煤红外快速热解过程中床层对二次反应的影响

doi:10.11949/0438-1157.20191264

化工学报 ›› 2020, Vol. 71 ›› Issue (2): 736-745.DOI: 10.11949/0438-1157.20191264

煤红外快速热解过程中床层对二次反应的影响

马金凤^1,²(),曾玺²(),王芳²,康国俊¹(),武荣成²,许光文^2,³

^1.中国矿业大学化学化工学院，江苏省煤基CO2捕集与地质储存重点实验室，江苏徐州 221116
^2.中国科学院过程工程研究所多相复杂系统国家重点实验室，北京 100190
^3.沈阳化工大学资源化工与材料教育部重点实验室，辽宁沈阳 110142

收稿日期:2019-10-24 修回日期:2019-12-13 出版日期:2020-02-05 发布日期:2020-02-05
通讯作者: 曾玺,康国俊
作者简介:马金凤（1992—），女，硕士研究生，jinfengma11@163.com
基金资助:
国家自然科学基金项目(21808227)

Effect of coal layer thickness on secondary reaction during its infrared rapid pyrolysis

Jinfeng MA^1,²(),Xi ZENG²(),Fang WANG²,Guojun KANG¹(),Rongcheng WU²,Guangwen XU^2,³

^1.Key Laboratory of Coal-based CO2 Capture and Geological Storage, School of Chemical Engineering and Technology, China University of Mining and Technology, Xuzhou 221116, Jiangsu, China
^2.State Key Laboratory of Multi-phase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China
^3.Key Laboratory on Resources Chemicals and Materials of Ministry of Education, Shenyang University of Chemical Technology, Shenyang 110142, Liaoning, China

Received:2019-10-24 Revised:2019-12-13 Online:2020-02-05 Published:2020-02-05
Contact: Xi ZENG,Guojun KANG

摘要/Abstract

摘要：

针对煤快速热解研究中样品添加量少(mg级)、焦油收集难等问题，本研究利用压片法制备微薄厚度(mm级)的煤层，并采用红外加热装置考察大添加量(g级)、微薄煤层的快速热解特性。对比堆积煤样和不同煤压片厚度(1.5~3 mm)与个数(1~2)的压片煤样热解特性发现，压片煤层热解过程的二次反应受到明显抑制，焦油产率急剧增加，在1000℃时达9.96%，为格金分析的1.5倍，实现油气产量的同步增长。模拟蒸馏分析发现，堆积状态下焦油以沥青质为主，而微薄煤层制焦油含大量轻油、酚油、萘油、洗油和蒽油。GC-MS和FTIR分析表明，随煤层厚度和个数的减少，焦油组分和含量提高，芳香烃类和含氧官能团吸收增加，进一步验证煤快速热解过程中煤层厚度对焦油产率和品质的影响，揭示在二次反应充分抑制下煤高温热解的初级反应特性。

关键词: 低阶煤, 热解, 红外加热, 二次反应, 焦油, 燃料, 固定床

Abstract:

Aiming at the problems of small sample addition amount (mg level) and difficult tar collection in the rapid pyrolysis of coal, this study uses the tablet method to prepare coal seams with a thin thickness (mm level) and uses an infrared heating device to investigate the large addition amount (g level), fast pyrolysis characteristics of thin coal seams. Compared to the stacking method of coals sample, in the experiment of thin coal layer, the effect of coal layer thickness on the secondary reaction was significantly inhibited, and the tar yield increased sharply, reaching 9.96% at 1000°C and 1.5 times of the Gray-King analysis. Furthermore, a synchronous increase in pyrolysis gas and tar was realized. The simulated distillation analysis shows that asphaltene was the main compound in the tar sample produced from the coal pyrolysis in the stacked state, while for the tar from the pyrolysis of tableting coal layer, it contained a large amount of light oil, phenol oil, naphthalene oil, washing oil and anthracene oil. From the GC-MS and FTIR analysis, it can be seen that with the decrease of thickness and number of the tableting layer, the kind of tar compounds and their corresponding contents increased, and the absorption of aromatic hydrocarbons and oxygen-containing functional groups was strengthened. All of these further verified the influence of coal layer on tar yield and quality in coal fast pyrolysis, and also revealed the primary reaction characteristics of high-temperature coal pyrolysis under the full suppression of secondary reaction.

