煤热解气体主产物及热解动力学分析

第44卷 第6期

煤田地质与勘探 Vol. 44 No.6 2016年12月 COAL GEOLOGY & EXPLORA TION Dec . 2016

收稿日期: 2015-12-25

基金项目: 山西省煤层气联合研究基金资助项目(2013012005)

Foundation item ：Shanxi Provincial Basic Research Program—Coal Bed Methane Joint Research Foundation(2013012005)

第一作者简介: 刘钦甫(1964—)，男，河南人，博士，教授，从事煤田地质学研究. E-mail ：lqf@https://www.360docs.net/doc/512082892.html,

引用格式: 刘钦甫, 崔晓南, 徐占杰, 等. 煤热解气体主产物及热解动力学分析[J]. 煤田地质与勘探, 2016, 44(6)：27–32.

LIU Qinfu, CUI Xiaonan, XU Zhanjie , et al. Main gases and kinetics of coal pyrolysis[J]. Coal Geology & Exploration, 2016, 44(6)：27–32. 文章编号: 1001-1986(2016)06-0027-06

煤热解气体主产物及热解动力学分析

刘钦甫1，崔晓南2，徐占杰1，郑启明3，毋应科1

(1. 中国矿业大学(北京)地球科学与测绘工程学院，北京 100083；2.中国地质大学(北京)

能源学院，北京 100083；3.河南工程学院资源与环境工程系，河南 郑州451191)

摘要: 为了研究不同煤化程度煤的热解气相产物、热解动力参数，采用热重–红外光谱–质谱(TG-IR-MS)联用技术对4种不同热演化程度的煤进行了热解实验。实时记录了4种煤样在30~1 100℃、10/min ℃升温速率、氦气气氛下热解过程中释放的各种气体成分及其释放量的变化趋势。研究结果表明，随煤热演化程度升高，煤的失重率和最大失重速率逐渐降低，与煤的干燥无灰基挥发分呈正相关关系；随着热解温度的升高，煤中逐渐释放出水、甲烷、二氧化碳、氢气和二氧化硫等小分子气体，且随着煤化程度的升高，各种气体的释放峰逐渐向高温处偏移，说明煤的热稳定性逐渐升高。不同变质程度煤的热解动力学分析结果表明，随着煤变质程度增高，其活化能逐渐降低，说明其热效应强度和发生热解反应的能力在逐渐降低。

关 键 词：煤；热解；热重–红外–质谱联用技术；气相产物；热解动力学

中图分类号：P57 文献标识码：A DOI: 10.3969/j.issn.1001-1986.2016.06.005

Main gases and kinetics of coal pyrolysis

LIU Qinfu 1, CUI Xiaonan 2, XU Zhanjie 1, ZHENG Qiming 3, WU Yingke 1

(1. School of Geoscience and Surveying Engineering , China University of Mining and Technology (Beijing ), Beijing

100083, China ; 2. School of Energy Resources , China University of Geosciences (Beijing ), Beijing 100083, China ;

3. Department of Resources and Environment Engineering , Henan Institute of Engineering , Zhengzhou 451191, China ) Abstract: In order to study the gas products and kinetic parameters of coal pyrolysis, the pyrolysis experiment was carried out for four coal samples with different thermal evolution using Thermo Gravimetric-Infrared-Mass spec-trometry (TG-IR-MS). The variation trend of components and amount of released gases of four kinds of coal sam-ples during pyrolysis at temperature range of 30 to 1℃ 100 with the heating rate of 10/min under helium ℃℃ at-mosphere was recorded in real time. The thermal analysis results showed that the weight loss rate and the maximum weight loss rate of coal decreased gradually with the increase of the thermal evolution degree, and was positively related to the voltile of dry ash-free basis. Some small-molecule gases like H 2O, CH 4, CO 2, H 2 and SO 2 were re-leased gradually with pyrolysis temperature. With the increase of the coalification degree, the peaks of released gases gradually shifted to higher temperature. Pyrolysis kinetic analysis of coals with different coalification degree showed that the activation energy decreased with the metamorphism degree, illustrating that the heat effect strength and the ability of pyrolysis reactions decreased gradually.

Keywords: coal; pyrolysis; TG-IR-MS; gaseous products; kinetics

煤热解是指煤在隔绝空气或惰性气氛下加热，

在不同温度下发生的一系列物理化学反应的复杂过

程，有时也称煤的干馏或热分解。煤热解的研究已

久，包括煤的热解特性、热解动力学、加氢液化和

加催化剂等附加条件的热解等[1-6]。近年来，随着现

代精密测试技术的不断进步，研究更加复杂和深入，涉及到煤与生物质共热解、添加物对煤热解气相产物的影响、热解动力学等诸多领域[7-11]。朱孔远等[7]、L R Steven 等[8]对煤与生物质共热解进行了研究。杨会民等[9]研究宁夏原煤时发现，矿物质及其脱灰煤中Na 、Ca 和Fe 盐的添加会影响热解过程中主要气相产物H 2、CH 4和CO 2的生成量、释放温区、峰形万方数据