A new pore type,nano-scale organo-clay complex pore-fracture was first discovered based on argon ion polishing-field emission scanning electron microscopy,energy dispersive spectroscopy and three-dimensional reconstru...A new pore type,nano-scale organo-clay complex pore-fracture was first discovered based on argon ion polishing-field emission scanning electron microscopy,energy dispersive spectroscopy and three-dimensional reconstruction by focused ion-scanning electron in combination with analysis of TOC,R_(o)values,X-ray diffraction etc.in the Cretaceous Qingshankou Formation shale in the Songliao Basin,NE China.Such pore characteristics and evolution study show that:(1)Organo-clay complex pore-fractures are developed in the shale matrix and in the form of spongy and reticular aggregates.Different from circular or oval organic pores discovered in other shales,a single organo-clay complex pore is square,rectangular,rhombic or slaty,with the pore diameter generally less than 200 nm.(2)With thermal maturity increasing,the elements(C,Si,Al,O,Mg,Fe,etc.)in organo-clay complex change accordingly,showing that organic matter shrinkage due to hydrocarbon generation and clay mineral transformation both affect organo-clay complex pore-fracture formation.(3)At high thermal maturity,the Qingshankou Formation shale is dominated by nano-scale organo-clay complex pore-fractures with the percentage reaching more than 70%of total pore space.The spatial connectivity of organo-clay complex pore-fractures is significantly better than that of organic pores.It is suggested that organo-complex pore-fractures are the main pore space of laminar shale at high thermal maturity and are the main oil and gas accumulation space in the core area of continental shale oil.The discovery of nano-scale organo-clay complex pore-fractures changes the conventional view that inorganic pores are the main reservoir space and has scientific significance for the study of shale oil formation and accumulation laws.展开更多
Based on the results of drilling,tests and simulation experiments,the shales of the Cretaceous Qingshankou Formation in the Gulong Sag of the Songliao Basin are discussed with respect to hydrocarbon generation evoluti...Based on the results of drilling,tests and simulation experiments,the shales of the Cretaceous Qingshankou Formation in the Gulong Sag of the Songliao Basin are discussed with respect to hydrocarbon generation evolution,shale oil occurrence,and pore/fracture evolution mechanism.In conjunction with a substantial amount of oil testing and production data,the Gulong shale oil enrichment layers are evaluated and the production behaviors and decline law are analyzed.The results are drawn in four aspects.First,the Gulong shales are in the stage of extensive hydrocarbon expulsion when R_(0) is 1.0%-1.2%,with the peak hydrocarbon expulsion efficiency of 49.5%approximately.In the low-medium maturity stage,shale oil migrates from kerogen to rocks and organic pores/fractures.In the medium-high maturity stage,shale oil transforms from adsorbed state to free state.Second,the clay mineral intergranular pores/fractures,dissolution pores,and organic pores make up the majority of the pore structure.During the transformation,clay minerals undergo significant intergranular pore/fracture development between the minerals such as illite and illite/smectite mixed layer.A network of pores/fractures is formed by organic matter cracking.Third,free hydrocarbon content,effective porosity,total porosity,and brittle mineral content are the core indicators for the evaluation of shale oil enrichment layers.Class-I layers are defined as free hydrocarbon content equal or greater than 6.0 mg/g,effective porosity equal or greater than 3.5%,total porosity equal or greater than 8.0%,and brittle mineral content equal or greater than 50%.It is believed that the favourable oil layers are Q2-Q3 and Q8-Q9.Fourth,the horizontal wells in the core area of the light oil zone exhibit a high cumulative production in the first year,and present a hyperbolic production decline pattern,with the decline index of 0.85-0.95,the first-year decline rate of 14.5%-26.5%,and the single-well estimated ultimate recovery(EUR)greater than 2.0×10^(4)t.In practical exploration and production,more efforts will be devoted to the clarification of hydrocarbon generation and expulsion mechanisms,accurate testing of porosity and hydrocarbon content/phase of shale under formation conditions,precise delineation of the boundary of enrichment area,relationship between mechanical properties and stimulated reservoir volume,and enhanced oil recovery,in order to improve the EUR and achieve a large-scale,efficient development of shale oil.展开更多
