抽提前/后成熟页岩对氮气、二氧化碳的吸附特征及其对孔隙研究的意义
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摘要
选择了成熟度、有机质类型与矿物组成较为接近但有机碳含量(TOC)有明显差异的两个成熟页岩进行了氮气、二氧化碳气体等温吸附分析,并考察了抽提前/后吸附特征的变化,尝试说明影响成熟页岩孔隙发育的主要因素。初步的结果表明,页岩的比表面积主要取决于微孔的发育程度,而孔体积则与大孔的发育程度关系密切;微孔发育程度与页岩的有机碳含量有密切的关系;页岩抽提后对两种气体的吸附量相对于抽提前均显著增加,抽提前/后样品在60°C及110°C干燥等不同前处理方式下获得的氮气等温吸附数据表明,残留沥青对孔隙发育具有明显的制约作用。
Two mature shale samples, which show similar organic matter type, mineralogy and maturation level but different total organic carbon content(TOC),have been investigated using the adsorption of nitrogen and carbon dioxide to determine main factors that could influence pore structures of shales. Moreover, the comparison of gas adsorption was performed between extracted sample and un-extracted sample. Preliminary results suggest that micropores contribute more to the total specific surface area than mesopores, whereas macropores have a close relationship with the pore volume. Specific surface area of micropores shows a good correlation with TOC values of gas shales. The gas adsorption capacity of extracted samples is much larger than that of un-extracted samples. Nitrogen isothermal adsorption data of shale samples obtained by various pretreatment methods, such as drying of extracted and un-extracted samples at 60 °C and 110 °C, respectively, show that residual bitumens in shales have significant restrictions for the development of pores.
Two mature shale samples, which show similar organic matter type, mineralogy and maturation level but different total organic carbon content(TOC),have been investigated using the adsorption of nitrogen and carbon dioxide to determine main factors that could influence pore structures of shales. Moreover, the comparison of gas adsorption was performed between extracted sample and un-extracted sample. Preliminary results suggest that micropores contribute more to the total specific surface area than mesopores, whereas macropores have a close relationship with the pore volume. Specific surface area of micropores shows a good correlation with TOC values of gas shales. The gas adsorption capacity of extracted samples is much larger than that of un-extracted samples. Nitrogen isothermal adsorption data of shale samples obtained by various pretreatment methods, such as drying of extracted and un-extracted samples at 60 °C and 110 °C, respectively, show that residual bitumens in shales have significant restrictions for the development of pores.
引文
[1]王社教,王兰生,黄金亮,李新景,李登华.上扬子区志留系页岩气成藏条件[J].天然气工业,2009,29(5):45-50.Wang She-jiao,Wang Lan-sheng,Huang Jin-liang,Li Xin-jing,Li Deng-hua.Accumulation conditions of shale gas reservoirs in Silurian of the Upper Yangtze region[J].Nat Gas Ind,2009,29(5):45-50(in Chinese with English abstract).
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[9]杨峰,宁正福,张世栋,胡昌蓬,杜立红,刘慧卿.基于氮气吸附实验的页岩孔隙结构表征[J].天然气工业,2013,33(4):135-140.Yang Feng,Ning Zheng-fU?Zhang Shi-dong,Hu Chang-peng,Du Li-hong,Liu Hui-qing.Characterization of pore structures in shales through nitrogen adsorption experiment[J].Nat Gas Ind,2013,33(4):135-140(in Chinese with English abstract).
[10]Lu X C,Li F C,Watson A T.Adsorption measurements in Devonian shales[J].Fuel,1995,74(4):599-603.
[11]Chalmers G R L,Bustin R M,Power I M.Characterization of gas shale pore systems by porosimetry,pycnometry,surface area,and field emission scanning electron microscopy/transmission electron microscopy image analyses:Examples from the Barnett,Woodford,Haynesville?Marcellus,and Doig units[J].AAPG Bulletin,2012,96(6):1099-1119.
