Halite and gypsum minerals in saline shale make the retention mechanism and chemical fractionation of residual oil unique. The Dongpu Depression in North China is a typically saline lacustrine basin with developing ha...Halite and gypsum minerals in saline shale make the retention mechanism and chemical fractionation of residual oil unique. The Dongpu Depression in North China is a typically saline lacustrine basin with developing halite and gypsum. The effect of gypsum minerals on residual oil content and chemical fractionation remains unclear. In this study, shale samples with different gypsum contents were used in organic geochemical experiments, showing that the high total organic matter (TOC) content and type II kerogen leads to a high residual oil content, as shown by high values of volatile hydrocarbon (S1) and extractable organic matter (EOM). XRD and FE-SEM result indicate that the existence of gypsum in saline shale contributes to an enhanced pore space and a higher residual oil content in comparison to non-gypsum shale. Additionally, the increase in the gypsum mineral content leads to an increase in the saturated hydrocarbon percentage and a decrease in polar components percentage (resins and asphaltene). Furthermore, thermal simulation experiments on low-mature saline shale show that the percentage of saturated hydrocarbons in the residual oil is high and remains stable and that the storage space is mainly mesoporous (> 20 nm) in the oil expulsion stage. However, the saturated hydrocarbons percentage decreases rapidly, and oil exists in mesopores (> 20 nm and < 5 nm) in the gas expulsion stage. In general, gypsum is conducive to the development of pore space, the adsorption of hydrocarbons and the occurrence of saturated hydrocarbon, leading to large quantities of residual oil. The data in this paper should prove to be reliable for shale oil exploration in saline lacustrine basins.展开更多
The composition of gas released under vacuum by crushing from the gas shale of Longmaxi Formation in Upper Yangtze Plate,Southern China was systematically investigated in this study.The effect of residual gas release ...The composition of gas released under vacuum by crushing from the gas shale of Longmaxi Formation in Upper Yangtze Plate,Southern China was systematically investigated in this study.The effect of residual gas release on pore structures was checked using low-pressure nitrogen adsorption techniques.The influence of particle size on the determination of pore structure characteristics was considered.Using the Frenkel-Halsey-Hill method from low-pressure nitrogen adsorption data,the fractal dimensions were identified at relative pressures of 0‒0.5 and 0.5‒1 as D1 and D2,respectively,and the evolution of fractal features related to gas release was also discussed.The results showed that a variety component of residual gas was released from all shale samples,containing hydrocarbon gas of CH4(29.58%‒92.53%),C2H6(0.97%‒2.89%),C3H8(0.01%‒0.65%),and also some non-hydrocarbon gas such as CO2(3.54%‒67.09%)and N2(1.88%‒8.07%).The total yield of residual gas was in a range from 6.1μL/g to 17.0μL/g related to rock weight.The geochemical and mineralogical analysis suggested that the residual gas yield was positively correlated with quartz(R^2=0.5480)content.The residual gas released shale sample has a higher surface area of 17.20‒25.03 m^2/g and the nitrogen adsorption capacity in a range of 27.32‒40.86 ml/g that is relatively higher than the original samples(with 9.22‒16.30 m^2/g and 10.84‒17.55 ml/g).Clearer hysteresis loop was observed for the original shale sample in nitrogen adsorption-desorption isotherms than residual gas released sample.Pore structure analysis showed that the proportions of micro-,meso-and macropores were changed as micropores decreased while meso-and macropores increased.The fractal dimensions D1 were in range from 2.5466 to 2.6117 and D2 from 2.6998 to 2.7119 for the residual gas released shale,which is smaller than the original shale.This factor may indicate that the pore in residual gas released shale was more homogeneous than the original shale.The results indicated that both residual gas and their pore space have few contributions to shale gas production and effective reservoir evaluation.The larger fragments samples of granular rather than powdery smaller than 60 mesh fraction of shale seem to be better for performing effective pore structure analysis to the Longmaxi shale.展开更多
基金funded by the National Natural Science Foundation of China (NSFC) (41872128)the Science Foundation of China University of Petroleum, Beijing (No. 2462020YXZZ021).
