；(b) HCN信号强度随浓度变化的线性关系Fig. 3(a) Spectral absorption curves of HCN in the 5-20×10⁻⁶ mol/mol range; (b) Linear relationship of HCN signal intensity as a function of concentration

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图 4 烟煤在不同升温速率下释放的HCN浓度变化

Figure 4. Changes in HCN concentrations released by bituminous coal at different heating rates

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图 5 三种煤样在升温速率为20 °C/min下释放的HCN浓度变化

Figure 5. Changes in HCN concentrations released by the three coal samples at a warming rate of 20°C/min

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图 6 不同粒径的烟煤在升温速率为30 °C/min下的浓度变化

Figure 6. Concentration variation of bituminous coal with different particle sizes at a heating rate of 30°C/min

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图 7 褐煤在三种升温速率(a)10 °C/min(b)20 °C/min(c)30 °C/min下的浓度及热失重变化

Figure 7. Changes in the concentration and thermal weight loss of lignite at three heating rates (a)10°C/min (b)20°C/min (c)and 30°C/min

下载: 全尺寸图片幻灯片

表 1 不同煤种的工业分析

Table 1. Industrial analysis of different coal types

	全硫/S_td	灰分/ A_d	挥发分/V_daf
山西褐煤	1	26	33
山东烟煤	1.95	9.59	31.32
山东无烟煤	3.85	13.1	10.19

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表 2 不同煤种在不同升温速率下的热解动力学参数

Table 2. Kinetic parameters of pyrolysis of different coal types at different heating rates

煤种	β， °C/min	T， °C	E，kJ/mol	A, min⁻¹	R²
褐煤	10	421-654	14.875	12.018	0.932
	10	654-899	29.092	109.600	0.933
	20	409-632	9.667	5.898	0.975
	20	632-880	25.396	141.629	0.968
	30	453-647	22.932	107.295	0.931
	30	647-894	30.971	458.678	0.951
烟煤	10	420-640	27.519	133.482	0.990
	10	640-870	31.750	244.656	0.965
	20	443-661	22.617	103.486	0.975
	20	661-890	27.552	182.316	0.942
	30	460-643	20.100	114.484	0.933
	30	643-890	27.061	369.150	0.941
无烟煤	10	475-708	44.614	1163.052	0.959
	10	708-890	43.431	653.392	0.950
	20	481-648	45.240	2450.536	0.942
	20	650-890	37.665	670.213	0.949
	30	480-650	42.587	2383.327	0.927
	30	650-890	37.556	1024.036	0.931

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