By conducting experimental analyses, including thermal pyrolysis, micro-/nano-CT, argon-ion polishing field emission scanning electron microscopy (FE-SEM), confocal laser scanning microscopy (CLSM), and two-dimensiona...By conducting experimental analyses, including thermal pyrolysis, micro-/nano-CT, argon-ion polishing field emission scanning electron microscopy (FE-SEM), confocal laser scanning microscopy (CLSM), and two-dimensional nuclear magnetic resonance (2D NMR), the Gulong shale oil in the Songliao Basin was investigated with respect to formation model, pore structure and accumulation mechanism. First, in the Gulong shale, there are a large number of pico-algae, nano-algae and dinoflagellates, which were formed in brackish water environment and constituted the hydrogen-rich oil source materials of shale. Second, most of the oil-generating materials of the Qingshankou Formation shale exist in the form of organo-clay complex. During organic matter thermal evolution, clay minerals had double effects of suppression and catalytic hydrogenation, which expanded shale oil window and increased light hydrocarbon yield. Third, the formation of storage space in the Gulong Shale was related to dissolution and hydrocarbon generation. With the diagenesis, micro-/nano-pores increased, pore diameter decreased and more bedding fractures appeared, which jointly gave rise to the unique reservoir with dual media (i.e. nano-scale pores and micro-scale bedding fractures) in the Gulong shale. Fourth, the micro-/nano-scale oil storage unit in the Gulong shale exhibits independent oil/gas occurrence phase, and shows that all-size pores contain oils, which occur in condensate state in micropores or in oil-gas two phase (or liquid) state in macropores/mesopores. The understanding about Gulong shale oil formation and accumulation mechanism has theoretical and practical significance for advancing continental shale oil exploration in China.展开更多
Taking tight oil in Gaotaizi and Fuyu oil layers of the Upper Cretaceous Qingshankou Formation in northern Songliao Basin as an example, based on analyses of nuclear magnetic resonance and high pressure mercury inject...Taking tight oil in Gaotaizi and Fuyu oil layers of the Upper Cretaceous Qingshankou Formation in northern Songliao Basin as an example, based on analyses of nuclear magnetic resonance and high pressure mercury injection, experiment methods of supercritical carbon dioxide displacement and extraction are firstly employed to quantify crude oil mobility in tight sand reservoirs with different lithologies and oil contents. The results show that, under the conditions of simulating the Cretaceous Qingshankou Formation in the northern Songliao Basin at a temperature of 76-89 °C and a pressure of 35-42 MPa, the lower limit of the porosity of the movable oil is4.4%, and the lower limit of the permeability is 0.015′10-3 mm2. The lower limit of the average pore throat radius is 21 nm. On this basis,a classification standard for three types of tight sand reservoirs is proposed. Type I reservoirs are characterized by the movable fluid saturation larger than 40%, the movable oil ratio(ratio of movable oil to total oil) greater than 30% and the starting pressure gradient in the range of 0.3-0.6 MPa/m; Type II reservoirs are characterized by the movable fluid saturation in the range of 10%–40%, the movable oil ratio in the range of 5%–30% and the starting pressure gradient in the range of 0.6–1.0 MPa/m; Type III reservoirs are characterized by the movable fluid saturation less than 10% in general, the movable oil ratio less than 5%, and the starting pressure gradient greater than1.0 MPa/m. The fluid mobility in tight sand reservoirs is mainly affected by diagenesis and sedimentary environment. Reservoirs with depth lower than 2000 m are dominated by type I reservoir, whereas those with greater depth are dominated by type I and II reservoirs.Reservoirs in inner delta-front facies are dominated by type I reservoir, whereas those in outer delta-front facies and shore-shallow lacustrine facies are dominated by type II and III reservoirs.展开更多
1 Introduction The technology breakthrough in the exploration of shale gas and tight oil has greatly extended the global fossil fuel resources （Jia et al., 2012; Zou et al., 2012; Qiu et al., 2013）. Although shale o...1 Introduction The technology breakthrough in the exploration of shale gas and tight oil has greatly extended the global fossil fuel resources （Jia et al., 2012; Zou et al., 2012; Qiu et al., 2013）. Although shale oil has been the global hot topic in the study of unconventional resources, there are varied definitions with respect to shale oil by different researchers.展开更多
