鄯善低温煤焦油成分的谱学分析与评价
收稿日期: 2015-03-09
修回日期: 2016-01-22
网络出版日期: 2016-03-05
基金资助
国家自然科学基金资助项目(21276219);新疆科技厅重点实验室开放课题(2015KL022).
Spectral Analysis and Evaluation of Shanshan Coal Tar
Received date: 2015-03-09
Revised date: 2016-01-22
Online published: 2016-03-05
利用核磁共振(NMR)和傅里叶变换红外光谱(FT-IR)对新疆鄯善地区原煤干馏制取的煤焦油进行了研究.NMR研究结果表明鄯善煤焦油的芳碳率farC为0.44;平均碳数N为2.87;取代指数s为0.33;缩合指数Q为0.74,这与缩合芳香环上连接的烷基侧链较多、链长较短有关;含氧官能团主要以芳醚形式存在;羧基、甲氧基脱落或者消失.选择了5个红外光谱参数B1~B5,用Ominic软件对谱图进行了矢量归一化并积分,获得了IR相关的部分结构参数.通过对NMR和IR结构参数的分析,推测鄯善原煤的处于中等变质程度,其类型属于以镜质体为主的腐殖型煤;成烃机理主要是长链烃断裂;由生烃机理推测其原煤的生气潜力大于生油潜力,其生气潜力碳主要为甲基单元.
关键词： 核磁共振(NMR); 傅里叶变换红外光谱(FT-IR); 结构参数; 煤焦油; 鄯善
洪琨 , 马凤云 , 赵新 , 钟梅 , 刘景梅 , 刘月娥 , 和鲁 . 鄯善低温煤焦油成分的谱学分析与评价[J]. 波谱学杂志, 2016 , 33(1) : 96 -105 . DOI: 10.11938/cjmr20160109
The composition and structure parameters of coal tar distilled from the coal of the Shanshan area, Xinjiang were studied by NMR spectroscopy and Fourier transform infrared (FT-IR) spectrometry. With the structure parameters calculated from the spectra, and coalification degree and hydrocarbon generation capacity of the crude coal were evaluated. The result showed that the average rate of aromatic carbon (farC) was 0.44, carbon number (N) was 2.87, replace index (s) was 0.33 and condensation index (Q) was 0.74. It was found that there were many alkyl-side chains connecting to the condensation aromatic nuclei. Five IR parameters (B1~B5) were chosen to process the spectra with vector normalization and integral in the Ominic software. The NMR and IR data indicated that the crude coal is medium in metamorphic grade, and belongs to humic coal mainly composed of vitrinite. The oxygen-containing functional groups exist mainly in the form of aryl ethers. Carboxyl and methoxy groups either fall out or disappear. According to the hydrocarbon generation mechanism, these data indicated that the gas potentiality of the coal tar is higher than its oil potential; and the gas potential carbon is mainly the methyl units.
Key words： NMR; FT-IR; structure parameters; coal tar; Shanshan
[1] Xie K C, Li W Y, Zhao W. Coal chemical industry and its sustainable development in China[J]. Energy, 2010(11): 4 349－4 353.
[2] Li Che(李彻), Zhang Chuan-ming(张传名), Zhou Yue-gui(周月桂). Trial-changing a 220 t/h oil fired boiler to firing coal tar(220 t/h燃油锅炉改烧煤焦油的实验研究)[J]. Generating Equipment(发电设备), 2007, 21(3): 177－180.
[3] Zhang Tong-xiang(张同翔), Ren You-zhong(任有中), Qian Jian-qing(钱剑清), et al. Elementary investigation on emulsified coal-tar oil as fuel(乳化煤焦油作为锅炉燃料的初步研究)[J]. Boiler Technology(锅炉技术), 2004, 35(3): 45－48.
[4] Shui Heng-fu(水恒福). The Separation and Purification of Coal Tar(煤焦油分离与精制)[M]. Beijing(北京): Chemical Industry Press(化学工业出版社), 2007.
[5] Zhang Yang(张飏), Sun Hui-qing(孙会青), Bai Xiao-yan(白效言). The basic property and comprehensive utilization of the low temperature coal tar(低温煤焦油的基本特性及性和利用)[J]. Coal Combustion(煤炭燃烧), 2009, 15(6): 57－59.
[6] Zhang Jun-min(张军民), Liu Gong(刘弓). Comprehensive utilization of low-temperature coal tar(低温煤焦油的综合利用)[J]. Coal conversion(煤炭转化),2010, 33(3): 92－96.
[7] Palmer T J, Vahrman M. The smaller molecules obtainable from coal and their significance: Part 4. Composition of low-temperature tars[J]. Fuel, 1972, 51: 22－26.
[8] Mei Yuan-fei(梅远飞), Zhao Xin(赵新), Sun Wan-fu(孙万赋), et al. The spectra analysis of Ili coal tar(伊犁煤焦油成分的谱学分析)[J]. Journal of Shihezi University(石河子大学学报), 2011, 29(3): 384－389.
[9] Mei Yuan-fei(梅远飞), Zhao Xin(赵新), Sun Wan-fu(孙万赋), et al. Spectal analysis of coal tar from Xiaohuangshan region(小黄山煤焦油成分的谱学分析)[J]. Chinese J Magn Reson(波谱学杂志), 2011, 28(3): 339－348.
[10] Zhang Zhen-fang(张振芳), Gao Han-bin(高汉宾). Magnetic Resonance Imaging Principle and Test Method(核磁共振原理与试验方法)[M]. Wuhan(武汉): Wuhan University Press(武汉大学出版社), 2008.
