常压下矿物低温催化混合酯水解及生烃动力学研究
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摘要
未熟烃源岩中的脂肪酸是重要的生烃母质,其在自然界中主要以脂肪酸酯的形式存在。本文采用不同的方法对未熟烃源岩进行有机质抽提并分析有机质四组分,考察抽提前后未熟烃源岩低温催化混合酯水解率及生烃率的变化,初步分析有机质组分对催化反应的影响;选择十六烷酸甲酯和十八烷酸甲酯组成的混合酯为模型反应物,对低压下矿物低温催化混合酯水解及生烃的影响因素进行研究,并进行活性评价;以抽提有机质后的江汉未熟烃源岩为催化剂,模拟其地质条件,采用连串反应动力学模型,对未熟烃源岩低温催化混合脂肪酸酯水解及生烃进行动力学研究,用连串反应模型处理未熟烃源岩低温催化混合酯的水解反应为一级反应,生烃反应为零级反应,该模型更符合实际地质条件下矿物低温催化混合脂肪酸酯水解及生烃的一般规律;考察6种天然矿物和7种未熟烃源岩低温催化酯水解及生烃的作用,对天然矿物组分和未熟烃源岩就低温催化混合酯水解及生烃的作用进行关联;并考察不同比例复配的粘土和碳酸盐矿物的低温催化作用。实验结果表明,未熟烃源岩低温催化混合酯的水解及生烃率趋势与6种天然矿物含量加权处理关系较好。不同比例复配的粘土矿物和碳酸盐矿物体现了不同的催化作用,在本课题实验条件下当粘土矿物与碳酸盐矿物比例为1:1时达到最高的生烃效率。
Fatty acids in immature source rocks are regarded as one of the important precursors for the process of hydrocarbon generating. It has been found that main forms of the fatty acids existing in nature are fatty acid esters. In this paper, different approaches are used for organic extraction of immature source rocks and the four components in organic matter are analyzed, and the changes of hydrolysis and hydrocarbon generating rates are studied of mixed esters catalyzed by immature source rocks before and after extraction at low temperature, to analyze preliminarily the affect of organic components on catalytic reaction. mixed ester consisting of palmitic acid methyl ester and tetradecanoic acid methyl ester is chosen as the model reaction compound, to study the influencing factors of its hydrolysis and hydrocarbon-generating reaction catalyzed by mineral at low temperature and low pressure. the mixed fatty acid esters are chosen as the model reactor and consecutive reaction is chosen as the kinetic model, to study the kinetics of its hydrolysis and hydrocarbon generating reaction catalyzed by Ji source rocks firstly extracted with organic solvents under simulation conditions. The study suggests that both hydrolysis and the hydrocarbon generation can be treated as consecutive reaction; the hydrolysis reaction is first order reaction while the hydrocarbon generation reaction is zero order reaction, and the consecutive model is more in line with the general law of hydrolysis and hydrocarbon generation of mixed fatty acid esters catalyzed by minerals under the actual geological conditions. Investigate the hydrolysis and hydrocarbon generation of mixed ester catalyzed by six kinds of natural minerals and seven kinds of immature source rocks at low temperature. Associate natural minerals with immature source rocks in this reaction. Furthermore, the effect of different ratios of carbonate minerals clay minerals and carbonate minerals on hydrolysis and hydrocarbon generation of mixed ester catalyzed by minerals was investigated. As the results show, the tendency of hydrolysis and hydrocarbon generation rate of mixed ester catalyzed by immature oil source rocks is similar to the weighted contents of six kinds of nature minerals which were chosen. Different ratios of carbonate minerals clay minerals show the different efficiency of catalytic. When the ratio value at 1:1, the composite minerals reach the best hydrocarbon-generating efficiency.
