热成因天然气生成动力学模拟及其地质应用
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摘要
如何定量研究天然气形成、运移和聚集是当前天然气地球化学研究的一个热点。
天然气生成动力学模拟以干酪根(煤或原油)热解实验为基础,借助生烃动力学模
型和碳同位素动力学模型,结合具体盆地演化史,能定量地预测地质历史时期盆地
天然气组分和碳同位素组成,恢复天然气的成藏史。本研究利用黄金管限定体系对
四类不同类型有机质(正十八烷、煤、泥岩、碳酸盐岩)进行了生烃动力学模拟,
并结合具体地质条件探讨了天然气的生成过程。
限定体系下正十八烷裂解动力学研究显示,大量的气态烃并非直接来源于正十
八烷的裂解,而是主要来源于中间产物的二次裂解,裂解残余正构烷烃与初始正十
八烷相比存在较大的碳同位素分馏;正十八烷在相对低温条件下的裂解和聚合作用
与高温阶段导致轻烃和多环芳烃生成的歧化反应可能是造成热解实验中普遍存在
的气态烃碳同位素组成发生倒转的主要原因;甲烷生成动力学研究显示,由正构烷
烃裂解生成甲烷的最低门限在170℃,大量生成要到200℃,说明在地质条件下,
饱和烃是很难转化成气的。
鄂尔多斯盆地古生界两套烃源岩的热解实验表明,上古生界煤系烃源岩和下古
生界海相碳酸盐岩都具有较强的生气能力,烃源岩热解气中以干气为主(甲烷占
90%以上),其中二叠系煤的生气能力最强,甲烷最高产率约为270 mL/g TOC。经
动力学计算,二叠系煤的甲烷生成活化能分布范围为40-63 kcal/mol,频率因子为
1.01×10~11s~-1:二叠系泥岩的甲烷生成活化能分布范围为40-64 kcal/mol,频率因子
为1.51×10~11S~-1:奥陶系灰岩的甲烷生成活化能分布范围为39-63 kcal/mol,频率因
子为6.51×10~10S~-1,并在此基础上计算了样品生成甲烷的碳同位素动力学参数。
结合盆地具体埋藏史的动力学研究表明,二叠系煤系烃源岩的主生气期集中在
晚侏罗-早白垩世末期;盆地中部奥陶系灰岩主生气期集中在中侏罗-早白垩世末
期。在抬升过程中,二叠系煤系源岩在一定的时段内仍有一定量的气体生成。中部
气田C-P层位天然气为煤成气,源岩为C-P的煤系地层;奥陶系风化壳气藏属混源
气,以石炭一二叠系煤成气为主,奥陶系油型气为辅,定量计算表明,在中部气田大
部分地区,石炭.二叠系来源的天然气比例大于70%。
It is presently a hot spot to quantificationally study the formation, migration and accumulation of natural gas. The kinetic simulation of natural gas generation, based on pyrolysis experiments and by means of hydrocarbons generation kinetics and carbon isotope kinetics, can quantificationally predict the compositions of gas components and stable carbon isotope and reveal the history of gas accumulation according to the evolution history of a basin. Recently it is widely applied in the geochemical study of natural gas. In this paper kinetic pyrolyses on four types of organic matter (n-octadecane, coal, mudstone, carbonate rock)were carried out in gold tube confining-system, and the behaviour of natural gas generation are discussed combined with the geological condition.The kinetic study on the pyrolysis of n-octadecane shows that secondary cracking of pyrolysates from n-octadecane largely contributes to the amount of methane generation, much more than primary cracking of n-octadecane. The large shift in the carbon isotope values of the residual alkanes from the initial n-octodecane precursor indicates that the δ~(13)C values of over mature solid bitumen thermally generated in paleo-oil reservoir should not be directly used for oil and source rock correlation. Cracking and polymerization in the relatively low temperatures and disproportionation reactions leading to light hydrocarbons and polyaromatic hydrocarbons at high temperatures are probably causes for the carbon isotope reversal of gaseous hydrocarbons which is commonly observed in pyrolysis experiments. The kinetic study of methane generation implicates that methane from n-alkane hydrocarbons cracking begins to generate at 170 ℃ and the main peak of the generation is at 200 ℃ in sedimentary basins.
