天然气地球科学 ›› 2020, Vol. 31 ›› Issue (9): 13161325.doi: 10.11764/j.issn.1672-1926.2020.03.004
张文军1,2,3,4(),何坤3,4(),李贤庆1,2,米敬奎3,4,胡国艺3,4
Wen-jun ZHANG1,2,3,4(),Kun HE3,4(),Xian-qing LI1,2,Jing-kui MI3,4,Guo-yi HU3,4
摘要:
为了探讨含铁矿物对水—有机质生气的影响,基于黄金管热模拟装置,选用了高熟干酪根样品开展了3组有水体系(干酪根+水、干酪根+黄铁矿+水、干酪根+磁铁矿+水)的恒温热解实验。气体产物的定量分析结果表明,黄铁矿和磁铁矿的加入均导致干酪根在有水体系下气态烃产率一定程度的降低。比如,水—黄铁矿体系和水—磁铁矿体系在Easy%RO=3.08%时CH4产率相比单独有水体系分别降低8.5 mL/gTOC和13.3 mL/gTOC。水—黄铁矿体系CO2产率及碳稳定同位素值明显高于单独有水体系和水—磁铁矿体系,含铁矿物(尤其是磁铁矿)加入的热解体系的H2S产率明显低于单独有水体系。气体组成分析结果表明,含铁矿物的加入明显提高了烃类气体的干燥系数,同时导致异构烷烃相对含量的降低。水—磁铁矿体系气体产物氢同位素值相对低于单独有水体系,表明磁铁矿的加入促进了早期H2的生成而与有机质之间发生了加氢作用。这些结果表明,含铁矿物的加入可能抑制了碳正离子的反应,水—有机质的加氢生气可能主要是自由基反应。
中图分类号:
1 | TISSOT B P, WELTE D H. Petroleum Formation and Occurrence[M]. Berlin:Springer Verlag, 1984:330-381. |
2 | LEWAN M D, WINTERS J C, MCDONALD J H. Generation of oil-like pyrolyzates from organicrich shales[J]. Science,1979, 203(4383): 897-899. |
3 | LEWAN M D. Experiments on the role of water in petroleum formation[J]. Geochimica et Cosmochimica Acta,1997,61(17): 3691-3723. |
4 | BEHAR F, LEWAN M D, LORANT M, et al. Comparison of artificial maturation of lignite in hydrous and nonhydrous conditions[J]. Organic Geochemistry, 2003, 34(4):575-600. |
5 | PAN C C,GENG A S,ZHONG N N, et al.Kerogen pyrolysis in the presence and absence of water and minerals:Amounts and compositions of bitumen and liquid hydrocarbons[J]. Fuel, 2009, 88(5):909-919. |
6 | GAO L, SCHIMMELMANN A. TANG Y C,et al. Isotope rollover in shale gas observed in laboratory pyrolysis experiments: Insight to the role of water in thermogenesis of mature gas[J]. Organic Geochemistry, 2014, 68:95-106. |
7 | HE K, ZHANG S C, MI J K, et al. Pyrolysis involving n-hexadecane, water and minerals: Insight into the mechanisms and isotope fractionation for water-hydrocarbon reaction[J].Jou-rnal of Analytical and Applied Pyrolysis,2018,130:198-208. |
8 | LEWAN M D, ROY S. Role of water in hydrocarbon generation from Type-I kerogen in Mahogany oil shale of the Green River Formation[J].Organic Geochemistry,2011,42(1): 31-41. |
9 | HOERING T C. Thermal reactions of kerogen with added water, heavy water and pure organic substances[J]. Organic Geochemistry,1984,5(4): 267-278. |
10 | SCHIMMELMANN A, BOUDO J P, LEWAN M D, et al. Experimental controls on D/H and 13C/12C ratios of kerogen, bitumen and oil during hydrous pyrolysis[J]. Organic Geochemistry,2001,32(8): 1009-1018. |
11 | LEIF R N, SIMONEIT B R T. The role of alkenes produced during hydrous pyrolysis of a shale[J]. Organic Geochemistry,2000, 31(11): 1189-1208. |
12 | SEEWALD J S. Organic-inorganic interactions in petroleum-producing sedimentary basins[J]. Nature,2003, 426(6964): 327-333. |
13 | ZHANG S C, HE K, HU G Y, et al. Unique chemical and isotopic characteristics and origins of natural gases in the Paleozoic marine formations in the Sichuan Basin, SW China: Isotope fractionation of deep and high mature carbonate reservoir gases[J]. Marine and Petroleum Geology, 2018, 89: 68-82. |
14 | HE K, ZHANG S C, MI J K, et al. Carbon and hydrogen isotope fractionation for methane from non-isothermal pyrolysis of oil in anhydrous and hydrothermal conditions[J]. Energy Exploration & Exploitation, 2019, 37(5): 1558-1576. |
15 | SEEWALD J S, EGLINTON L B, OEG Y L. An experimental study of organic-inorganic interactions during vitrinite maturation[J]. Geochimica et Cosmochimica Acta,2000, 64(9): 1577-1591. |
16 | SEEWALD J S. Aqueous geochemistry of low molecular weight hydrocarbons at elevated temperatures and pressures: Constraints from mineral buffered laboratory experiments[J]. Geochimica et Cosmochimica Acta,2001,65(10):1641-1664. |