Fatty acids in immature source rocks are regarded as one of the important precursors for the process of hydrocarbon generating. It has been found that main forms of the fatty acids existing in nature are fatty acid esters. In this paper, different approaches are used for organic extraction of immature source rocks and the four components in organic matter are analyzed, and the changes of hydrolysis and hydrocarbon generating rates are studied of mixed esters catalyzed by immature source rocks before and after extraction at low temperature, to analyze preliminarily the affect of organic components on catalytic reaction. mixed ester consisting of palmitic acid methyl ester and tetradecanoic acid methyl ester is chosen as the model reaction compound, to study the influencing factors of its hydrolysis and hydrocarbon-generating reaction catalyzed by mineral at low temperature and low pressure. the mixed fatty acid esters are chosen as the model reactor and consecutive reaction is chosen as the kinetic model, to study the kinetics of its hydrolysis and hydrocarbon generating reaction catalyzed by Ji source rocks firstly extracted with organic solvents under simulation conditions. The study suggests that both hydrolysis and the hydrocarbon generation can be treated as consecutive reaction; the hydrolysis reaction is first order reaction while the hydrocarbon generation reaction is zero order reaction, and the consecutive model is more in line with the general law of hydrolysis and hydrocarbon generation of mixed fatty acid esters catalyzed by minerals under the actual geological conditions. Investigate the hydrolysis and hydrocarbon generation of mixed ester catalyzed by six kinds of natural minerals and seven kinds of immature source rocks at low temperature. Associate natural minerals with immature source rocks in this reaction. Furthermore, the effect of different ratios of carbonate minerals clay minerals and carbonate minerals on hydrolysis and hydrocarbon generation of mixed ester catalyzed by minerals was investigated. As the results show, the tendency of hydrolysis and hydrocarbon generation rate of mixed ester catalyzed by immature oil source rocks is similar to the weighted contents of six kinds of nature minerals which were chosen. Different ratios of carbonate minerals clay minerals show the different efficiency of catalytic. When the ratio value at 1:1, the composite minerals reach the best hydrocarbon-generating efficiency.
引文
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[29]魏黔钧.亚铁离子对碳酸盐岩有机质成烃演化的催化作用模拟实验研究[J].天然气地球科学,2005,16(3):306-309
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[32]陈小东,王先彬.压力对有机质成熟和油气生成的影响[J].地球科技进展,1999,14(1):31-36
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[34]杨天宇,王涵云.岩石中有机质高温高压模拟实验[J].石油与天气地质,1987,8(4):380-389
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[36] Braun R L, Burnham A K. Mathematical model of oil generation, degradation and expulsion [J]. Energy Fuels, 1990, 4: 132-146