To determine geochemical indicators for depositional environment favored by terrestrial petroleum source rocks, we selected 40 source rock samples from the Late Cretaceous Qingshankou Formation （Kzqn） and the first ...To determine geochemical indicators for depositional environment favored by terrestrial petroleum source rocks, we selected 40 source rock samples from the Late Cretaceous Qingshankou Formation （Kzqn） and the first member of Nenjiang Formation （K2n1） in the Songliao Basin to qualify saturate fraction and aromatic fraction using GC-HRT （gas chromatography high resolution time-of-flight mass spectrometry） and quantify important biomarkers using GC-MS. The results reveal that source rocks from the 1st member of Qingshankou Formation （K2qn1） are characterized by not only high contents of terpanes, regular steranes and 4-methylsteranes but also high contents of dinosteranes, C31 steranes and aryl isoprenoids. Presence of specific biomarkers like elementary sulfur and lanostanes indicates a depositional environment of lagoon characterized by water stratification and high salinity. In the 2nd-3rd members of Qingshankou Formation （K2qn2＋3）, source rocks contain lower contents of biomarkers, indicating a depositional environment of shallow fresh-water lake delta. Source rocks in the K2n1 contain high contents of terpanes, regular steranes and 4-methylsteranes but lower contents of dinosteranes, C31 steranes and aryl isoprenoids, indicating a depositional environment of fresh-brackish open lake characterized by low salinity and poor water stratification, where organic matter is seriously altered by bacteria. Overall analysis shows that primary geochemical indicators for terrestrial petroleum source rocks are as follows： 1） C30 hopanes 〉 1500 ppm; 2） gammacerane 〉190 ppm; 3） C27 steranes 〉200 ppm; 4） 4-methylsteranes 〉 100 ppm; 5） aryl isoprenoids 〉 3 ppm; 6） dehydroxyl-vitamin E 〉 10 ppm.展开更多
Crude oil hydrocarbon composition characteristics and oil viscosity prediction are important bases in petroleum exploration. A total of 54 oil/heavy-oil samples and 17 oil sands were analyzed and quantified using both...Crude oil hydrocarbon composition characteristics and oil viscosity prediction are important bases in petroleum exploration. A total of 54 oil/heavy-oil samples and 17 oil sands were analyzed and quantified using both comprehensive 2D gas chromatog raphy （GCxGC） and comprehensive 2D gas chromatography/time-of-flight mass spectrometry （GCxGC/TOFMS）. The results show that crude oil in the West slope is mainly heavy oil and its hydrocarbon composition is characterized overall by paraf fins 〉 mono-aromatics 〉 naphthenes 〉 non-hydrocarbons 〉 di-aromatics 〉 tri-aromatics 〉 tetra-aromatics. Aromatics are most abundant and non-hydrocarbons are least abundant, whilst content differences among paraffins, naphthenes, aromatics, and non-hydrocarbons are less than 15%. There are two types of heavy oil, secondary type and mixing type. Biodegradation is the main formation mechanism of heavy oil. Biodegradation levels cover light biodegradation, moderate biodegradation, and se- vere biodegradation. With increasing biodegradation, paraffin content decreases while contents of aromatics and non- hydrocarbons increase. In contrast, naphthene content increases first and then decreases with increasing biodegradation. In se- vere biodegradation stage, naphthenes decrease more quickly than aromatics and non-hydrocarbons. This provides a new method for studying oil/heavy-oil biodegradation mechanism and biodegradation resistance of different hydrocarbons at dif- ferent biodegradation stages. In the Longhupao-Daan terrace and Qijia-Gulong depression, most crude oil is conventional oil. Its composition is dominated by paraffins with the lowest content of aromatics. In some casual oil wells from the Long- hupao-Daan terrace, crude oil from Saertu oil reservoirs is moderately biodegraded whereas crude oil from Putaohua oil reser voir is lightly biodegraded. Chemical parameters using saturate hydrocarbons and aromatics are usually not suitable for deter mining organic type and thermal maturity of biodegraded oil, especially of moderately or severely biodegraded oil, whilst Ts/（Ts＋Tm） ratio can be used to determine thermal maturity of both conventional crude oil and heavy oil.展开更多
