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地球科学进展  2009, Vol. 24 Issue (8): 882-890    DOI: 10.11867/j.issn.1001-8166.2009.08.0882
综述与评述     
煤中矿物/金属元素在生气过程中的催化作用
吴艳艳,秦  勇
中国矿业大学资源与地球科学学院,江苏  徐州  221116
Catalysis of Mineral/Metal Elements during Coal Bed Gas Generation
Wu Yanyan, Qin Yong
College of Mineral Resources and Geoscience, China University of Mining & Technology, Xuzhou  221116, China
 全文: PDF(1058 KB)  
摘要:

传统煤化作用理论认为,煤层气生成是煤中有机质在地层温度/压力或微生物作用下发生降解或裂解的结果,近年来国内外相关研究成果却对这一传统理论提出了重大质疑。为此,从沉积有机质中具有催化作用的矿物/金属元素、催化模拟实验与其结果表征、催化作用机制3个方面,总结了国内外关于有机质催化生气作用研究的进展,讨论了本领域今后研究工作的重点和发展方向。认为在模拟煤中有机质的矿物/金属元素催化生气时,应考虑有机质和无机质之间的相互作用,兼顾矿物与矿物之间的反应,使之尽可能接近于真实的地层条件; 以地质学和化学两大学科的理论为基础,借鉴化工界研究成果,在微观层面上深入研究煤中有机质—无机质作用的态—态催化作用、选键催化作用和微观反应机理。建议重视煤岩学、煤中矿物学、煤无机/有机地球化学与催化化学的综合研究,探究煤中矿物/金属元素催化生气的实质,寻找催化生气的判识标志,针对具体对象建立定量的催化反应速率数学模型和催化生气产率数学模型。

关键词: 煤层气成因 矿物 金属元素 催化作用    
Abstract:

It is traditionally assumed that the Coal Bed Gas (CBG) formation is the effect of thermolysis (cracking) of the bulk coal organic matter by stratum temperature/pressure or animalcule. However, some researchers have debated the validity of that view. The advances in research on CBG catalytic generation are selectively summarized in three aspects: The minerals/metal elements as the gas generation catalyzer;  the catalytic simulated experiment and its results token;  the catalysis mechanism. Then the research emphases and development direction are discussed. The reaction under geological condition is more complicated than the lab condition. Therefore, during the gas generating simulation process, we should not just study the effect of some natural minerals but also consider the reaction between organic and inorganic and the effect during the different inorganic minerals in the idiographic geological condition, and try best to make the condition close to the actual stratum condition. It is advised that based on geology and chemistry, the results of chemical industry be used to investigate the microcosmic state-state and bond-selective catalysis between organic and inorganic matters. Importance should be attached to the integration of coal petrology, mineralogy in coal, coal organic and inorganic geochemistry, catalytic chemistry to explore the catalysis essential of mineral/metal elements, and to search the catalytic symbol aiming at the idiographic object to set up quantificational catalytic reaction speed and gas productivity math model.

Key words: Coal bed gas origin     Mineral    Metal elements    Catalysis
收稿日期: 2009-01-10 出版日期: 2009-08-10
:  P618.11   
基金资助:

国家自然科学基金项目“黔西—滇东煤层气成藏效应及其地质选择过程”(编号:40730422)资助.

通讯作者: 吴艳艳     E-mail: wuyanyan24@gmail.com
作者简介: 吴艳艳(1982-),女,江苏扬州人,博士生,主要从事煤地球化学方面的研究. E-mail:wuyanyan24@gmail.com
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引用本文:

吴艳艳,秦勇. 煤中矿物/金属元素在生气过程中的催化作用[J]. 地球科学进展, 2009, 24(8): 882-890.

Wu Yanyan, Qin Yong. Catalysis of Mineral/Metal Elements during Coal Bed Gas Generation. Advances in Earth Science, 2009, 24(8): 882-890.