[11] Chen Lin(陈琳), Meng Xue-song(孟雪松), Wu Hong-xin(吴洪新), et al. Study on a kind of low-temperature coal tar by high resolution NMR(一种低温煤焦油的高分辨核磁共振研究)[J]. Speciality petrochemicals(精细石油化工), 2013, 30(6): 18－81.
[12] GB475-2008. Method for manual sampling of commercial coal(商品煤样人工采取方法)[S]. 2008.
[13] GB474-2008. Method for preparation of coal sample(煤样的制备方法)[S]. 2008.
[14] Zou Gang-ming(邹纲明), Ling Kai-cheng(凌开成), Li Xiang-lan(李香兰). Study on reaction and mechanism in coprocessing of Yanzhou coal and tar(烟煤和低温煤焦油共处理反应及机理研究)[J]. Journal of Fuel Chemistry and Technology(燃料化学学报), 1996, 24(5): 447－451.
[15] Cheng Ke-ming(程克明), Gu Xin-zhang(顾信章). The geochemical properties of asphaltenes and it classification with respect to the organic matter in the source rocks(沥青质的地球化学性质及其对母岩有机质的分类意义)[J]. Petroleum Exploration and Development(石油勘探与开发), 1983,10(5): 23－33.
[16] Yang Tao(杨涛). Structure Characterization of Asphaltene and Its Influence on the Flowability of Crude Oil with Comb-Type Copolymers(沥青质结构表征及其存在对梳型聚合物改善原油流动性的影响)[D]. Shanghai(上海): East China University of Science(华东理工大学), 2013.
[17] Chilingarian G V, Yen Bitumens T F. Asphalts and tar sands[J]. Developments in Petroleum Science, 1978, 8: 155－190.
[18] Cai Yun-kai(蔡云开). 1H NMR analysis of asphaltene in coal of different ranks and its geochemical significance(不同煤级煤的沥青质1H NMR分析及其地球化学意义)[J]. Geoscience(现代地质), 1992, 6(3): 338－346.
[19] Mei Yuan-fei(梅远飞). Study on Spectroscopy and Performance Potential of Hydrocarbon in Xinjiang Coal(新疆地产煤的谱学及其生烃潜能的研究)[D]. Urumqi(乌鲁木齐): Xinjiang University(新疆大学), 2011.
[20] Wang Yan-bin(王延斌), Han De-xin(韩德馨), Liu Xian-wei(刘咸卫). Research on 13C NMR of major macerals of coals in bohaiwan basin(渤海湾彭迪C-P煤有机分13C NMR研究)[J]. Journal of China University of Mining & Technlogy(中国矿业大学学报), 1999, 28(1): 37－40.
[21] Wu Fan(吴帆), Peng Pu(彭朴), Lu Wan-zhen(陆婉珍). A datebase for NMR chemical shift of hydrocarbons and chemical shift distribution of each subgroup(烃类化合物NMR化学位移数据库及各类碳氢原子化学位移统计分布)[J]. Chinese J Magn Reson(波谱学杂志), 1996, 13(4): 393－402.
[22] Zhang Peng-zhou(张蓬洲), Li Li-yun(李丽云), Ye Chao-hui(叶朝辉). Solid state 13C NMR study of Chinese coals(用固体高分辨核磁共振研究煤结构I.我国－些煤的结构特征)[J]. Journal of Fuel Chemistry and Technology(燃料化学学报), 1993, 21(3): 310－315.
[23] Qin Kuang-zong(秦匡宗), Wu Xiao-ling(吴肖令). Hydrocarbon format ion machanism of fushun oil shale during pyrolysis-a study with solid state 13C NMR spectroscopic techniques(抚顺油页岩热解成烃机理-固体13C NMR技术的应用)[J]. Petroleum Processing Section(石油学报: 石油加工), 1990, 6(1): 36－44.
[24] Huang Di-fan(黄第藩), Qin Kuang-zong(秦匡宗), Wang Tie-guan(王铁冠), et al. Oil from Coal: Formation and Mechanism(煤成油的形成和成烃机理)[M]. Beijing(北京): Petroleum Industry Press(石油工业出版社), 1995.
[25] Xie Ke-chang(谢克昌). Coal Structure and Its Reactivity(煤的结构与反应性)[M]. Beijing(北京): Science Press(科学出版社). 2002.
[26] Yang Qi(杨起). The Coal Metamorphism in China(中国煤变质作用)[M]. Beijing(北京): China Coal Industry Publishing House(煤炭工业出版社). 1996.
[27] Sobkowiak M, Reisser E, Given P, et al. Determination of aromatic and aliphatic CH groups in coal by FT-IR. 1, Studies of coal extracts[J]. Fuel, 1984, 63: 1 245－1 252.
[28] Reisser E, Starsinic M, Squires E, et al. Determination of aromatic and aliphatic CH groups in coal by FT-IR. 2, Studies of coals and vitrinite concentrates [J]. Fuel, 1984, 63: 1 253－1 261.
[29] Zhang Ke(张科), Yao Su-ping(姚素平), Hu Wen-xuan(胡文瑄), et al. Analysis on infrared spectra characteristic of coal and discussion of coalification mechanism(煤红外光谱的精细解析及其煤化作用机制)[J]. Coal Geology & Exploration(煤田地质与勘探), 2009, 37(6): 8－13.
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