TSR反应中地球化学条件的热力学估算
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摘要
从化学热力学的角度,通过热力学计算和绘制热力学相图,针对硫酸盐热化学还原反应(TSR反应)和H_2S对碳酸盐岩的溶蚀两个化学反应过程,判别其发生的可能性、方向和物理化学条件,求取不同温度下CaSO_4 (或SO_4~(2-))被直接还原为H_2S的离子浓度、pH和氧化还原条件;指出在地质体系中,当CaCO_3处于沉淀–溶解的边界时,少量酸性流体的加入就会使沉淀转为溶解,而当Ca~(2+)和CO_3~(2-)浓度升高时,又达到新的沉淀–溶解平衡。H_2S对CaCO_3的溶蚀在深度约为1000 m时达到最佳效果,长期、多次的TSR反应才能产生充足的酸性流体(即H_2S),这是溶蚀改造碳酸盐岩储层达到明显效果的必要条件。
According to the principle of thermodynamics, thermodynamic phase diagrams are calculated and drawn, the possibility, direction and physicochemical conditions of the two chemical reaction processes of TSR reaction and dissolution of carbonate rocks by H_2 S are determined, and the direct reduction of CaSO_4(or SO_4~(2-)) to H_2S at different temperatures is obtained. It shows that when CaCO_3 is at the boundary between precipitation and dissolution in geological system, a small amount of acidic fluid will make the precipitated CaCO_3 dissolved, and when the concentration of Ca2+ and CO_3~(2-) increases, a new equilibrium of precipitation and dissolution will be achieved. When the depth of dissolution of CaCO_3 is about 1000 m, H_2S achieves the best effect. Only long-term and repeated TSR reactions can produce sufficient acidic fluid(H_2S), which is the necessary condition for dissolution modification of carbonate reservoirs to achieve obvious results.
According to the principle of thermodynamics, thermodynamic phase diagrams are calculated and drawn, the possibility, direction and physicochemical conditions of the two chemical reaction processes of TSR reaction and dissolution of carbonate rocks by H_2 S are determined, and the direct reduction of CaSO_4(or SO_4~(2-)) to H_2S at different temperatures is obtained. It shows that when CaCO_3 is at the boundary between precipitation and dissolution in geological system, a small amount of acidic fluid will make the precipitated CaCO_3 dissolved, and when the concentration of Ca2+ and CO_3~(2-) increases, a new equilibrium of precipitation and dissolution will be achieved. When the depth of dissolution of CaCO_3 is about 1000 m, H_2S achieves the best effect. Only long-term and repeated TSR reactions can produce sufficient acidic fluid(H_2S), which is the necessary condition for dissolution modification of carbonate reservoirs to achieve obvious results.
引文
[1]朱光有,张水昌,梁英波,等.TSR对深部碳酸盐岩储层的溶蚀改造--四川盆地深部碳酸盐岩优质储层形成的重要方式.岩石学报,2006,22(8):2182?2194
[2]朱光有,张水昌,梁英波,等.四川盆地高含H2S天然气的分布与TSR成因证据.地质学报,2006,80(8):1208?1218
[3]Orr W L.Changes in sulfur content and isotopic ratios of sulfur during petroleum maturation-study of Big Horn basin paleozoic oils.AAPG Bulletin,1974,58(11):2295?2318
[4]王一刚,窦立荣,文应初,等.四川盆地东北部三叠系飞仙关组高含硫气藏H2S成因研究.地球化学,2002,31(6):517?524
[5]张水昌,朱光有,何坤.硫酸盐热化学还原作用对原油裂解成气和碳酸盐岩储层改造的影响及作用机制.岩石学报,2011,27(3):809?826
[6]Helgeson H C,Kirkham D H.Theoretical prediction of the thermodynamic behavior of aqueous electrolytes at high pressures and temperatures IV.American Journal of Science,1981,281:1249?1516
[7]Hill C A.H2S-related porosity and sulfuric acid oilfield karst.Alburquerque:AAPG Special Volumes,1995:301?306
[8]Hill C A.Sulfuric acid speleogenesis of carlsbad cavern and its relationship to hydrocarbons,Delaware basin,New Mexico and Texas.AAPG Bulletin,1990,74(74):1685?1694
[9]Seewald J S.Organic-inorganic interactions in petroleum-producing sedimentary basins.Nature,2003,426:327?333
[10]戴金星.中国含硫化氢的天然气分布特征、分类及其成因探讨.沉积学报,1985,3(4):109?120
[11]戴金星,胡见义,贾承造,等.科学安全勘探开发高硫化氢天然气田的建议.石油勘探与开发,2004,31(2):1?4
[12]Machel H G.Bacterial and thermochemical sulfate reduction in diagenetic settings-old and new insights.Sedimentary Geology,2001,140(1/2):143?175
[13]Worden R H,Smalley P C,Oxtoby N H.Gas souring by thermochemical sulfate reduction at 140°C.AAPGBulletin,1995,79(6):854?863
