干酪根组成结构及其热解生油特性的红外光谱研究

王擎; 许祥成; 迟铭书; 张宏喜; 崔达; 柏静儒

干酪根组成结构及其热解生油特性的红外光谱研究

东北电力大学油页岩综合利用教育部工程研究中心, 吉林吉林 132012

基金项目: 国家自然科学基金(51276034),长江学者和创新团队发展计划(IRT13052)资助项目

详细信息

通讯作者:
王擎,Tel:0432-64807366,Fax:0432-64806281,E-mail:rlx888@126.com.

中图分类号: O657
计量
- 文章访问数: 508
- HTML全文浏览量: 15
- PDF下载量: 583
- 被引次数: 0
出版历程
- 收稿日期: 2015-03-27
- 修回日期: 2015-06-16
- 刊出日期: 2015-10-31

FT-IR study on composition of oil shale kerogen and its pyrolysis oil generation characteristics

Northeast Dianli University, Engineering Research Centre of Oil Shale Comprehensive Utilization Ministry of Education, Jilin 132012, China

Funds: The project was supported by the National Natural Science Foundation of China (51276034) and the Program for Changjiang Scholars and Innovvative Research Team in University (IRT13052).

摘要

摘要: 对五种不同地区油页岩中干酪根进行了固体KBr压片红外吸收光谱分析,并通过曲线分峰拟合建立了干酪根中脂肪烃区域结构参数的定量测定方法。利用TG-FTIR联用分析技术对干酪根在20 ℃/min升温速率下热解挥发分析出组分在线定性分析,得到了脂肪烃结构参数随热裂解过程的反应特性及变化规律。研究表明,油页岩中干酪根由脂肪烃结构、芳香烃结构和含氧等官能团三部分组成。脂肪烃结构相对含量为18.5%~78.2%,并均以含长链亚甲基结构为主。随着演化程度的加深,干酪根中脂肪烃含量逐渐减少,生油能力也不断降低。干酪根热分解主要发生在350~520 ℃,520 ℃后热失重现象趋于平缓,在此温度下各样品残余半焦的质量分数为19.5%~52.2%。在线红外分析结果表明,干酪根热裂解过程中先析出游离水,随后发生解聚和脱水反应,主要的烷基侧链不断脱落、环化及含氧基团逐渐断裂生成各种烷烃类、羧酸类、醇类和醛类等物质,直至形成更加稳定的类石墨态结构。
- 干酪根 /
- 红外光谱 /
- 脂肪烃 /
- 热解机理 /
- 化学结构
Abstract: Five oil shale kerogens from different regions were analyzed by KBr-FTIR spectra, and a quantitative determination method of structural parameters of kerogen aliphatic hydrocarbon was established by peak-fitting analysis. Thermogravimetric (TG) and Fourier transform infrared spectroscopy (FT-IR) analysis was used to online analyze devolatilization components of kerogen pyrolyzed at 20 ℃/min. The reactivity characteristic and variation of structural parameters of aliphatic hydrocarbon with pyrolysis time were obtained. The results show that the oil shale kerogen was composed of aliphatic hydrocarbon, aromatic hydrocarbon and oxygen functional groups. The relative content of aliphatic hydrocarbon structure, mainly long chain methylene, reaches 18.5%~78.2%. With increasing degree of kerogen evolution, the content of aliphatic hydrocarbon and capacity of oil generation decrease. The decomposition of kerogen mainly occurs during 350~520 ℃. The thermal weightless is mild when above 520 ℃ at which mass fraction of the residual char is 19.5%~52.2%. FT-IR analysis shows that free water releases out firstly during pyrolysis, subsequently depolymerization and dehydration reactions occur, and in which main side chains of alkane fall off and cyclization and oxygen-containing groups break into various of hydrocarbons, acids, alcohols, aldehydes, etc. until more stable graphite-like structure is formed.
- shale kerogen /
- FT-IR spectroscopy /
- aliphatic hydrocarbon /
- pyrolysis mechanism /
- chemical structure

HTML全文

参考文献(20)

马玲, 尹秀英, 孙昊, 付宝山. 世界油页岩资源开发利用现状与发展前景[J]. 世界地质, 2012, 31(4): 772-777. (MA Lin, YIN Xiu-yin, SUN Hao, FU Bao-shan. Present status of oil shale resource utilization in the world and its development prospects. Glob Geol, 2012, 31(4): 772-777.)

MARSHALL C P, LOVE G D, SNAPE C E, HILL A C, ALLWOOD A C, WALTER M R, KRANENDONK M J V, BOWDEN S A, SYLÜA S P, SUMMONS R E. Structural characterization of kerogen in 3.4 Ga Archaean cherts from the Pilbara Craton, Western Australia[J]. Prec Res, 2007, 155: 1-23.

RU X, CHENG Z Q, SONG L H, WANG H Y, LI J F. Experimental and computational studies on the average molecular structure of Chinese Huadian oil shale kerogen[J]. J Mol Str, 2012, 1030: 10-18.

马骁轩, 冉勇. 茂名油页岩中干酪根的热模拟地球化学演变及表征[J]. 地球化学, 2013, 42(4): 373-378. (MA Xiao-xuan, RAN Yong. Simulation and characterization of thermal evolution of kerogen in Maoming oil shale[J]. Geochem, 2013, 42(4): 373-378.)

