新峪焦精煤中硫在族组分间的赋存规律研究

秦志宏; 张豪非; 戴冬瑾; 赵翠翠; 张丽芳

新峪焦精煤中硫在族组分间的赋存规律研究

中国矿业大学化工学院, 江苏徐州 221116

基金项目: National Natural Science Foundation of China (51274201); National Basic Research Program of China (973 Program, 2012CB214900); the Coal Joint Fund from National Science Foundation of China and Shenhua Group Corporation Limited (U1361116).

详细信息

通讯作者:
秦志宏, qinzh1210@163.com

中图分类号: TQ533.6
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出版历程
- 收稿日期: 2014-09-02
- 修回日期: 2014-09-27
- 刊出日期: 2014-11-30

Study on occurrence of sulfur in different group components of Xinyu clean coking coal

School of Chemical Engineering and Technology, China University of Mining & Technology, Xuzhou 221116, China

Funds: National Natural Science Foundation of China (51274201); National Basic Research Program of China (973 Program, 2012CB214900); the Coal Joint Fund from National Science Foundation of China and Shenhua Group Corporation Limited (U1361116).

摘要

摘要: 为从煤的本体组成结构方面来阐述煤中硫的赋存与分布规律,以高含有机硫的新峪焦精煤为对象,采用萃取反萃取的煤全组分分离方法和XPS、GC/MS等分析技术,对原煤和各族组分中的不同形态无机硫和有机硫含量进行了研究,重点考察了有机硫在煤有机质本体中的赋存规律.结果表明,无机硫的分布主要依赖于其自身在煤主体中的粒径大小和密度高低,与煤族组分本身结构关联较小.无论是原煤还是族组分,其有机硫均以噻吩型硫占主导;共轭结构为主的分子外环境,使共轭结构类有机硫的电子结合能降低,而使脂肪结构类硫的电子结合能升高,反之亦然.有机硫在煤中分布总体均衡,不会因为族组分结构不同而产生较大差异;但有机硫的类型硫赋存比例则与族组分本身的结构特征有所关联,不过其差别相对较小.轻质族组分中只含有一种有机硫小分子化合物,且相对丰度较小.
- 煤炭 /
- 硫 /
- 赋存 /
- 族组分
Abstract: This paper illustrates the occurrence and distribution of sulfur in coal from the perspective of composition and structure of the coal body. With the organic sulfur-rich Xinyu clean coking coal as the sample, and the method of separating all group components from coal through extraction and stripping process as well as X-ray photoelectron spectroscopy (XPS) and gas chromatography/mass spectrometer (GC/MS) analysis techniques, the content of inorganic sulfur and organic sulfur of different forms in raw coal and various group components isstudied and the occurrence of organic sulfur in organic matter of coal is carefully observed. The results show the distribution of inorganic sulfur is mainly dependent upon its particle size and density in coal and has less relationship with the structure of group components of coal. Thiophene sulfur is the major form of organic sulfur either in raw coal or group components. The external environment of molecules dominated by conjugated structure can decrease the electron binding energy of organic sulfur in conjugated structure, while increase that of sulfur in aliphatic structure. The distribution of organic sulfur in coal is balanced as a whole and will not be significantly influenced by structural differences of group components. However, the occurrence of organic sulfur compounds is associated with the structure of group components, showing relatively small difference. And there is only one type of small molecule organic sulfur compounds in light component, with small abundance.
- coal /
- sulfur /
- occurrence /
- group components

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参考文献(24)

任德贻, 雷加锦, 唐跃刚, 郭国莉, 姚玉琴. 煤显微组分中有机硫的微区分析和分布特征[J].煤田地质及勘测, 1993, 21(1): 27-29.(REN De-yi, LEI Jia-jin, TANG Yue-gang, GUO Guo-li, YAO Yu-qin. The microarea analysis and distribution characteristics of the organic sulfur in macerals[J]. Coal Geology & Exploration, 1993, 21(1): 27-29.)

王峰, 宋恩民, 张莲影. 利用四氯乙烯脱除煤中有机硫的机理探讨[J]. 煤炭加工与综合利用, 1998, (5): 12-13.(WANG Feng, SONG En-min, ZHANG Lian-ying. Study on the mechanism of removing organic sulfur in coal with tetrachlorethylene[J]. Coal Processing & Comprehensive Utilization, 1998, (5): 12-13.)

陈鹏. 中国煤中硫的赋存特征及脱硫[J]. 煤炭转化, 1994, 17(4): 1-8.(CHEN Peng. Characteristics and distribution of sulfur in Chinese coals and desulfurization[J]. Coal Conversion, 1994, 17(4): 1-8.)

尤先锋, 刘生玉, 吴争鸣, 任军, 谢克昌. 煤热解过程中氮和硫化合物分配及生成机理[J]. 煤炭转化, 2001, 24(3): 1-5.(YOU Xian-feng, LIU Sheng-yu, WU Zheng-ming, REN Jun, XIE Ke-chang. Study of nitrogen and sulfur distribution and functional forms during coal pyrolysis[J]. Coal Conversion, 2001, 24(3): 1-5.)

朱雪莉. 煤中硫的赋存规律[J]. 科技情报开发与经济, 2010, 20(17): 183-185.(ZHU Xue-li. Talking about the occurrence regularity of sulfur in coal[J]. Sci-Tech Information Development & Economy, 2010, 20(17): 183-185.)