17 | MILESI V, PRINZHOFER A, GUYOT F, et al. Contribution of siderite-water interaction for the unconventional generation of hydrocarbon gases in the Solimoes Basin, north-west Brazil[J]. Marine and Petroleum Geology,2016, 71: 168-182. |
18 | CAI Y W, ZHANG S C, HE K, et al. Effects of U-ore on the chemical and isotopic composition of products of hydrous pyrolysis of organic matter[J]. Petroleum Science,2017,14(2):315-329. |
19 | 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):282-287. |
ZHANG J L, ZHANG P Z. Discussion of pyrite catalysis on the hydrocarbon generation process[J]. Advance in Earth Scicences, 1996,11(3):282-287. | |
20 | MA X X, ZHENG J J, ZHENG G D, et al. Influence of pyrite on hydrocarbon generation during pyrolysis of type-III kerogen[J]. Fuel, 2016, 167:329-336. |
21 | REEVES E P, SEEWALD J S, SYLVA S P. Hydrogen isotope exchange between n-alkanes and water under hydrothermal conditions[J]. Geochimica et Cosmochimica Acta,2012,77: 582-599. |
22 | 毛榕,米敬奎,张水昌,等.不同煤系源岩生烃特征的黄金管热模拟实验对比研究[J].天然气地球科学,2012,23(6):1127-1134. |
MAO R, MI J K, ZHANG Y C, et al. Study on the hydrocaron generation characteristics of different coaly source rocks by gold-tube pyrolysis experiments[J].Natural Gas Geoscien-ce,2012,23(6):1127-1134. | |
23 | MI J K, ZHANG S C, HE K. Experimental investigations about the effect of pressure on gas generation from coal[J]. Organic Geochemistry, 2014,74:116-122. |
24 | KISSIN Y V. Free-radical reactions of high molecular weight isoalkanes[J]. Industrial and Engineering Chemistry Research, 1987, 26(8):1633-1638. |
25 | KISSIN Y V. Catagenesis and composition of petroleum: Origin of n-alkanes and isoalkanes in petroleum crudes[J]. Geochimica et Cosmochimica Acta,1987,51(9): 2445-2457. |
26 | 于林平,潘长春,刘金钟,等.氧化作用对气态烃组成和碳同位素组成的影响[J].地球化学,2005,34(3):269-277. |
YU L P, PAN C C, LIU J Z, et al. Effects of oxidation on gaseous hydrocarbon composition and carbon isotope composition [J]. Geochemistry, 2005,34(3):269-277. | |
27 | HE K, ZHANG S C, MI J K, et al. Mechanism of catalytic hydropyrolysis of sedimentary organic matter with MoS2[J]. Petroleum Science, 2011,8(2):134-142 |
28 | SACKETT W M. Carbon and hydrogen isotope effects during the thermocatalytic production of hydrocarbons in laboratory simulation experiments[J]. Geochimica et Cosmochimica Acta, 1978,42(6):571-580. |
29 | CRAMER B, KROOSS B M, LITTKLE R. Modelling isotope fractionation during primary cracking of natural gas: A reaction kinetic approach[J]. Chemical Geology,1998, 149(3): 235-250. |
30 | HE K, ZAHNG S C, MI J K, et al. The evolution of chemical groups and isotopic fractionation at different maturation stages during lignite pyrolysis[J]. Fuel, 2018,211: 492-506. |
31 | TANG Y C, PERRY J K, JENDEN P D, et al. Mathematical modeling of stable carbon isotope ratios in natural gases[J]. Geochimica et Cosmochimica Acta,2000, 64(15): 2673-2687. |
32 | 王晓峰,刘文汇,徐永昌,等.水在有机质形成气态烃演化中作用的热模拟实验研究[J].自然科学进展,2006,16(10):1275-1281. |
WANG X F, LIU W H, XU Y C, et al. Thermal simulation experimental study on the role of water in the evolution of organic matter forming gaseous hydrocarbons[J]. Progress in Natural Science, 2006,16(10):1275-1281. | |
33 | 孙丽娜,张明峰,吴陈君,等.水对不同生烃模拟实验系统产物的影响[J].天然气地球科学,2015,26(3):524-532. |
SUN L N, ZHANG M F, WU C J, et al. The effect of water medium on the products of different pyrolysis system[J]. Natural Gas Geoscience, 2015,26(3):524-532. | |
34 | 马跃, 李术元, 王娟,等. 水介质条件下油页岩热解机理研究[J]. 燃料化学学报, 2011,39(12):881-886. |
MA Y, LI S Y, WANG J, et al. Mechanism of oil shale pyrolysis under high pressure water[J].Journal of Fuel Chemistry and Technology, 2011,39(12):881-886. |
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