链接本文:

http://www.adearth.ac.cn/CN/10.11867/j.issn.1001-8166.2009.08.0882        http://www.adearth.ac.cn/CN/Y2009/V24/I8/882

[1] Mango F D, Hightower J W. The catalytic decomposition of petroleum into natural gas[J].Geochimica et Cosmochimica Acta,1997, 61: 5 347-5 350.
[2] Andresen B, Barth T, Irwin H. Yields and carbon isotopic composition of pyrolysis products from artificial maturation processes[J].Chemical Geology,1993,106:103-119.
[3] Mango F D, Hightower J W, James A T. Role of transition-metal catalysis in the formation of natural gas[J].Nature, 1994,368:536-538.
[4] Price L C, Schoel M. Constrains on the origins of hydrocarbon gas from compositions of gases at their site of origin[J].Nature, 1995,378:368-371.
[5] Elie M, Cathelineau M, Ruck R, et al. Interactions Between Clay Minerals and Kerogen During Confined Pyrolysis: Mineralogical and Chemical Evidences[R].209th ACS National Meeting, Division of Geochemistry, Anaheim, CA,1995:61.
[6] Ramaswamy G. A field evidence for mineral-catalyzed formation of gas during coal maturation[J].Oil and Gas Journal,2002, 100(38): 32-36.
[7] Liu Wenhui, Wang Wanchun. The organic (biogenic) and inorganic (non-biogenic) sources of hydrocarbons-thought on theory of oil and gas formation[J].Bulletin of Mineralogy, Petrology and Geochemistry,2000, 19(3): 179-186.[刘文汇, 王万春. 烃类的有机(生物)与无机(非生物)来源—油气成因理论思考之二[J]. 矿物岩石地球化学通报, 2000, 19(3): 179-186.]
[8] Qin Yong. Advances in overseas geological research on coalbed gas: Origin and reservoir characteristics of coalbed gas[J].Earth Science Frontiers,2005, 12(3): 289-298.[秦勇. 国外煤层气成因与储层物性研究进展与分析[J]. 地学前缘, 2005, 12(3): 289-298.]
[9] Medina J C, Butala S J, Bartholomew C H, et al. Low temperature iron-and nickel-catalyzed reactions leading to coalbed gas formation[J].Geochimica et Cosmochimica Acta,2000, 64(4):643-649.
[10] Medina J C, Butala S J, Bartholomew C H,et al. Iron-catalyzed CO2 hydrogenation as a mechanism for coalbed gas formation[J].Fuel,2000,79: 89-93.
[11] Dembieki J H. Mineral matrix effete during analytical pyrolysis of source rocks[J].Association Petroleum Geochemistry Exploration Bulletin, 1990, 6:78-105.
[12] Dembieki J H. The effects of the mineral matrix on the determination of kinetic parameters using modified rock eval pyrolysis[J].Organic Geochemistry,1992, 18(4): 531-539.
[13] Gao Xianzhi, Zhang Wanxuan, Zhang Houfu. Study of the influence of minerals on pyrolysis[J].Experimental Petroleum Geology,1990, 12(2): 201-205.[高先志, 张万选, 张厚福. 矿物质对热解影响的研究[J]. 石油实验地质, 1990, 12(2):201-205.]
[14] Cao Huiti, Zhang Yigang, Xu Xiang,et al. A new understanding of hydrocarbon generation mechanism of carbonate rocks[J]. Experimental Petroleum Geology,1991, 13(3): 223-237.[曹慧缇, 张义纲, 徐翔,等.碳酸盐岩生烃机制的新认识[J]. 石油实验地质, 1991, 13(3): 223-237.]
[15] Li Zhong. On the catalysis of clay minerals in the process of oil and gas generation[J].Experimental Petroleum Geology, 1992, 14(1): 59-63.[李忠. 试论油气生成过程中粘土矿物的催化作用[J]. 石油实验地质, 1992, 14(1):59-63.]
