Influence of carbonyl containing groups on the low-temperature pyrolysis of low-rank coal

doi:10.10685/j.issn.1000-6613.2017-2433

Chemical Industry and Engineering Progress ›› 2018, Vol. 37 ›› Issue (11): 4257-4264.DOI: 10.10685/j.issn.1000-6613.2017-2433

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Influence of carbonyl containing groups on the low-temperature pyrolysis of low-rank coal

LIU Tao, WANG Hongchao, CHANG Guozhang, GUO Qingjie

Key Laboratory of Clean Chemical Processing of Shandong Province, College of Chemical Engineering, Qingdao University of Science & Technology, Qingdao 266042, Shandong, China

Received:2017-11-24 Revised:2017-12-25 Online:2018-11-05 Published:2018-11-05

低阶煤羰基结构对其低温热解过程的影响

刘涛, 王洪超, 常国璋, 郭庆杰

青科技大学化工学院, 清洁化工过程山东省高校重点实验室, 山东青岛 266042

通讯作者: 郭庆杰,教授。E-mail:qj_guo@yahoo.com。
作者简介:刘涛(1989-),男,博士研究生。
基金资助:
山东省重点研发计划（2016GSF117005）及山东省自然基金重点项目（ZR2015QZ02）。

Abstract

Abstract: In order to explore the influence of carbonyl containing groups (CCPs) on the low-temperature pyrolysis process of low-rank coal, the content/structure of CCPs and other chemical structures for four kinds of low-rank coals (LRC) which had similar elementary composition were characterized by ¹³C NMR. The influence of CCPs on the LRCs' low-temperature pyrolysis process was investigated in a TGA and a fixed-bed pyrolysis reactor. The results showed that the four LRCs had similar elementary composition and the main frame structure. However, there were big differences in the content and structure of carbonyl containing groups. The mole percent order of CCPs in aromatic structure of the four LRC was BS > BT > ER > QJ, while that in aliphatic structure was just in the reverse order. The results of TG-FTIR showed that CCPs in aliphatic structure resulted in the weight loss in low-temperature stage (30-350℃). A mount of CO₂ was produced at the same time. The CCPs in aromatic structure promoted the generation of small molecule aromatic and aliphatic hydrocarbons and the weight loss in high-temperature stage (350-550℃). The results of low-temperature pyrolysis experiments showed that there was a positive correlation between the tar/phenolic yield and the CCPs content in aromatic structure.

Key words: low-rank coal, carbonyl containing group, low-temperature pyrolysis, aliphatic structure, aromatic structure

摘要： 为探究含羰基官能团（CCP）含量和结构对低阶煤（LRC）低温热解过程的影响，本文利用¹³C NMR对4种元素组成相似的LRC结构进行了表征，并利用TG-FTIR和固定床热解反应装置研究了CCP结构对其低温热解过程的影响。研究结果表明，4种LRC元素组成和主要骨架结构类似，CCP结构存在较大差异，芳香结构中CCP摩尔分数大小顺序为BS > BT > ER > QJ，而脂肪结构中CCP含量与之相反。CCP结构和含量对LRC的低温热解过程有着明显的影响，TG-FTIR实验表明，LRC中脂肪结构CCP能够显著促进低温区（30～350℃）CO₂的生成，且含量越高在低温区失重量越大；而芳香结构CCP则促进了高温区（350～550℃）小分子芳烃和脂肪烃的生成，且含量越高，LRC在高温区失重速率越大。低温热解实验证明，热解焦油产率和酚类物质含量与LRC中芳香结构CCP含量呈正相关，与脂肪结构CCP含量呈负相关关系。

关键词: 低阶煤, 含羰基官能团, 低温热解, 脂肪结构, 芳香结构

CLC Number:

TQ546.1

LIU Tao, WANG Hongchao, CHANG Guozhang, GUO Qingjie. Influence of carbonyl containing groups on the low-temperature pyrolysis of low-rank coal[J]. Chemical Industry and Engineering Progress, 2018, 37(11): 4257-4264.