Key words: low rank coal, pyrolysis, infrared heating, secondary reaction, tar, fuel, fixed-bed

中图分类号:

TQ 530.2

马金凤, 曾玺, 王芳, 康国俊, 武荣成, 许光文. 煤红外快速热解过程中床层对二次反应的影响[J]. 化工学报, 2020, 71(2): 736-745.

Jinfeng MA, Xi ZENG, Fang WANG, Guojun KANG, Rongcheng WU, Guangwen XU. Effect of coal layer thickness on secondary reaction during its infrared rapid pyrolysis[J]. CIESC Journal, 2020, 71(2): 736-745.

图/表 13

图1 常见的煤热解过程及床层和挥发分的相互作用

Fig.1 Common pyrolysis process and interaction between volatiles and char bed

表1 实验用煤的工业分析、元素分析和格金分析

Table 1 Result of proximate, ultimate and G-K analyses of Datong coal

Proximate analysis /

%(mass)

Ultimate analysis/%(mass)

G-K/

%(mass)

M_ad

A_ad

V_ad

O_daf^①

图2 煤红外快速热解实验装置流程图

Fig.2 Schematics of adopted IR heating system for coal pyrolysis

表2 热解实验条件汇总

Table 2 Detailed experiment conditions in this study

序号	样品质量/g	煤样			温度/℃	目的
序号	样品质量/g	样品状态	煤层厚度/ mm	放置压片数量	温度/℃	目的
1	3	堆积	13	—	600~1000	文献常见方法
2	3	压片	3	1	600~1000	验证压片法抑制二次反应可行性
3	3	压片	1.5	2	600~1000	验证临近煤层对二次反应的影响
4	1.5	压片	1.5	1	600~1000	二次反应最小化研究

图3 大同煤热重分析

Fig.3 Thermogravimetric analysis of adopted Datong coal

图4 煤堆积状态下温度对产物分布和气体组成的影响

Fig.4 Effect of temperature on product yield and gas composition for stacking pyrolysis of coal particles

图5 等质量压片状态下温度对产物分布和气体组成的影响

Fig.5 Effect of temperature on product yield and gas composition for pyrolysis of tableting coal layer

图6 同等质量下煤层厚度对热解产物产率及气体组分的影响

Fig.6 Effect of thickness on product yield and gas composition for pyrolysis of tableting coal layer

图7 单个压片煤层热解过程中产率分布和气体组成

Fig.7 Product yield and gas composition of single tableting coal layer pyrolysis at different pyrolysis temperature

图8 1000℃高温下各热解实验的焦油产率及与理论产量的比值a—质量为3 g、堆积状态厚度为13 mm煤样热解实验； b—质量为3 g、厚度3 mm的煤压片热解实验； c—总质量为3 g、两个厚度为1.5 mm的煤压片热解实验； d—质量为1.5 g、单个厚度为1.5 mm的煤压片热解实验

Fig.8 Tar yield and ratio between experiment and theory yield at 1000℃ for different experiments

图9 1000℃高温下各实验制备焦油的模拟蒸馏分析

Fig.9 Comparison of distilling fractions in tar from pyrolysis experiments at 1000℃

图10 1000℃时各焦油样品的GC-MS分析1—甲苯; 2—环己酮; 3—苯酚; 4—3-甲基苯酚; 5—2,4-二甲基苯酚; 6—3,5-二甲基苯酚; 7—7-甲基-1-萘酚; 8—2-甲基萘; 9—1-甲基萘; 10—萘; 11—2-萘酚; 12—菲; 13—3-甲基-5-乙基苯酚

Fig.10 GC-MS analysis of tar samples prepared at 1000℃

图11 1000℃下各实验制备焦油的FTIR分析a—质量为3 g、堆积状态厚度为13 mm的煤样热解实验； b—质量为3 g、厚度3 mm的煤压片热解实验； c—总质量为3 g、两个厚度为1.5 mm的煤压片热解实验； d—质量为1.5 g、单个厚度为1.5 mm的煤压片热解实验

Fig.11 FTIR analysis of tar samples from pyrolysis experiment at 1000℃

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煤红外快速热解过程中床层对二次反应的影响

Effect of coal layer thickness on secondary reaction during its infrared rapid pyrolysis

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