基金Supported by Central Government Guided Local Science and Technology Innovation Fund Program(ZY20B13)。
文摘A new pore type,nano-scale organo-clay complex pore-fracture was first discovered based on argon ion polishing-field emission scanning electron microscopy,energy dispersive spectroscopy and three-dimensional reconstruction by focused ion-scanning electron in combination with analysis of TOC,R_(o)values,X-ray diffraction etc.in the Cretaceous Qingshankou Formation shale in the Songliao Basin,NE China.Such pore characteristics and evolution study show that:(1)Organo-clay complex pore-fractures are developed in the shale matrix and in the form of spongy and reticular aggregates.Different from circular or oval organic pores discovered in other shales,a single organo-clay complex pore is square,rectangular,rhombic or slaty,with the pore diameter generally less than 200 nm.(2)With thermal maturity increasing,the elements(C,Si,Al,O,Mg,Fe,etc.)in organo-clay complex change accordingly,showing that organic matter shrinkage due to hydrocarbon generation and clay mineral transformation both affect organo-clay complex pore-fracture formation.(3)At high thermal maturity,the Qingshankou Formation shale is dominated by nano-scale organo-clay complex pore-fractures with the percentage reaching more than 70%of total pore space.The spatial connectivity of organo-clay complex pore-fractures is significantly better than that of organic pores.It is suggested that organo-complex pore-fractures are the main pore space of laminar shale at high thermal maturity and are the main oil and gas accumulation space in the core area of continental shale oil.The discovery of nano-scale organo-clay complex pore-fractures changes the conventional view that inorganic pores are the main reservoir space and has scientific significance for the study of shale oil formation and accumulation laws.
基金Supported by the National Natural Science Foundation Project(42090020,42090025)Strategic Research of Oil and Gas Development Major Project of Ministry of Science and TechnologyPetroChina Scientific Research and Technological Development Project(2019E2601).
文摘Based on the results of drilling,tests and simulation experiments,the shales of the Cretaceous Qingshankou Formation in the Gulong Sag of the Songliao Basin are discussed with respect to hydrocarbon generation evolution,shale oil occurrence,and pore/fracture evolution mechanism.In conjunction with a substantial amount of oil testing and production data,the Gulong shale oil enrichment layers are evaluated and the production behaviors and decline law are analyzed.The results are drawn in four aspects.First,the Gulong shales are in the stage of extensive hydrocarbon expulsion when R_(0) is 1.0%-1.2%,with the peak hydrocarbon expulsion efficiency of 49.5%approximately.In the low-medium maturity stage,shale oil migrates from kerogen to rocks and organic pores/fractures.In the medium-high maturity stage,shale oil transforms from adsorbed state to free state.Second,the clay mineral intergranular pores/fractures,dissolution pores,and organic pores make up the majority of the pore structure.During the transformation,clay minerals undergo significant intergranular pore/fracture development between the minerals such as illite and illite/smectite mixed layer.A network of pores/fractures is formed by organic matter cracking.Third,free hydrocarbon content,effective porosity,total porosity,and brittle mineral content are the core indicators for the evaluation of shale oil enrichment layers.Class-I layers are defined as free hydrocarbon content equal or greater than 6.0 mg/g,effective porosity equal or greater than 3.5%,total porosity equal or greater than 8.0%,and brittle mineral content equal or greater than 50%.It is believed that the favourable oil layers are Q2-Q3 and Q8-Q9.Fourth,the horizontal wells in the core area of the light oil zone exhibit a high cumulative production in the first year,and present a hyperbolic production decline pattern,with the decline index of 0.85-0.95,the first-year decline rate of 14.5%-26.5%,and the single-well estimated ultimate recovery(EUR)greater than 2.0×10^(4)t.In practical exploration and production,more efforts will be devoted to the clarification of hydrocarbon generation and expulsion mechanisms,accurate testing of porosity and hydrocarbon content/phase of shale under formation conditions,precise delineation of the boundary of enrichment area,relationship between mechanical properties and stimulated reservoir volume,and enhanced oil recovery,in order to improve the EUR and achieve a large-scale,efficient development of shale oil.