[37] Cecil B, Stanton R, Allshouse S, et al. Effects of pressure on coalification. Ninth International Congress of Carboniferous Stratigraphy and Geology [J]. University of Illinois, Urbana, Illinois, 1979:32-38
[38] Sajgo C S, McEvoy J, Wolef G A, et al. Influence of temperature and pressure on maturation process-I, preliminary report [J]. Org Geochem, 1986, 10: 331-337
[39]丁福臣,王剑秋,钱家麟.压力下生油岩热解动力学研究[J].石油学报,1991,12(3):44-51
[40]李生杰.褐煤煤化作用的加压加热模拟实验及其意义[J].石油实验地质,1988,10(1):72-79
[41]范善发,周中毅,韩林林,等.压力对盆地深部有机质演化的影响[M].南京:江苏科学技术出版社,1992:246-249
[42] Ritter U K, Myhr M B, Vinge T, et al. Experimental heating and kinetic models of source rocks: comparison of different methods [J]. Org Geochem, 1995, 23(1): 1-9
[43] Ungerer P, Pelet R. Extrapolation of the kinetics of oil and gas formation from laboratory experiments to sedimentary basins [J]. Nature, 1987, 327(1): 52-54
[44]卢双舫,郭春萍,申家年,等.化学动力学法在黄骅坳陷未熟-低熟油资源评价中的应用[J].石油地质,2005,(6):18-23
[45] Braum R. Oil and gas evolution kinetics for oil shale and petroleum source rock determined from pyrolysis-TQMS data at two heating rates [J]. Energy and Fuel, 1992, (6):468-474
[46]高喜龙,肖贤明,王建宝.用开放体系的热解方法对烃源岩生烃动力学的研究[J].地球化学,2003,32(5):485-490
[47]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
[48] Johns W D. The role of the clay minerals matrix in petroleum generation during burial diagenesis[J]. Dev Sedimental, 1982, 35: 655-664
[49]张在龙,王广利,劳永新,等.未熟烃源岩中矿物低温催化脂肪酸脱羧生烃动力学模拟实验研究[J].地球化学,2000,29(4):322-326
[50]张在龙,叶天旭,任永宏,等.未熟烃源岩低温催化脂肪酸酯生烃动力学研究[J].中国石油大学学报,2005,29(5):104-116
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[2] Cooper J E, Bray E E. A postulated role of fatty acids in petroleum formations . Geochim Geochim Cosmochim Acta. 1963; 27: 1113-1127
[3] Eisma E, Jurg J W. Petroleum hydrocarbons generation fatty acid . Scinece,1964; 144-3625, 1451-1452
[4] Shimoyama A, Johns W D. Formation of alkanesfrom fatty acid in the presence of CaCO3 . Geochem Cosmochem Acta, 1972, 36: 87-91
[5]王铁冠,钟宁宁,侯读杰,等.低熟油气形成机理与分布[M].北京:石油出版社,1995:5-19
[6]黄第藩,张大江,王培荣,等.中国未成熟石油成因机制和成藏条件[M].北京:石油工业出版社,2003:3-12
[7]史继扬,向明菊.未熟和低熟烃源岩中脂肪酸的赋存形式与分布特征[J].科学通报,2000,45(16):1771-1775
[8]史继扬,向明菊,屈定创.未熟-低熟烃源岩中脂肪酸的热模拟实验及演化[J].科学通报,2001,46(18):1567-1571
[9] Brook B T. Active surface catalysts in the formation of petroleum . AAPG Bull, 1948; 32(12): 2269-2286
[10] Brook B T. Evidence of catalytic action in petroleum formation. Ind Eng Chem, 1952; 44(11): 2570-2577
[11] Johns W D.The role of the clay minerals matrix in petroleum generation during burial diagenesis[C]. Dev Sedimental, 1982, 35: 655-664
[12]张枝焕,高先志,方朝亮.粘土矿物对干酪根热解产物的影响及其作用机理[J].石油大学学报(自然科学版), 1995, 19(5): 11-17
[13]李忠.试论油气形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
[14] Li SY, Guo SH, Tan XF. Characteristics and kinetics of catalytic degradation of immature kerogen in the presence of mineral and salt[J]. Org Geochem, 1998, 29(5-7): 1431-1439
[15]施继锡,傅家谟,李本超,等.矿物包裹体在碳酸盐岩区油气评价中的意义[J].沉积学报, 1987, 5(1):86-91
[16]解启来,周中毅,陆明勇.碳酸盐矿物结合有机质—一种重要的成烃物质[J].矿物学报, 2000, 20(1):59-62
