不同镜惰比低阶煤燃烧特性及动力学分析

王小令; 王绍清; 陈昊; 赵云刚; 沙吉顿; 邓金松

doi:10.12438/cst.2021-1477

不同镜惰比低阶煤燃烧特性及动力学分析

中国矿业大学(北京) 地球科学与测绘工程学院, 北京　100083

基金项目:

国家自然科学基金资助项目（42030807）；山西省重点研发计划资助项目（201903D321084）

详细信息

作者简介:
王小令: （1994—），男，重庆梁平人，博士研究生。E-mail：1021736917@qq.com

通讯作者:
王绍清: （1979—），男，辽宁朝阳人，教授，博士。E-mail：wangzq@cumtb.edu.cn

中图分类号: TQ533
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出版历程
- 收稿日期: 2022-05-27
- 网络出版日期: 2023-08-08
- 刊出日期: 2023-09-18

The combustion characteristics and kinetic analysis of low-rank coals with different vitrinite/inertinite ratio

School of Geosciences and Surveying Engineering, China University of Mining and Technology-Beijing, Beijing 100083, China

Funds:

National Natural Science Foundation of China（42030807）； Key Research and Development Program of Shanxi Province (201903D321084)

摘要

摘要:
为解释显微组分对低阶煤燃烧特性的影响，以一系列不同镜惰比低阶煤为研究对象，利用热重−质谱−差热（TG-MS-DTA）联用技术，研究了样品在空气气氛下的燃烧特性、热量变化过程以及气体逸出行为。结果表明：煤的显微组分含量对煤燃烧达到最大反应速率时的温度影响不大，但对反应最大速率的大小有影响，富惰质组煤燃烧的反应最大速率更大。同时，煤中较多矿物使得反应达到最大速率时温度更高。燃烧过程呈现出明显的两个阶段，第一阶段（400 ℃之前）缓慢放热，对应脱挥发分过程，第二阶段（400 ℃之后）快速放热，对应固定碳燃烧过程，燃烧放热特征呈现出缓慢到快速放热的转变。不同镜惰比煤在燃烧过程中主要释放CO₂、CO、H₂O等气体，但释放的相对含量不同，脱挥发分阶段，有较少的CO₂、CO气体释放，H₂O的释放相对量较多。而在固定碳燃烧阶段，CO₂大量释放，CO释放量略低，H₂O最少。其中，富惰质组煤在燃烧过程中释放相对更多的CO₂，在相同条件下，燃烧更加充分。此外，还借助Coats-Redfern积分法对煤燃烧过程进行动力学计算，得到随着镜惰比含量减小，反应活化能增加的趋势，但这并不影响富惰质组煤在固定碳燃烧阶段能快速燃烧的特性，这可能是由于惰质组中大量丝质体形成的细胞胞腔结构，增大了与O₂的接触面积，燃烧反应充分。
- 低阶煤 /
- 燃烧行为 /
- 动力学 /
- 不同镜惰比 /
- 热重-质谱-差热
Abstract:
To explain the effect of maceral composition on the combustion characteristics of coal, a series of low-rank coals with different vitrinite/inertinite ratio were collected as the research object, and the combustion characteristics, heat change process and gas escape behavior of the samples under air atmosphere were investigated using thermoanalytical methods (TG-MS-DTA). The results show that the maceral content has little effect on the temperature of the maximum reaction rate. However, it has an effect on the value of the maximum reaction rate, and the maximum reaction rate of the inertinite-rich coal is larger. Meanwhile, higher minerals in coal allow the reaction to reach its maximum rate at a higher temperature. The combustion process shows two obvious stages. The first stage (before 400 ℃) is exothermic slowly, corresponding to the devolatilization process, and the second stage (after 400 ℃) is exothermic rapidly, corresponding to the fixed-carbon combustion process. The exothermic characteristics of coal combustion show a slow to fast exothermic transition. Coal with different vitrinite/inertinite ratio mainly release CO₂, CO, H₂O during the combustion process, however, the relative content of the released gas is different. In the devolatilization stage, there is less CO₂ and CO released, while more H₂O release. In the fixed-carbon combustion stage, a large amount of CO₂ is released, the amount of CO released is slightly lower, and H₂O is the lowest. Among them, the inertinite-rich coal releases relatively more CO₂ during the combustion process and burns more completely under the same conditions. In addition, the kinetic calculation of the coal combustion process is carried out with the Coats-Redfern method, and the trend of reaction activation energy increases as the vitrinite/inertinite ratio decreases. However, it does not affect the inertinite-rich coal in the fixed-carbon combustion stage. The ability to burn rapidly may be due to the cell lumen structure formed by a large number of fusinites, which enlarges the contact area between the surface of coal particles and O₂, and the combustion reaction is sufficient.
- low-rank coal /
- combustion behavior /
- kinetics /
- different Vitrinite/Inertinite ratio /
- TG-MS-DTA