文摘Halite and gypsum minerals in saline shale make the retention mechanism and chemical fractionation of residual oil unique. The Dongpu Depression in North China is a typically saline lacustrine basin with developing halite and gypsum. The effect of gypsum minerals on residual oil content and chemical fractionation remains unclear. In this study, shale samples with different gypsum contents were used in organic geochemical experiments, showing that the high total organic matter (TOC) content and type II kerogen leads to a high residual oil content, as shown by high values of volatile hydrocarbon (S1) and extractable organic matter (EOM). XRD and FE-SEM result indicate that the existence of gypsum in saline shale contributes to an enhanced pore space and a higher residual oil content in comparison to non-gypsum shale. Additionally, the increase in the gypsum mineral content leads to an increase in the saturated hydrocarbon percentage and a decrease in polar components percentage (resins and asphaltene). Furthermore, thermal simulation experiments on low-mature saline shale show that the percentage of saturated hydrocarbons in the residual oil is high and remains stable and that the storage space is mainly mesoporous (> 20 nm) in the oil expulsion stage. However, the saturated hydrocarbons percentage decreases rapidly, and oil exists in mesopores (> 20 nm and < 5 nm) in the gas expulsion stage. In general, gypsum is conducive to the development of pore space, the adsorption of hydrocarbons and the occurrence of saturated hydrocarbon, leading to large quantities of residual oil. The data in this paper should prove to be reliable for shale oil exploration in saline lacustrine basins.
基金This work was financially supported by the National Natural Science Foundation of China(41802158)projects of China Geological Survey(DD20160183,DD20190085)+2 种基金Major State Research Development Program of China(2016YFC0600202)Fundamental Research Funds for Chinese Academy of Geological Sciences(JYYWF20181201)the CGS-CSC Scholarship Fund(201908575013).
文摘The composition of gas released under vacuum by crushing from the gas shale of Longmaxi Formation in Upper Yangtze Plate,Southern China was systematically investigated in this study.The effect of residual gas release on pore structures was checked using low-pressure nitrogen adsorption techniques.The influence of particle size on the determination of pore structure characteristics was considered.Using the Frenkel-Halsey-Hill method from low-pressure nitrogen adsorption data,the fractal dimensions were identified at relative pressures of 0‒0.5 and 0.5‒1 as D1 and D2,respectively,and the evolution of fractal features related to gas release was also discussed.The results showed that a variety component of residual gas was released from all shale samples,containing hydrocarbon gas of CH4(29.58%‒92.53%),C2H6(0.97%‒2.89%),C3H8(0.01%‒0.65%),and also some non-hydrocarbon gas such as CO2(3.54%‒67.09%)and N2(1.88%‒8.07%).The total yield of residual gas was in a range from 6.1μL/g to 17.0μL/g related to rock weight.The geochemical and mineralogical analysis suggested that the residual gas yield was positively correlated with quartz(R^2=0.5480)content.The residual gas released shale sample has a higher surface area of 17.20‒25.03 m^2/g and the nitrogen adsorption capacity in a range of 27.32‒40.86 ml/g that is relatively higher than the original samples(with 9.22‒16.30 m^2/g and 10.84‒17.55 ml/g).Clearer hysteresis loop was observed for the original shale sample in nitrogen adsorption-desorption isotherms than residual gas released sample.Pore structure analysis showed that the proportions of micro-,meso-and macropores were changed as micropores decreased while meso-and macropores increased.The fractal dimensions D1 were in range from 2.5466 to 2.6117 and D2 from 2.6998 to 2.7119 for the residual gas released shale,which is smaller than the original shale.This factor may indicate that the pore in residual gas released shale was more homogeneous than the original shale.The results indicated that both residual gas and their pore space have few contributions to shale gas production and effective reservoir evaluation.The larger fragments samples of granular rather than powdery smaller than 60 mesh fraction of shale seem to be better for performing effective pore structure analysis to the Longmaxi shale.