[17]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(1): 223-237
[18]张在龙,任永宏,闫忠良,等.天然矿物低温催化脂肪酸酯生烃反应动力学研究[J].地球化学, 2005, 34(3): 263-268
[19]妥进才,黄杏珍,马万怡,等。碳酸盐岩中石油形成的滞后现象[M].石油勘探与开发,1994;21(6):1-5
[20] V Luca Cation. Migratio in Smectite Minerals: Electron Spin Resonance of Exchanged Fe3+ Probes. Clay and Clay Minerals. 1989; 37(4): 325-332
[21] J A Helsen, Characterization of Iron(Ⅱ)and Iron(Ⅲ) Exchanged Montmorillonite And Hectorite Using the Mossbauer Effect. Clay Minerals. 1983; 18: 117-125
[22]张在龙,孙燕华,劳永新,等.未熟生油岩中含铁矿物对脂肪酸低温催化脱羧生烃的作用[M].科学通报,1998;43(24): 2649-2653
[23]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[M].天然气地球化学,2004;15(3):317-19
[24] R Davey, and C D Curtis. Mossbauer and chemical investigations of mudrocks. Clay Minerals, 1989; 24(1): 53-65
[25]王广利.矿物低温催化脂肪酸脱羧生烃动力学研究[D].东营:中国石油大学(华东),1999
[26]张国防,吴德云,马金钰.盐湖相石油的早期生成[M].石油勘探与开发,1993,20(5):42-48
[27]张国防,吴德云,马金钰.盐湖相石油早期生成[J].石油实验地质,1995,17(4):357-366
[28]张在龙,劳永新,王培建.盐水对未熟生油岩中脂肪酸催化脱羧生烃的影响[J].石油大学学报,2000,24(6):57-60
[29]魏黔钧.亚铁离子对碳酸盐岩有机质成烃演化的催化作用模拟实验研究[J].天然气地球科学,2005,16(3):306-309
[30]郝石生,贾振远.碳酸盐岩油气形成和分布[M].北京:石油工业出版社,1989:10-12
[31]周世新,夏燕青,罗斌杰,等.脂肪酸盐生烃热模拟研究及其意义[J].沉积学报,1997,15(2):118-121
[32]陈小东,王先彬.压力对有机质成熟和油气生成的影响[J].地球科技进展,1999,14(1):31-36
[33] Monthioux M, Landais P, Monin J C. Comparison between natural and artifical maturation series of humic coals from the Mahakam delta, Indonesia [J]. Org Geochem, 1985, 8: 275-292
[34]杨天宇,王涵云.岩石中有机质高温高压模拟实验[J].石油与天气地质,1987,8(4):380-389
[35]黄健全,周中毅,范善发.盆地深部油气形成的高温高压模拟实验研究[M].南京:江苏科学技术出版社,1992:244-245
[36] Braun R L, Burnham A K. Mathematical model of oil generation, degradation and expulsion [J]. Energy Fuels, 1990, 4: 132-146
[37] Cecil B, Stanton R, Allshouse S, et al. Effects of pressure on coalification. Ninth International Congress of Carboniferous Stratigraphy and Geology [J]. University of Illinois, Urbana, Illinois, 1979:32-38
[38] Sajgo C S, McEvoy J, Wolef G A, et al. Influence of temperature and pressure on maturation process-I, preliminary report [J]. Org Geochem, 1986, 10: 331-337
[39]丁福臣,王剑秋,钱家麟.压力下生油岩热解动力学研究[J].石油学报,1991,12(3):44-51
[40]李生杰.褐煤煤化作用的加压加热模拟实验及其意义[J].石油实验地质,1988,10(1):72-79
[41]范善发,周中毅,韩林林,等.压力对盆地深部有机质演化的影响[M].南京:江苏科学技术出版社,1992:246-249
[42] Ritter U K, Myhr M B, Vinge T, et al. Experimental heating and kinetic models of source rocks: comparison of different methods [J]. Org Geochem, 1995, 23(1): 1-9
[43] Ungerer P, Pelet R. Extrapolation of the kinetics of oil and gas formation from laboratory experiments to sedimentary basins [J]. Nature, 1987, 327(1): 52-54
[44]卢双舫,郭春萍,申家年,等.化学动力学法在黄骅坳陷未熟-低熟油资源评价中的应用[J].石油地质,2005,(6):18-23
[45] Braum R. Oil and gas evolution kinetics for oil shale and petroleum source rock determined from pyrolysis-TQMS data at two heating rates [J]. Energy and Fuel, 1992, (6):468-474
[46]高喜龙,肖贤明,王建宝.用开放体系的热解方法对烃源岩生烃动力学的研究[J].地球化学,2003,32(5):485-490
[47]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
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