基金Supported by the Central Guiding Local Science and Technology Development Special Project(ZY20B13)。
文摘By conducting experimental analyses, including thermal pyrolysis, micro-/nano-CT, argon-ion polishing field emission scanning electron microscopy (FE-SEM), confocal laser scanning microscopy (CLSM), and two-dimensional nuclear magnetic resonance (2D NMR), the Gulong shale oil in the Songliao Basin was investigated with respect to formation model, pore structure and accumulation mechanism. First, in the Gulong shale, there are a large number of pico-algae, nano-algae and dinoflagellates, which were formed in brackish water environment and constituted the hydrogen-rich oil source materials of shale. Second, most of the oil-generating materials of the Qingshankou Formation shale exist in the form of organo-clay complex. During organic matter thermal evolution, clay minerals had double effects of suppression and catalytic hydrogenation, which expanded shale oil window and increased light hydrocarbon yield. Third, the formation of storage space in the Gulong Shale was related to dissolution and hydrocarbon generation. With the diagenesis, micro-/nano-pores increased, pore diameter decreased and more bedding fractures appeared, which jointly gave rise to the unique reservoir with dual media (i.e. nano-scale pores and micro-scale bedding fractures) in the Gulong shale. Fourth, the micro-/nano-scale oil storage unit in the Gulong shale exhibits independent oil/gas occurrence phase, and shows that all-size pores contain oils, which occur in condensate state in micropores or in oil-gas two phase (or liquid) state in macropores/mesopores. The understanding about Gulong shale oil formation and accumulation mechanism has theoretical and practical significance for advancing continental shale oil exploration in China.
基金Supported by the PetroChina Science and Technology Project(2012E-2603-06)
文摘Taking tight oil in Gaotaizi and Fuyu oil layers of the Upper Cretaceous Qingshankou Formation in northern Songliao Basin as an example, based on analyses of nuclear magnetic resonance and high pressure mercury injection, experiment methods of supercritical carbon dioxide displacement and extraction are firstly employed to quantify crude oil mobility in tight sand reservoirs with different lithologies and oil contents. The results show that, under the conditions of simulating the Cretaceous Qingshankou Formation in the northern Songliao Basin at a temperature of 76-89 °C and a pressure of 35-42 MPa, the lower limit of the porosity of the movable oil is4.4%, and the lower limit of the permeability is 0.015′10-3 mm2. The lower limit of the average pore throat radius is 21 nm. On this basis,a classification standard for three types of tight sand reservoirs is proposed. Type I reservoirs are characterized by the movable fluid saturation larger than 40%, the movable oil ratio(ratio of movable oil to total oil) greater than 30% and the starting pressure gradient in the range of 0.3-0.6 MPa/m; Type II reservoirs are characterized by the movable fluid saturation in the range of 10%–40%, the movable oil ratio in the range of 5%–30% and the starting pressure gradient in the range of 0.6–1.0 MPa/m; Type III reservoirs are characterized by the movable fluid saturation less than 10% in general, the movable oil ratio less than 5%, and the starting pressure gradient greater than1.0 MPa/m. The fluid mobility in tight sand reservoirs is mainly affected by diagenesis and sedimentary environment. Reservoirs with depth lower than 2000 m are dominated by type I reservoir, whereas those with greater depth are dominated by type I and II reservoirs.Reservoirs in inner delta-front facies are dominated by type I reservoir, whereas those in outer delta-front facies and shore-shallow lacustrine facies are dominated by type II and III reservoirs.
文摘1 Introduction The technology breakthrough in the exploration of shale gas and tight oil has greatly extended the global fossil fuel resources （Jia et al., 2012; Zou et al., 2012; Qiu et al., 2013）. Although shale oil has been the global hot topic in the study of unconventional resources, there are varied definitions with respect to shale oil by different researchers.
