Kinetic Analysis and Applications to Thermochemical Sulfate Reduction of Methane: Taking Puguang Gas Reservoirs as an Example
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摘要: 热化学硫酸盐还原反应(TSR)对气藏有改造作用.以高压釜模拟实验为基础，选取甲烷与硫酸钙反应的动力学模型求取动力学参数，并结合普光地区的热史和埋藏史再现地质条件下甲烷与硫酸盐岩的反应过程，得出在距今130 Ma(早白垩世)的飞仙关组甲烷发生了硫酸盐还原反应，反应起始温度210 ℃，持续至30 Ma前反应终止；TSR的累积消耗甲烷量仅2.4%，说明在飞仙关组TSR对甲烷的后期损耗较少，因此并不影响甲烷的后期保存，这对于较深的碳酸盐岩储层依然具有勘探意义.Abstract: Thermochemical sulfate reduction (TSR) has modified the role of the gas reservoir. Selecting kinetics model on the basis of the high pressure thermal simulation experiment, we have obtained the dynamic parameters and reproduced rock reaction of methane with sulfate in the geological conditions by considering the burial and thermal evolution history of the Puguang area. It is concluded in this study that TSR of CH4 of Feixianguan Formations began from 130 Ma, at paleo 210 ℃, and terminated 30 Ma ago; The cumulative amount of methane consumed by the TSR only amounted to 2.4%, which indicates that Feixianguan TSR in the late lost less methane without affecting the later storage of methane. So, it is of exploration significance for deep carbonate reservoirs.
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Key words:
- CH4 /
- kinetics of chemical reactions /
- puguang gas reservoirs /
- petroleum geology
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图 1 不同温度时CH4-CaSO4反应体系气体产物
Fig. 1. Different temperatures for CH4-CaSO4 reaction gas product composition
图 4 普光气藏飞仙关组甲烷转化率-地质年代关系曲线
Fig. 4. Methane conversion rate-geological age curve of Feixianguan Formation in Puguang
图 5 普光地区埋藏史、热史曲线
Fig. 5. Curves of the burial and thermal evolution history of the Puguang area
图 6 甲烷消耗率与埋深和镜质体反射率的关系
Fig. 6. Relation of CH4 ratio with embedded depth and vitrinite reflectance of source
表 1 TSR的动力学参数
Table 1. Kinetic parameters of TSR
活化能(kJ/mol) 指前因子(min-1) 反应分数(%) 300 4.74×1016 0.053 046 310 1.84×1017 0.022 600 320 5.95×1010 0.155 865 330 1.49×109 0.315 458 340 8.42×109 0.403 557 350 1.03×1017 0.049 100 
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