刘涛, 王洪超, 常国璋, 郭庆杰. 低阶煤羰基结构对其低温热解过程的影响[J]. 化工进展, 2018, 37(11): 4257-4264.

References

[1] 傅雪梅, 路露, 葛燕燕, 等. 我国褐煤资源及其物性特征[J]. 煤炭科学技术, 2012, 40(10):104-107. FU Xuemei, LU Lu, GE Yanyan, et al. China lignite resources and physical features[J]. Coal Science and Technology, 2012, 40(10):104-107.
[2] 郭志航. 褐煤热解分级转化多联产工艺的关键问题研究[D]. 杭州:浙江大学, 2015. GUO Zhihang. Research on key issues of lignite pyrolysis-based staged conversion polygeneration technology[D]. Hangzhou:Zhejiang University, 2015.
[3] 朱学栋, 朱子彬, 韩崇家,等. 煤的热解研究Ⅲ. 煤中官能团与热解生成物[J]. 华东理工大学学报, 2000(1):14-17. ZHU Xuedong, ZHU Zibin, HAN Chongjia, et al. Fundamental study of coal pyrolysis Ⅲ. functional group and pyrolysis products[J]. Journal of East China University of Science and Technology, 2000(1):14-17.
[4] HARRY N S. Pyrolysis of brown coals. 4. Relation between acidic groups and evolved carbon oxeyes[J]. Fuel, 1980, 59(5):302-304.
[5] 朱学栋, 朱子彬, 张成芳, 等. 煤的热解研究Ⅳ.官能团热解模型[J]. 华东理工大学学报, 2001(2):113-116. ZHU Xuedong, ZHU Zibin, ZHANG Chengfang, et al. Fundamental study of coal pyrolysis IV. functional group pyrolysis model[J]. Journal of East China University of Science and Technology, 2001(2):113-116.
[6] MACPHEE J A, CHARLAND J P,GIROUX L. Application of TG-FTIR to the determination of organic oxygen and its speciation in the Argonne premium coal samples[J]. Fuel Processing Technology, 2006, 87:335-341.
[7] YOSHIDA T, MAEKAWA Y. Characterization of coal structure by CP/MAS carbon-13 NMR spectrometry[J]. Fuel Processing Technology, 1987, 15:385-395
[8] SONG C, HOU L, SAINI A K, et al. CPMAS ¹³C NMR and pyrolysis-GC-MS studies of structure and liquefaction reactions of Montana subbituminous coal[J]. Fuel Processing Technology, 1993, 34(3):249-276.
[9] 荣国斌. 波普数据表-有机化合物的结构解析[M]. 上海:华东理工大学出版社, 2002. RONG Guobin. Structure determination of organic compounds tables of spectral data[M]. Shanghai:East China University of Science and Technology Press, 2002.
[10] TREVOR J Morgan, RAFAEL K. Pyrolysis of coals and biomass:analysis of thermal breakdown and its products[J]. Chem. Rev., 2014, 114:1547-1607.
[11] MIURA K, MAE K, LI W, et al. Estimation of hydrogen bond distribution in coal through the analysis of OH stretching bonds in diffuse reflectance infrared spectrum measured by in-situ technique[J]. Energy & Fuels, 2001, 15:599-610.
[12] ESKAY T P, BRITT P F, BUCHANAN Ⅲ A C. Pyrolysis of aromatic carboxylic acids:potential involvement of anhydrides in retrograde reactions in low-rank coal[J]. Energy & Fuels, 1997, 11:1278-1287.
[13] MOCHIDA I, OKUMA O, YOON S H. Chemicals from direct coal liquefaction[J]. Chemical Review, 2014, 114:1637-1672.

Influence of carbonyl containing groups on the low-temperature pyrolysis of low-rank coal

低阶煤羰基结构对其低温热解过程的影响

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