康西栋, 杨起, 张瑞生, 周春光, 汤达祯, 刘大锰. 华北晚古生代煤中有机硫的赋存状态及其成因[J]. 中国地质大学学报, 1999, 24(4): 413-415.(KANG Xi-dong, YANG Qi, ZHANG Rui-sheng, ZHOU Chun-guang, TANG Da-zhen, LIU Da-meng. Occurrence state and origin of organic sulfur in late Paleozoic coal, North China[J]. Earth Science-Journal of China University of Geosciences, 1999, 24(4): 413-415.)

秦志宏. 煤有机质溶出行为与煤嵌布结构模型[M]. 徐州: 中国矿业大学出版社, 2008.(QIN Zhi-hong. Dissolution behavior of organic matters in coal and coal inbuilt state structural model[M]. Xuzhou: China University of Mining and Technology Press, 2008.)

秦志宏. 基于萃取与反萃取的温和化煤族组分分离方法: 中国, 200710022120[P]. 2011-03-30.(QIN Zhi-hong. A mild separation method of coal group components based on extraction and stripping process: CN, 200710022120[P]. 2011-03-30.)

QIN Z H, HOU C L, CHEN J, ZHANG L Y, MA J Q. Group separation of coal components and new ideas of coal utilization as petroleum[J]. Int J Min Sci Technol, 2009, 19(5): 636-641.

KOZLOWSKI M. XPS study of reductively and non-reductively modified coal[J]. Fuel, 2004, 83(3): 259-265.

PIETRZAK R, WACHOWSKA H. The influence of oxidation with HNO₃ on the surface composition of high sulphur coals XPS study[J]. Fuel Process Technol, 2006, 87(11): 1021-1029.

MARINOV S P, TYULIEV G, STEFANOVA M, CARLEER R, YPERMAN J. Low rank coals sulphur functionality study by AP-TPR/TPO coupled with MS and potentiometric detection and by XPS[J]. Fuel Process Technol, 2004, 85(4): 267-277.

刘艳华, 车得福, 徐通模. 利用X射线光电子能谱确定煤及其残焦中硫的形态[J]. 西安交通大学学报, 2004, 38(1): 101-104.(LIU Yan-hua, CHE De-fu, XU Tong-mo. X-Ray photoelectron spectroscopy determination of the forms of sulfur in coal and its chars[J]. Journal of Xi’an Jiaotong University, 2004, 38(1): 101-104.)

GRZYBEK T, PIETRZAK R, WACHOWSKA H. X-ray photoelectron spectroscopy study of oxidized coals with different sulphurcontent[J]. Fuel Process Technol, 2002, 77-78: 1-7.

OLIVELLA M A, PALACIOS J M, VAIRAVAMURTHY A, DEL RÍO J C, DE LAS HERAS F X C. A study of sulfur functionalities in fossil fuels using destructive-(ASTM and Py-GC-MS) and non-destructive-(SEM-EDX, XANES and XPS) techniques[J]. Fuel, 2002, 81(4): 405-411.

朱应军, 郑明东. 炼焦用精煤中硫形态的XPS分析方法研究[J]. 选煤技术, 2010, (3): 55-57.(ZHU Ying-jun, ZHENG Ming-dong.Research on XPS method for analyzing form of sulfur in clean coking coal[J]. Coal Preparation Technology, 2010, (3): 55-57.)

URBAN N R, ERNST K, BERNASCONI S. Addition of sulfur to organic matter during early diagenesis of lake sediments[J]. Geochim Cosmochim Acta, 1999, 63(6): 837-853.

马玲玲, 秦志宏, 张露, 刘旭, 陈航. 煤有机硫分析中XPS分峰拟合方法及参数设置[J]. 燃料化学学报, 2014, 42(3): 277-283.(MA Ling-ling, QIN Zhi-hong, ZHANG Lu, LIU Xu, CHEN Hang. Peak fitting methods and parameter settings in xps analysis for the organic sulfur in coal[J]. Journal of Fuel Chemistry and Technology, 2014, 42(3): 277-283.)

陈娟. 煤全组分族分离产物的形成过程及应用特性研究[D]. 徐州: 中国矿业大学, 2011.(CHEN Juan. Study on formation and application characteristics of products of coal all-components group separation[D]. Xuzhou: China University of Mining and Technology, 2011.)

徐光宪, 王祥云. 物质结构[M]. 2版. 北京: 科学出版社, 2010.(XU Guang-xian, WANG Xiang-yun. Structure of matter[M]. 2nd ed. Beijing: Science Press, 2010.)

王建祺, 吴文辉, 冯大明. 电子能谱学(XPS/XAES/UPS)引论[M]. 北京: 国防工业出版社, 1992.(WANG Jian-qi, WU Wen-hui, FENG Da-ming. Electronic spectroscopy (XPS/XAES/UPS) introduction[M]. Beijing: National Defense Industry Press, 1992.)

郭用猷, 张冬菊, 刘艳华. 物质结构基本原理[M]. 2版. 北京: 高等教育出版社, 2011.(GUO Yong-you, ZHANG Dong-ju, LIU Yan-hua. Fundamental structure principles of substances[M]. 2nd ed. Beijing: Higher Education Press, 2011.)

潘承璜, 赵良仲. 电子能谱基础[M]. 北京: 科学出版社, 1981.(PAN Cheng-huang, ZHAO Liang-zhong. Electron spectroscopy foundation[M]. Beijing: Science Press, 1981.)

刘世宏, 王当憨, 潘承璜. X射线光电子能谱分析[M]. 北京: 科学出版社, 1988.(LIU Shi-hong, WANG Dang-han, PAN Cheng-huang. X-ray photoelectron spectroscopy[M]. Beijing: Science Press, 1988.)

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