CCl_4溶剂下CO_2超临界萃取枣庄煤的产物分析
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摘要
在CCl_4夹带剂作用下CO_2超临界萃取枣庄煤,为煤超临界萃取产物的利用提供了的理论依据,同时对煤的成煤环境进行分析。萃取物中共检测出48种有机化合物。其中包括7种芳烃类(占35.382%)、9种酯类(占36.148%)、19种烷烃类(占14.410%)、1种酸酐类(占0.376%)、1种脂肪酸类(占2.199%)、1种烯烃类(占0.382%)、1种酮类(占1.953%)和9种其他物质(占9.151%)。其中卤代烃(占3.007%),检测出一种环八硫(占1.397%)。检测出的正烷烃具有偶碳优势,从而可推测成煤环境多出现在碳酸盐岩和蒸发岩系中,盐湖或高含盐地层中。检测到生物标志物:2,6,10,14-四甲基十六烷(植烷)占1.028%。扫描电镜观察萃取前后的煤表面形貌变化,比表面测试表明萃余煤的比表面积和孔径分布变大,XRD显示出θ为29.5°时有机峰减弱至不明显。
The theoretical basis for the utilization of the supercritical extraction of coal were provided by CO_2 supercritical extraction of Zaozhuang coal under the action of carbon tetrachloride,and the coal forming environment were analyzed. 48 kinds of organic compounds were detected in extract including 7 kinds of aromatic(35. 382%),9 kinds of esters(36. 148%),19 kinds of alkanes(14. 410%),one type of acid anhydride(0. 376%),one species of fatty acids(2. 199%),a kinds of alkenes(0. 382%),a sort of ketones(1. 953%) and 9 kinds of some others(9. 151%). Other substances were mainly for halogenated hydrocarbons(3. 007%),a ring of eight sulfurs was detected(1. 397%). N-alkanes detected are advantage of even carbon,so that the coal forming environment mostly occurs in carbonate and evaporite rocks series and in Saline Lake or high salt formation. 2,6,10,14-tetramethyl-hexadecane(phytane) is detected that a kind of biomarkers(1. 028%). Surface morphology of coal before and after extraction was observed by scanning electron microscope. The surface aperture test shows that the specific surface area and pore size distribution of the coal residue become larger. XRD shows that peaks of organic are weakened to not obvious when θ is 29. 5°.
The theoretical basis for the utilization of the supercritical extraction of coal were provided by CO_2 supercritical extraction of Zaozhuang coal under the action of carbon tetrachloride,and the coal forming environment were analyzed. 48 kinds of organic compounds were detected in extract including 7 kinds of aromatic(35. 382%),9 kinds of esters(36. 148%),19 kinds of alkanes(14. 410%),one type of acid anhydride(0. 376%),one species of fatty acids(2. 199%),a kinds of alkenes(0. 382%),a sort of ketones(1. 953%) and 9 kinds of some others(9. 151%). Other substances were mainly for halogenated hydrocarbons(3. 007%),a ring of eight sulfurs was detected(1. 397%). N-alkanes detected are advantage of even carbon,so that the coal forming environment mostly occurs in carbonate and evaporite rocks series and in Saline Lake or high salt formation. 2,6,10,14-tetramethyl-hexadecane(phytane) is detected that a kind of biomarkers(1. 028%). Surface morphology of coal before and after extraction was observed by scanning electron microscope. The surface aperture test shows that the specific surface area and pore size distribution of the coal residue become larger. XRD shows that peaks of organic are weakened to not obvious when θ is 29. 5°.
引文
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[2]袁新华,熊玉春,宗志敏,等.分子煤化学与煤衍生物的定向转化[J].煤炭转化,2001,24(1):1-4.
[3]佟斌,郭树才,胡浩权.不同溶剂神府煤超临界萃取研究[J].煤炭转化,1993,16(2):70-76.
[4]殷甲楠,张凤桐,樊丽华,等.低阶煤有机溶剂萃取的研究进展[J].洁净煤技术,2014,20(6):100-103.
[5]李淑芬,全灿,唐韶坤,等.分析型超临界萃取中改性及研究进展[J].化学通报,2004,6:403-407.
[6]佟斌,郭树才,胡浩权.以水、甲苯及其混合溶剂超临界萃取煤的研究[J].燃料化学通报,1993,21(4):407-411.
[7]赵宗彬,陈受斯,张振桴.煤的超临界萃取研究[J].煤炭转化,1996,19(1):88-95.
[8]薛丁丁,刘振学,于洪观,煤的超临界流体萃取研究进展[J].应用化工,2013,42(8):1501-1504.
[9]周世宁,林柏泉.煤层瓦斯赋存与流动理论[M].北京:煤炭工业出版社,1999:11-12.
[10]林壬子,王培荣,戴允键,等.矿物燃料中多环芳烃的石油地球化学意义[C]//有机地球化学论文集.北京:地质出版社,1987:129-140.
[11]GATHITU B B,CHEN Weiyin,MCCLURE M.Effect of coal interaction with supercritical CO2:Physical structure[J].Ind Eng Chem Res,2009,48:5024-5034.
[12]LARSEN J W.The effects of dissolved C2on coal structure and properties[J].International Journal of Coal Geology,2004,57:63-70.
[13]IWAI Yoshio,AMIYA Michitaka,MUROZONO Tadaaki,et al.Drying of coals by using supercritical carbon dioxide[J].Ind Eng Chem Res,1998,37:2893-2896.
[14]IWAI Yoshio,MUROZONO Tadaaki,KOUJINA Yasutake,et al.Physical properties of low rank coals dried with supercritical carbon dioxide[J].Journal of Supercritical Fluids,2000,18:73-79.
[15]杨涛.超临界CO2抽提对煤的改性实验研究[D].太原:太原理工大学,2010.
[16]陈润,秦勇.超临界CO2与煤中矿物的流固耦合及其地质意义[J].煤炭科学技术,2012,40(10):17-21.