Pyrolysis experiments on two type of Paleozoic source rock in Ordos Basin show that both the Upper Paleozoic coal-measure source rock and Lower Paleozoic marine carbonate source rock have larger gas producing capacity. Pyrolysis gases of the source rocks are dominated by dry gases (methane accounts for over 90% of the total gases). Among them the Permian coal have the biggest gas producing capacity with the highest yield of 270 mL/g TOC. Pyrolysis yields were used to model methane generation with a series of parallel, first-order reactions with activations energies between 40 and 63 kcal/mol and a single frequency factor of 1.01 X 1011 s"1 for Permian coal, activations energies between 40 and 64 kcal/mol and a single frequency factor of 1.51 X 10n s"1 for Permian mudstone and activations energies between 39 and 63 kcal/mol and a single frequency factor of 6.51 X 1010 s"1 for Ordovician limestone. Based on these kinetic parameters, the carbon isotope kinetic parameters were calculated for methane.Extrapolating these parameters to the geological condition in Ordos Basin, hydrocarbon generation history of different source rocks were simulated through hydrocarbon-generating kinetic calculation. Results show that the Permian coal-measure source rock in Ordos Basin entered the "main gas window" between the Late Jurassic and the Early Cretaceous, while Ordovician limestone in the center of Ordos Basin entered the "main gas window" between the Middle Jurassic and the Early Cretaceous. The Permian coal-measure source rock can still generate a significant amount of gas in the process of tectonic uplifting. Natural gases in C-P reservoir are coal-formed gas derived from the C-P coal-measure source rock. The gases in the Ordovician weathering crust are mixed gases which were mainly derived from Upper Paleozoic coal-measure source rock. The quantificational calculation result implicates that over 70% of gas in the weathering crust in the Central gas field is from Carboniferous-Permian beds.
天然气生成动力学模拟以干酪根(煤或原油)热解实验为基础,借助生烃动力学模
型和碳同位素动力学模型,结合具体盆地演化史,能定量地预测地质历史时期盆地
天然气组分和碳同位素组成,恢复天然气的成藏史。本研究利用黄金管限定体系对
四类不同类型有机质(正十八烷、煤、泥岩、碳酸盐岩)进行了生烃动力学模拟,
并结合具体地质条件探讨了天然气的生成过程。
限定体系下正十八烷裂解动力学研究显示,大量的气态烃并非直接来源于正十
八烷的裂解,而是主要来源于中间产物的二次裂解,裂解残余正构烷烃与初始正十
八烷相比存在较大的碳同位素分馏;正十八烷在相对低温条件下的裂解和聚合作用
与高温阶段导致轻烃和多环芳烃生成的歧化反应可能是造成热解实验中普遍存在
的气态烃碳同位素组成发生倒转的主要原因;甲烷生成动力学研究显示,由正构烷
烃裂解生成甲烷的最低门限在170℃,大量生成要到200℃,说明在地质条件下,
饱和烃是很难转化成气的。
鄂尔多斯盆地古生界两套烃源岩的热解实验表明,上古生界煤系烃源岩和下古
生界海相碳酸盐岩都具有较强的生气能力,烃源岩热解气中以干气为主(甲烷占
90%以上),其中二叠系煤的生气能力最强,甲烷最高产率约为270 mL/g TOC。经
动力学计算,二叠系煤的甲烷生成活化能分布范围为40-63 kcal/mol,频率因子为
1.01×10~11s~-1:二叠系泥岩的甲烷生成活化能分布范围为40-64 kcal/mol,频率因子
为1.51×10~11S~-1:奥陶系灰岩的甲烷生成活化能分布范围为39-63 kcal/mol,频率因
子为6.51×10~10S~-1,并在此基础上计算了样品生成甲烷的碳同位素动力学参数。
结合盆地具体埋藏史的动力学研究表明,二叠系煤系烃源岩的主生气期集中在
晚侏罗-早白垩世末期;盆地中部奥陶系灰岩主生气期集中在中侏罗-早白垩世末
期。在抬升过程中,二叠系煤系源岩在一定的时段内仍有一定量的气体生成。中部
气田C-P层位天然气为煤成气,源岩为C-P的煤系地层;奥陶系风化壳气藏属混源
气,以石炭一二叠系煤成气为主,奥陶系油型气为辅,定量计算表明,在中部气田大
部分地区,石炭.二叠系来源的天然气比例大于70%。