[12]Chalmers G R L,Bustin R M.The organic matter distribution and methane capacity of the lower Cretaceous strata of northeastern British Columbia,Canada[J].Int J Coal Geol,2007,70(1):223-239.
[13]Chalmers G R L,Bustin R M.Lower Cretaceous gas shales in northeastern British Columbia,Part I:Geological controls on methane sorption capacity[J].Bull Can Pet Geol,2008,56(1):1-21.
[14]Ross D J K,Bustin R M.Shale gas potential of the Lower Jurassic Gordondale Member,northeastern British Columbia,Canada[J].Bull Can Pet Geol,2007,55(2):176-177.
[15]Ross D J K,Bustin R M.The importance of shale composition and pore structure upon gas storage potential of shale gas reservoirs[J].Mar Pet Geol,2009,26(6):916-927.
[16]Zhang T W,Ellis G S,Ruppel S Cs Milliken K?Yang R.Effect of organic-matter type and thermal maturity on methane adsorption in shale-gas systems[J].Org Geochem,2012,47:120-131.
[17]Wang S B,Song Z G,Cao T T,Song X.The methane sorption capacity of Paleozoic shales from the Sichuan Basin,China[J].Mar Pet Geol,2013,44:112-119.
[18]张小东,秦勇,桑树勋.不同煤级煤及其萃余物吸附性能的研究[J].地球化学,2006,35(5):567-574.Zhang Xiao-dong,Qin Yong,Sang Shu-xun.Adsorption capacity of different metamorphism coals and their residues[J].Geochimica,2006,35(5):567-574(in Chinese with English abstract).
[19]Jarvie D M,Hill R J,Ruble T E,Pollastro R M.Unconventional shale-gas systems:The Mississippian Barnett Shale of north-central Texas as one model for thermogenic shale-gas assessment[J].AAPG Bulletin,2007,91(4):475-499.
[20]Valenza J J,Drenzek N,Marques F,Pagels M,Mastalerz M.Geochemical controls on shale microstructure[J].Geology,2013,41(5):611-614.
[21]Gregg S,Sing K S.Adsorption,Surface Area and Porosity[M].New York:Academic Press,1983:1-303.
[22]Brunauer SEmmett P H,Teller E.Adsorption of gases in multimolecular layers[J].J Am Chem Soc,1938,60(2):309-319.
[23]Barrett E P,Joyner L G,Halenda P P.The determination of pore volume and area distributions in porous substances.I.Computations from nitrogen isotherms[J].J Am Chem Soc,1951,73(1):373-380.
[24]Brunauer SDeming L S,Deming W E,Teller E.On a theory of the van der Waals adsorption of gases[J].J Am Chem Soc,1940,62(7):1723-1732.
[25]Chalmers G R,Bustin R M,Power I M.Characterization of gas shale pore systems by porosimetry,pycnometry,surface area,and field emission scanning electron microscopy/transmission electron microscopy image analyses:Examples from the Barnett,Woodford,Haynesville,Marcellus,and Doig units[J].AAPG Bulletin,2012,96(6):1099-1119.
[26]Curtis M E,Sondergeld C H,Ambrose R J,Rai C S.Microstructural investigation of gas shales in two and three dimensions using nanometer-scale resolution imaging[J].AAPG Bulletin,2012,96(4):665-677.
[27]Loucks R G,Reed R M,Ruppel S C,Jarvie D M.Morphology,genesis,and distribution of nanometer-scale pores in siliceous muds tones of the Mississippian Barnett Shale[J].J Sediment Res,2009,79(12):848-861.
[28]吉利明,邱军利,夏燕青,张同伟.常见黏土矿物电镜扫描微孔隙特征与甲烷吸附性[J].石油学报,2012,33(2):249-256.Ji Li-ming?Qiu Jun-li,Xia Yan-qing,Zhang Tong-wei.Micro-pore characteristics and methane adsorption properties of common clay minerals by electron microscope scanning[J].Acta Pet Sin,2012,33(2):249-256(in Chinese with English abstract).