基金supported by Major State Basic Research Development Program of China (Grant No. 2009CB219308) and Petro China Daqing Oilfield Company Ltd.
文摘To determine geochemical indicators for depositional environment favored by terrestrial petroleum source rocks, we selected 40 source rock samples from the Late Cretaceous Qingshankou Formation （Kzqn） and the first member of Nenjiang Formation （K2n1） in the Songliao Basin to qualify saturate fraction and aromatic fraction using GC-HRT （gas chromatography high resolution time-of-flight mass spectrometry） and quantify important biomarkers using GC-MS. The results reveal that source rocks from the 1st member of Qingshankou Formation （K2qn1） are characterized by not only high contents of terpanes, regular steranes and 4-methylsteranes but also high contents of dinosteranes, C31 steranes and aryl isoprenoids. Presence of specific biomarkers like elementary sulfur and lanostanes indicates a depositional environment of lagoon characterized by water stratification and high salinity. In the 2nd-3rd members of Qingshankou Formation （K2qn2＋3）, source rocks contain lower contents of biomarkers, indicating a depositional environment of shallow fresh-water lake delta. Source rocks in the K2n1 contain high contents of terpanes, regular steranes and 4-methylsteranes but lower contents of dinosteranes, C31 steranes and aryl isoprenoids, indicating a depositional environment of fresh-brackish open lake characterized by low salinity and poor water stratification, where organic matter is seriously altered by bacteria. Overall analysis shows that primary geochemical indicators for terrestrial petroleum source rocks are as follows： 1） C30 hopanes 〉 1500 ppm; 2） gammacerane 〉190 ppm; 3） C27 steranes 〉200 ppm; 4） 4-methylsteranes 〉 100 ppm; 5） aryl isoprenoids 〉 3 ppm; 6） dehydroxyl-vitamin E 〉 10 ppm.
基金supported by National Basic Research Program of China(Grant No.2006CB701404)CNPC Grand S&T Special Project(Grant No.2012E-2603)
文摘Crude oil hydrocarbon composition characteristics and oil viscosity prediction are important bases in petroleum exploration. A total of 54 oil/heavy-oil samples and 17 oil sands were analyzed and quantified using both comprehensive 2D gas chromatog raphy （GCxGC） and comprehensive 2D gas chromatography/time-of-flight mass spectrometry （GCxGC/TOFMS）. The results show that crude oil in the West slope is mainly heavy oil and its hydrocarbon composition is characterized overall by paraf fins 〉 mono-aromatics 〉 naphthenes 〉 non-hydrocarbons 〉 di-aromatics 〉 tri-aromatics 〉 tetra-aromatics. Aromatics are most abundant and non-hydrocarbons are least abundant, whilst content differences among paraffins, naphthenes, aromatics, and non-hydrocarbons are less than 15%. There are two types of heavy oil, secondary type and mixing type. Biodegradation is the main formation mechanism of heavy oil. Biodegradation levels cover light biodegradation, moderate biodegradation, and se- vere biodegradation. With increasing biodegradation, paraffin content decreases while contents of aromatics and non- hydrocarbons increase. In contrast, naphthene content increases first and then decreases with increasing biodegradation. In se- vere biodegradation stage, naphthenes decrease more quickly than aromatics and non-hydrocarbons. This provides a new method for studying oil/heavy-oil biodegradation mechanism and biodegradation resistance of different hydrocarbons at dif- ferent biodegradation stages. In the Longhupao-Daan terrace and Qijia-Gulong depression, most crude oil is conventional oil. Its composition is dominated by paraffins with the lowest content of aromatics. In some casual oil wells from the Long- hupao-Daan terrace, crude oil from Saertu oil reservoirs is moderately biodegraded whereas crude oil from Putaohua oil reser voir is lightly biodegraded. Chemical parameters using saturate hydrocarbons and aromatics are usually not suitable for deter mining organic type and thermal maturity of biodegraded oil, especially of moderately or severely biodegraded oil, whilst Ts/（Ts＋Tm） ratio can be used to determine thermal maturity of both conventional crude oil and heavy oil.