It is presently a hot spot to quantificationally study the formation, migration and accumulation of natural gas. The kinetic simulation of natural gas generation, based on pyrolysis experiments and by means of hydrocarbons generation kinetics and carbon isotope kinetics, can quantificationally predict the compositions of gas components and stable carbon isotope and reveal the history of gas accumulation according to the evolution history of a basin. Recently it is widely applied in the geochemical study of natural gas. In this paper kinetic pyrolyses on four types of organic matter (n-octadecane, coal, mudstone, carbonate rock)were carried out in gold tube confining-system, and the behaviour of natural gas generation are discussed combined with the geological condition.The kinetic study on the pyrolysis of n-octadecane shows that secondary cracking of pyrolysates from n-octadecane largely contributes to the amount of methane generation, much more than primary cracking of n-octadecane. The large shift in the carbon isotope values of the residual alkanes from the initial n-octodecane precursor indicates that the δ~(13)C values of over mature solid bitumen thermally generated in paleo-oil reservoir should not be directly used for oil and source rock correlation. Cracking and polymerization in the relatively low temperatures and disproportionation reactions leading to light hydrocarbons and polyaromatic hydrocarbons at high temperatures are probably causes for the carbon isotope reversal of gaseous hydrocarbons which is commonly observed in pyrolysis experiments. The kinetic study of methane generation implicates that methane from n-alkane hydrocarbons cracking begins to generate at 170 ℃ and the main peak of the generation is at 200 ℃ in sedimentary basins.
Pyrolysis experiments on two type of Paleozoic source rock in Ordos Basin show that both the Upper Paleozoic coal-measure source rock and Lower Paleozoic marine carbonate source rock have larger gas producing capacity. Pyrolysis gases of the source rocks are dominated by dry gases (methane accounts for over 90% of the total gases). Among them the Permian coal have the biggest gas producing capacity with the highest yield of 270 mL/g TOC. Pyrolysis yields were used to model methane generation with a series of parallel, first-order reactions with activations energies between 40 and 63 kcal/mol and a single frequency factor of 1.01 X 1011 s"1 for Permian coal, activations energies between 40 and 64 kcal/mol and a single frequency factor of 1.51 X 10n s"1 for Permian mudstone and activations energies between 39 and 63 kcal/mol and a single frequency factor of 6.51 X 1010 s"1 for Ordovician limestone. Based on these kinetic parameters, the carbon isotope kinetic parameters were calculated for methane.Extrapolating these parameters to the geological condition in Ordos Basin, hydrocarbon generation history of different source rocks were simulated through hydrocarbon-generating kinetic calculation. Results show that the Permian coal-measure source rock in Ordos Basin entered the "main gas window" between the Late Jurassic and the Early Cretaceous, while Ordovician limestone in the center of Ordos Basin entered the "main gas window" between the Middle Jurassic and the Early Cretaceous. The Permian coal-measure source rock can still generate a significant amount of gas in the process of tectonic uplifting. Natural gases in C-P reservoir are coal-formed gas derived from the C-P coal-measure source rock. The gases in the Ordovician weathering crust are mixed gases which were mainly derived from Upper Paleozoic coal-measure source rock. The quantificational calculation result implicates that over 70% of gas in the weathering crust in the Central gas field is from Carboniferous-Permian beds.
引文
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