[14]Zhang T,Amrani A,Ellis G S,et al.Experimental investigation on thermochemical sulfate reduction by H2S initiation.Geochimica et Cosmochimica Acta,2008,72(14):3518?3530
[15]Tang Y,Ellis G S,Zhang T,et al.Effect of aqueous chemistry on the thermal stability of hydrocarbons in petroleum reservoirs.Geochmica et Cosmochimica Acta,2005,69(10):A559
[16]范明,胡凯,蒋小琼,等.酸性流体对碳酸盐岩储层的改造作用.地球化学,2009,38(1):20?26
[17]罗厚勇,王万春,刘文汇.TSR模拟实验研究与地质实际的异同及可能原因分析.石油实验地质,2012,34(2):186?192
[18]岳长涛,李术元,丁康乐,等.甲烷和固态硫酸钙的热化学还原反应模拟实验初步研究.地球化学,2003,32(6):601?605
[19]张单明,秦善,刘波,等.碳酸盐岩?H2S平衡体系原位溶蚀模拟实验及其地质意义.北京大学学报(自然科学版),2015,51(4):745?754
[20]张建勇,刘文汇,范明,等.TSR产物对碳酸盐岩储层是否具有改良作用--实验地质学的依据.海相油气地质,2008,13(2):57?61
[21]张建勇,刘文汇,腾格尔,等.TSR对气态烃组分及碳同位素组成的影响--高温高压模拟实验的证据.石油实验地质,2012,34(1):66?70
[22]赵兴齐,陈践发,郭望,等.川东北飞仙关组高含H2S气藏油田水地球化学特征.中南大学学报(自然科学版),2014(10):3477?3488
[23]Cai C,Xie Z,Worden R H,et al.Methane-dominated thermochemical sulphate reduction in the Triassic Feixianguan Formation East Sichuan Basin,China:towards prediction of fatal HS concentrations.Marine&Petroleum Geology,2004,21(10):1265?1279
[24]胡安平,Li Maowen,杨春,等.川东北高含硫化氢气藏中储层沥青的特征.石油学报,2010,31(2):231?236
[2]朱光有,张水昌,梁英波,等.四川盆地高含H2S天然气的分布与TSR成因证据.地质学报,2006,80(8):1208?1218
[3]Orr W L.Changes in sulfur content and isotopic ratios of sulfur during petroleum maturation-study of Big Horn basin paleozoic oils.AAPG Bulletin,1974,58(11):2295?2318
[4]王一刚,窦立荣,文应初,等.四川盆地东北部三叠系飞仙关组高含硫气藏H2S成因研究.地球化学,2002,31(6):517?524
[5]张水昌,朱光有,何坤.硫酸盐热化学还原作用对原油裂解成气和碳酸盐岩储层改造的影响及作用机制.岩石学报,2011,27(3):809?826
[6]Helgeson H C,Kirkham D H.Theoretical prediction of the thermodynamic behavior of aqueous electrolytes at high pressures and temperatures IV.American Journal of Science,1981,281:1249?1516
[7]Hill C A.H2S-related porosity and sulfuric acid oilfield karst.Alburquerque:AAPG Special Volumes,1995:301?306
[8]Hill C A.Sulfuric acid speleogenesis of carlsbad cavern and its relationship to hydrocarbons,Delaware basin,New Mexico and Texas.AAPG Bulletin,1990,74(74):1685?1694
[9]Seewald J S.Organic-inorganic interactions in petroleum-producing sedimentary basins.Nature,2003,426:327?333
[10]戴金星.中国含硫化氢的天然气分布特征、分类及其成因探讨.沉积学报,1985,3(4):109?120
[11]戴金星,胡见义,贾承造,等.科学安全勘探开发高硫化氢天然气田的建议.石油勘探与开发,2004,31(2):1?4
[12]Machel H G.Bacterial and thermochemical sulfate reduction in diagenetic settings-old and new insights.Sedimentary Geology,2001,140(1/2):143?175
[13]Worden R H,Smalley P C,Oxtoby N H.Gas souring by thermochemical sulfate reduction at 140°C.AAPGBulletin,1995,79(6):854?863
[14]Zhang T,Amrani A,Ellis G S,et al.Experimental investigation on thermochemical sulfate reduction by H2S initiation.Geochimica et Cosmochimica Acta,2008,72(14):3518?3530
[15]Tang Y,Ellis G S,Zhang T,et al.Effect of aqueous chemistry on the thermal stability of hydrocarbons in petroleum reservoirs.Geochmica et Cosmochimica Acta,2005,69(10):A559
[16]范明,胡凯,蒋小琼,等.酸性流体对碳酸盐岩储层的改造作用.地球化学,2009,38(1):20?26
[17]罗厚勇,王万春,刘文汇.TSR模拟实验研究与地质实际的异同及可能原因分析.石油实验地质,2012,34(2):186?192
[18]岳长涛,李术元,丁康乐,等.甲烷和固态硫酸钙的热化学还原反应模拟实验初步研究.地球化学,2003,32(6):601?605
[19]张单明,秦善,刘波,等.碳酸盐岩?H2S平衡体系原位溶蚀模拟实验及其地质意义.北京大学学报(自然科学版),2015,51(4):745?754
[20]张建勇,刘文汇,范明,等.TSR产物对碳酸盐岩储层是否具有改良作用--实验地质学的依据.海相油气地质,2008,13(2):57?61
[21]张建勇,刘文汇,腾格尔,等.TSR对气态烃组分及碳同位素组成的影响--高温高压模拟实验的证据.石油实验地质,2012,34(1):66?70
[22]赵兴齐,陈践发,郭望,等.川东北飞仙关组高含H2S气藏油田水地球化学特征.中南大学学报(自然科学版),2014(10):3477?3488
[23]Cai C,Xie Z,Worden R H,et al.Methane-dominated thermochemical sulphate reduction in the Triassic Feixianguan Formation East Sichuan Basin,China:towards prediction of fatal HS concentrations.Marine&Petroleum Geology,2004,21(10):1265?1279
[24]胡安平,Li Maowen,杨春,等.川东北高含硫化氢气藏中储层沥青的特征.石油学报,2010,31(2):231?236
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