[16] Zhang Guofang, Wu Deyun, Ma Jinyu. A preliminary comprehensive assessment of hydrocarbon exploration by geochemical technique[J].Petroleum Exploration and Development,1993, 20 (5): 42-52.[张国防, 吴德云,马金钰. 盐湖相石油的早期生成[J]. 石油勘探与开发, 1993, 20 (5): 42-52.]
[17] Xie Qilai, Zhou Zhongyi, Lu Mingyong. Organic metter enclosed in carbonate minerals—A kind of important hydrocarbon producing matter[J].Acta Mineralogica Sinica, 2000, 20(1): 59-62.[解启来, 周中毅,陆明勇. 碳酸盐矿物结合有机质——一种重要的成烃物[J]. 矿物学报, 2000, 20(1): 59-62.]
[18] Zhao Guiyu, Li Shuyuan, Liu Luofu. A study on characteristics and kinetics of catalytic degradation from kerogen in carbonate rocks[J].Chinese Journal of Geology, 2005, 40(1): 47-54.[赵桂瑜, 李术元, 刘洛夫. 碳酸盐岩干酪根催化降解生烃过程及动力学研究[J]. 地质科学, 2005, 40(1): 47-54.]
[19] Wang Zhizhong, Liu Xuguang, Ling Daqi. Study of the coal liquefaction technology and development[J].Coal Processing & Comprehensive Utilization,1993,(1): 48-49.[王志忠, 刘旭光, 凌大琦. 我国煤直接液化技术的研究与开发[J]. 煤炭加工与综合利用, 1993,(1):48-49.]
[20] Hunt J M. Modeling oil generation with time-temperature index graphs based on the Arrhenius equation[J].AAPG Bulletin,1991,75:795-807.
[21] Zhang Jinglian, Zhang Pingzhong. A discussion of pyrite catalysis on the hydrocarbon generation process[J].Advances in Earth Sience,1996, 11(3):282-286.[张景廉, 张平中. 黄铁矿对有机质成烃的催化作用讨论[J]. 地球科学进展, 1996,11(3):282-286.]
[22] Lambert J M. Alternative interpretation of coal liquefaction catalysis by pyrite[J].Fuel,1982,61:777.
[23] Weng Sihao, Wu Youqing, Gao Jinsheng, et al. Catalyst in coal hydyoliquefaction I. On the transformation and the action mechanism of iron sulphide in hydrogenation[J].Journal of Fuel Chemistry and Technology,1990,18(2):97-100.[翁斯灏, 吴幼青, 高晋生,等. 煤加氢液化铁催化剂的穆斯保尔谱研究Ⅰ铁硫化物在加氢反应中的转化及活性机理[J]. 燃料化学学报,1990,18(2): 97-100.][24] Weng Sihao, Gao Jinsheng, Wu Youqing, et al. Mossbauer soectroscopic study of iron catalyst in coal hydroliquefaction II. On the transformation and the hydrogenation activity of ferric oxide under various reaction conditions[J].Journal of Fuel Chemistry and Technology,1990,18(2):103-108.[翁斯灏, 高晋生, 吴幼青,等.煤加氢液化铁催化剂的穆斯保尔谱研究Ⅱ氧化铁在不同反应条件下的转化及催化活性[J]. 燃料化学学报, 1990b, 18(2): 103-108.]
[25] Li Shuyuan, Lin Shijing, Guo Shaohui, et al. Effects of inorganic salts on the hydrocarbon generation from kerogens[J]. Geochimica,2002, 31(1): 15-19.[李术元, 林世静, 郭绍辉,等.无机盐类对干酪根生烃过程的影响[J]. 地球化学, 2002, 31(1):15-19.]
[26] Franklin H D, Peters W A, Howard J B,et al. Effect of calcium minerals on the rapid pyrolysis of a bituminous coal[J].Industrial Engineering Chemica Process Design & Development,1981,20(4):670-674.
[27] Zhu Tingyu, Liu Lipeng, Wang Yang, et al. Study on coal mild gasification with CaO catalyst[J].Journal of Fuel Chenistry and Technology,2000, 28(1):36-39.[朱廷钰,刘丽鹏,王洋,等.氧化钙催化煤温和气化研究[J]. 燃料化学学报, 2000, 28(1):36-39.]
[28] Mango F D.Transition metal catalysis in the generation of petroleum and natural gas[J].Geochimica et Cosmochimica Acta, 1992,56(1): 553-555.
[29] Mango F D.Transition metal catalysis in the generation of petroleum: A genetic anomaly in Ordovician oils[J].Geochimica et Cosmochimica Acta, 1992,56(10):3 851-3 854.