张学军, 严晓虎, 李佩珍, 苗得玉, 胡文, 刘庆. 干酪根中类脂肪链含量的测定及石油地质意义[J]. 沉积学报, 2004, 22(4): 711-717. (ZHANG Xue-jun, YAN Xiao-hu, LI Pei-zhen, MIAO De-yu, HU Wen, LIU Qing. The method of determination of aliphatic content in kerogen by quantitative FT-IR and its petroleum geology significance[J]. Acta Sed Sin, 2004, 22(4): 711-717.)

王擎, 闫宇赫, 贾春霞, 朱玉成. 甘肃油页岩红外光谱分析及热解特性[J]. 化工进展, 2014, 33(7): 1730-1734. (WANG Qing, YAN Yu-he, JIA Chun-xia, ZHU Yu-cheng. FT-IR analysis and pyrolysis characteristics of oil shale from Gansu province[J]. Chem Ind Eng Prog, 2014, 33(7): 1730-1734.)

WANG S Q, TANG Y G, SCHOBERT H H, GUO Y N, GAO W C, LU X K. FT-IR and simultaneous TG/MS/FT-IR study of Late Permian coals from Southern China[J]. J Anal Appl Pyrolysis, 2013, 100: 75-80.

谢芳芳, 王泽, 宋文立, 林伟刚. 吉林桦甸油页岩及热解产物的红外光谱分析[J]. 光谱学与光谱分析, 2011, 31(1): 91-94. (XIE Fang-fang, WANG Ze, SONG Wen-li, LIN Wei-gang. FT-IR analysis of oil shales from huadian Jilin and their pyrolysates[J]. Spectrosc Spect Anal, 2011, 31(1): 91-94.)

TONG J H, HAN X X, WANG S, JIANG X M. Evaluation of structural characteristics of Huadian oil shale kerogen using direct techniques (Solid-State 13C NMR, XPS, FT-IR and XRD)[J]. Energy Fuels, 2011, 25(9): 4006-4013.

薛向欣, 刘艳辉, 李勇, 姜亚洲. 红外光谱法研究油页岩及干酪根的生油能力[J]. 东北大学学报(自然科学版), 2010, 31(9): 1292-1295. (XUE Xiang-xin, LIU Yan-hui, LI Yong, JIANG Ya-zhou. Study on oil producibility from oil shale and kerogen by Infrared Spectra[J]. J Northeast Univ(NatSci), 2010, 31(9): 1292-1295.)

MIKNIS F P, LINDNER A W, GANNON A J. Solid state ¹³C-NMR studies of selected oil shales from Queensland, Australia[J]. Org Geochem, 1984, 7(3): 239-248.

汪瑗, 阿里木江·艾拜都拉. 波谱综合解析指导[M]. 北京: 化学工业出版社, 2008: 24-25. (WANG Yuan, ALIMJAN ABAYDULLA. Comprehensive analysis of spectrum guide[M]. Beijing: Chemical Industry Press, 2008: 24-25.)

傅家谟, 秦匡宗. 干酪根地球化学[M]. 广州: 广东科技出版社, 1995: 135-170. (FU Jia-mo, QIN Kuang-zong. Kerogen geochemistry[M]. Guangzhou: Guangdong Science and Technology Press, 1995: 135-170.)

冯杰, 李文英, 谢克昌. 傅立叶红外光谱法对煤结构的研究[J]. 中国矿业大学学报, 2002, 31(5): 362-366. (FENG Jie, LI Wen-ying, XIE Ke-chang. Research on coal structure using FT-IR[J]. J ChIn Univ Min Technol, 2002, 31(5): 362-366.)

SOLOMON P R, BEST P E, YU Z Z. A macromolecular network model for coal fluidity[J]. ACS Div Fuel Chem Prepr, 1989, 34(3): 895-906.

FRIEDEL R A, ORCHIN M. Ultraviolet spectra of aromatic compounds[A]. Applied Infrared Spectroscopy[C]. New York: C D N Kendall, 1966: 256-270.

KRISTIN N A, DINESH R K, KALPANA S K. An in situ FT-IR step-scan photoacoustic investigation of kerogen and minerals in oil shale[J]. Spectroch Acta Part A, 2012, 89(4): 105-113.

梁虎珍, 王传格, 曾凡桂, 李美芬, 相建华. 应用红外光谱研究脱灰对伊敏褐煤结构的影响[J]. 燃料化学学报, 2014, 42(2): 129-137. (LIANG Hu-zhen, WANG Chuan-ge, ZENG Fan-gui, LI Mei-fen, XIANG Jian-hua. Effect of demineralization on lignite structure from Yinmin coalfield by FT-IR investigation[J]. J Fuel Chem Technol, 2014, 42(2): 129-137.)

王传格, 张妮, 陈燕. 煤显微组分结构特征及其与热解行为的关系[J]. 煤炭转化, 2011, 34(3): 11-16. (WANG Chuan-ge, ZHANG Ni, CHEN Yan. Relationship between structural characterization of macerals and their thermal behavior[J]. Coal Convers, 2011, 34(3): 11-16.)

WANG H, JIANG X M, YUAN D Q, WAN P. Pyrolysis of coal water slurry volatile matter by using FG-DVC model[J]. J Chem Ind Eng (CHN), 2006, 57(10): 2428-2432.

施引文献

资源附件(0)

访问统计