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图 1 赵家庄煤中丝质体光学显微镜照片

Figure 1. Optical microscope image of fusinite in ZJZ coal

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图 2 XRD图谱分析

Figure 2. XRD spectra analysis

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图 3 不同镜惰比煤燃烧TG与DTG曲线

Figure 3. TG and DTG curves of coal combustion with different vitrinite/inertinite ratio

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图 4 不同镜惰比煤燃烧过程的DTA曲线

Figure 4. DTA curves of coal combustion with different vitrinite/inertinite ratio

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图 5 不同镜惰比煤燃烧过程中气体释放质谱

Figure 5. Mass spectrometry of coal combustion with different vitrinite/inertinite ratio

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图 6 不同镜惰比煤燃烧释放的3种主要气体

Figure 6. Three main released gases of coal combustion with different vitrinite/inertinite ratio

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图 7 不同镜惰比煤在最大反应速率温度下质谱信号强度

Figure 7. Mass spectrum signal intensity of coal with different vitrinite/inertinite ratio at maximum reaction rate temperature

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图 8 基于Coats-Redfern积分法得到的煤燃烧Arrhenius图

Figure 8. Arrhenius diagram of coal combustion based on Coats-Redfern

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表 1 煤样煤岩组分分析、工业分析、元素分析^[21]

Table 1 Petrological, proximate and ultimate analysis of coal samples^[21]

样品	煤岩分析（体积分数）/%				V/I	工业分析/%			R_o /%	元素分析/%
样品	镜质组	惰质组	类脂组	矿物	V/I	M_ad	A_ad	V_daf	R_o /%	C_daf	H_daf	O_daf^*	N_daf	S_t,d
ZJZ	8.8	88.8	0.4	2	0.10	8.7	7.34	28.69	0.55	82.08	3.78	13.00	1.02	0.12
MTH	40.0	51.6	3.6	4.8	0.76	2.72	12.18	34.95	0.68	83.57	4.72	9.39	1.53	0.69
DT	62.0	35.2	0.4	2.4	1.76	7.3	2.85	38.43	0.47	79.68	4.72	14.12	1.25	0.22
注：R_o为样品最大镜质组反射率；*为差减法计算。

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表 2 不同镜惰比煤的燃烧特征参数

Table 2 Characteristic parameters of coal combustion with different vitrinite/inertinite ratio

样品	T_i/℃	T_p/℃	T_f/℃	R_max/(%·℃⁻¹)
ZJZ	457.3	489.4	499.2	2.23
MTH	461	526.4	572.3	0.71
DT	437	490	514.9	1.16

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表 3 不同镜惰比煤燃烧动力学参数

Table 3 Kinetic parameters of coal combustion with different vitrinite/inertinite ratio

样品	T₁₀/℃	T₉₀/℃	方程	E/(kJ·mol⁻¹)	A/min⁻¹	R²
ZJZ	411.4	496.3	y=−16870x+9.1452	140.3	2.37×10⁹	0.9707
MTH	447.0	568.7	y=−14179x+4.2197	117.9	1.45×10⁷	0.9988
DT	385.4	517.0	y=−11535x+2.0218	95.9	1.31×10⁶	0.9844

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