[30] Mango F D. Transition metal catalysis in the generation of natural gas[J].Organic Geochemistry,1996, 24: 977-984.
[31] Xiao Zhihua, Hu Guoyi, Zhong Ningning, et al. Effect of microelement in mineral on hydrocarbon generation of organic matter[J].Journal of China University of Petroleum, 2008, 32(1): 33-36.[肖芝华, 胡国艺, 钟宁宁,等.矿物中的微量元素对有机质产气的影响[J]. 中国石油大学学报(自然科学版), 2008, 32(1): 33-36.]
[32] Zhang Min, Lin Renzi. On the catalysis of transition metals in the process of light hydrocarbons generaltion[J].Geological Science and Technology Information, 1994, 13(3):75-80.[张敏,林壬子. 试论轻烃形成过程中过渡金属的催化作用[J]. 地质科技情报, 1994,13(3):75-80.]
[33] Ning Zhanwu, Wang Weihua, Wen Meijuan, et al. Catalytic effects of transitional metals on the generation of hydrocarbon in organic matter[J]. Natural Gas Geoscience, 2004, 15(3):317-319.[宁占武, 王卫华, 温美娟,等.过渡金属对有机质热解生烃过程的影响[J]. 天然气地球科学, 2004, 15(3):317-319.]
[34] Lu Hongxuan, Meng Zifang, Li Bin, et al. Effect of trace element molybdenum on hydrocarbon generation from lignite by pyrolysis[J].Natural Gas Geoscience, 2007, 18(1):104-106.[卢红选,孟自芳,李斌,等.微量元素Mo对褐煤有机质热解成烃的影响[J]. 天然气地球科学, 2007,18(1):104-106.]
[35] Disnar J R, Sureau J F. Organic matter in ore genesis: Progress and perspectives[J].Organic Geochemistry,1990, 16(1/3): 577-599.
[36] Parnell J. Metal enrichment in bitumens from Carboniferous-hosted ore[J]. Chemical Geology,1992, 99(1/3):115-124.
[37] Du Letian. Introduction and analysis of foreign natural gas geoscience studies based on Sokolov's date[J].Natural Gas Geoscience,2007, 18(1):1-18.[杜乐天. 天然气地球科学研究成果介绍与分析——以索科洛夫的著作为主线[J]. 天然气地球科学,2007, 18(1): 1-18.]
[38] Chen Guangpo, Xu Guosheng, Wang Tianqi, et al. The relationship between hydrocarbon accumulation and metallization and a discussion on intergrated exploration[J].Earth Science Frontiers,2008, 15(2): 200-206.[陈广坡, 徐国盛, 王天奇,等.论油气成藏与金属成矿的关系及综合勘探[J]. 地学前缘, 2008, 15(2): 200-206.]
[39] Liao Daiwei. Catalysis Sience Introduction[M]. Beijing: Chemical Industry Press, 2006:31-34.[廖代伟. 催化科学导论[M].北京: 化学工业出版社, 2006:31-34]
[40] Fu Jiamo. Geochemistry\[M\]. Beijing: Science Press, 1990.[傅家谟. 煤成烃地球化学[M]. 北京: 科学出版社,1990.]
[41] Liu Luofu, Mao Dongfeng, Tuo Jincai. Advance in simulant experimentation of hydrocarbon generation[J].Bulletin of Mineralogy, Petrology and Geochemistry,1997, 16(1): 55-57. [刘洛夫, 毛东风, 妥进才,等.源岩生烃模拟实验的研究现状[J]. 矿物岩石地球化学通报, 1997, 16(1): 55-57.]
[42] Xiong Yongqiang, Geng Ansong, Wang Yunhe. Study on simulant experimentation of hydrocarbon generation in kerogen degtadation[J].Science in China (Series D) ,2001, 31(4): 315-320.[熊永强, 耿安松,王云鹤. 干酪根二次生烃动力学模拟实验研究[J]. 中国科学:D辑, 2001, 31(4): 315-320.]
[43] Liu Luofu, Li Shuyuan. Advances in the study of the mechanism of hydrocarbon generation from source rocks by catalysis[J].Geological Review,2000, 46(5): 491-498.[刘洛夫, 李术元. 烃源岩催化生烃机制研究进展[J]. 地质评论, 2000, 46(5): 491-498.]
[44] Lewan M D. Laboratory simulation of petroleum formation: Hydrous pyrolysis[C]//Enge l M H, Macko S A. Organic Geochemistry: Principles and Applications. New York: Plenum Press, 1993: 419-442.
[45] Farcasiu M, Smith C, Pradhan V R. Iron commpounds and iron catalysts: Activity in reactiond relevant to direct coal liquefaction[J].Fuel Processing Technology,1991,29:199-208.
[46] Ganguly B, Huggins E, Rao K R P, et al. Mossbauer studies of febased ultrafine coal liquefaction catalysts[J].American Chemical Society Division of Fuel Chemistry Prediction,1993,38:190-193.
[47] Suzuki T, Yamada H, Wantanebe Y. XRD study of iron exchanged into victorian brown coal[J].Energy and Fuels,1989,3:707-710.
[48] Rao V U S. An evaluation of particle size measurement techniques for dispersed iron catalystss[J].American Chemical Society Division of Fuel Chemistry Prediction,1993,38:184-185.
[49] Ibrahim M M, Seehra M S. Characterization of an iron-based catalysts for direct coal liquefaction[J].Energy and Fuls, 1994,8:48-50.
[50] Sun Linbing, Ni Zhonghai, Zhang Lifang, et al. Advances in iron-based catalysts for direct coal liquefaction[J].Coal Technology,2002, 21(11): 65-67.[孙林兵, 倪中海, 张丽芳,等.煤直接液化铁基催化剂的研究进展[J]. 煤炭技术,2002,21(11): 65-67.]
[51] Zhang Li′an, Zhu Jisheng, Xu Long, et al. Application of surface fractal to characterization of direct coal liquefaction catalysis[J].Coal Conversion,2000, 23(3):48-52.[张立安, 朱继升, 徐龙,等.分形学在煤直接液化催化剂表征中的应用[J]. 煤炭转化, 2000,23(3): 48-52.]
[52] Li Rongsheng, Zhen Kaiji, Wang Guojia, et al. Catalysis Basic[M]. Beijing: Science Press, 1990:219.[李荣生, 甄开吉, 王国甲. 催化作用基础[M]. 北京: 科学出版社, 1990:219.]
[53] Chai Yongming, An Gaojun, Liu Yunqi, et al. Transition metal sulfides hydrogenation catalysts: Active phase structure and mechanism of the catalytic reaction[J].Progress in Chemistry,2007,19(2/3):234-242.[柴永明,安高军,柳云骐,等.过渡金属硫化物催化剂催化加氢作用机理[J]. 化学进展,2007,19(2/3):234-242.]
[54] Bai Lugang, Yan Yongjie, Li Tingshen, et al. Catalysis coliquefaction of coal and biomass[J].Engineering Chemistry & Metallurgy,2000,21(2):198-203.[白鲁刚, 颜涌捷, 李庭深,等.煤与生物质共液化的催化反应[J].化工冶金,2000,21(2):198-203.]
[55] Li Shuyuan, Lin Shijing, Guo Shaohui, et al. Catalytic effects of minerals on hydrocarbon generation in kerogen degtadation[J].Journal of the University of Petroleum China,2002,26(1): 69-71.[李术元, 林世静, 郭绍辉,等.矿物质对干酪根热解生烃过程的影响[J].石油大学学报(自然科学版), 2002,26(1):69-71.]
[56] Jin Zhijun, Yang Lei, Zeng Jianhui, et al. Deep fluid activities and their effects on generation of hydrocarbon in Dongying deoression[J].Petroleum Exploration and Development,2002,29(2):42-44.[金之钧, 杨雷, 曾溅辉,等.东营凹陷深部流体活动及其生烃效应初探[J]. 石油勘探与开发, 2002,29(2):42-44.]
[57] Guo Zhanqian, Yang Xingke. Multi-mechanism of hydrocarbon generation of China′s petroliferous basins[J].Oil & Gas Geology, 2000,21(1):50-64.[郭占谦, 杨兴科. 中国含油气盆地的多种生烃机制[J]. 石油与天然气地质, 2000,21(1):50-64.]
[58] Guo Zhanqian, Yang Haibo. Chinese continental ctust is one with abundant hydrocarbons[J].XinJiang Petroleum Geology, 2005,26(3):326-330.[郭占谦,杨海博.中国陆壳是富烃陆壳[J]. 新疆石油地质, 2005,26(3):326-330.]

 

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[2] 刘华华, 蒋富清, 周烨, 李安春. 晚更新世以来奄美三角盆地黏土矿物的来源及其对古气候的指示[J]. 地球科学进展, 2016, 31(3): 286-297.
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