[2]熊伟,郭为,刘洪林,高树生,胡志明,杨发荣.页岩的储层特征以及等温吸附特征[J].天然气工业,2012,32(1):113-116.Xiong Wei,Guo Wei,Liu Hong-lin,Gao Shu-sheng,Hu Zhi-ming,Yang Fa-rong.Shale reservoir characteristics and isothermal adsorption properties[J].Nat Gas Ind,2012,32(1):113-116(in Chinese with English abstract).
[3]李武广,杨胜来,徐晶,董谦.考虑地层温度和压力的页岩吸附气含量计算新模型[J].天然气地球科学,2012,23(4):791-796.Li Wu-guang,Yang Sheng-lai?Xu Jing,Dong Qian.A new model for shale adsorptive gas amount under a certain geological conditions of temperature and pressure[J].Nat Gas Geosci?2012,23(4):791-796(in Chinese with English abstract).
[4]葛明娜,张金川,李晓光,唐玄,扬升宇.辽河东部凸起上古生界页岩含气性分析[J].断块油气田,2012,19(6):722-726.Ge Ming-na,Zhang Jin-chuan,Li Xiao-guang,Tang Xuan,Yang Sheng-yu.Gas-bearing property analysis on Upper Paleozoic shale in eastern Uplift of Liaohe Basin[J].Fault-Block Oil Gas Field,2012,19(6):722-726(in Chinese with English abstract).
[5]罗小平,刘军,徐国盛,马若龙,鲜志亮,徐猛.湘中拗陷泥盆-石炭系海相泥页岩地球化学特征及等温吸附性能[J].成都理工大学学报(自然科学版),2012,39(2):206-214.Luo Xiao-ping,Liu Jun,Xu Guo-sheng,Ma Ruo-long,Xian Zhi-rao,Xu Meng.Geochemical characteristics and isothermal adsorption properties of the Devonian-Carboniferous marine mud shale in the Xiangzhong depression?Hunan,China[J].J Chengdu Univ Technol(Sci Technol Ed),2012,39(2):206-214(in Chinese with English abstract).
[6]陈尚斌,朱炎铭,王红岩,刘洪林,魏伟,方俊华.川南龙马溪组页岩气储层纳米孔隙结构特征及其成藏意义[J].煤炭学报,2012,37(3):438-444.Chen Shang-bin,Zhu Yan-ming,Wang Hong-yan,LiuHong-lin,Wei Wei,Fang Jun-hua.Structure characteristics and accumulation significance of nanopores in Longmaxi shale gas reservoir in the southern Sichuan Basin[J].J China Coal Soc,2012,37(3):438-444(in Chinese with English abstract).
[7]刘岩,周文,邓虎成.鄂尔多斯盆地上三叠统延长组含气页岩地质特征及资源评价m.天然气工业,2013,33(3):19-23.Liu Yan,Zhou Wen,Deng Hu-cheng.Geological characteristics of gas-bearing shales in the Yanchang Formation and its resource assessment in the Ordos Basin[J].Nat Gas Ind,2013,33(3):19-23(in Chinese with English abstract).
[8]曲占庆,林珊珊,张杰,张东,苏程.多组分和吸附对页岩气储量计算的影响[J].特种油气藏,2012,19(3):114-116.Qu Zhan-qing,Lin Shan-shan,Zhang Jie,Zhang Dong,Su Cheng.Impacts of muti-component and adsoiption on shale gas reserve estimation[J].Spec Oil Gas Reser,2012,19(3):114-116(in Chinese with English abstract).
[9]杨峰,宁正福,张世栋,胡昌蓬,杜立红,刘慧卿.基于氮气吸附实验的页岩孔隙结构表征[J].天然气工业,2013,33(4):135-140.Yang Feng,Ning Zheng-fU?Zhang Shi-dong,Hu Chang-peng,Du Li-hong,Liu Hui-qing.Characterization of pore structures in shales through nitrogen adsorption experiment[J].Nat Gas Ind,2013,33(4):135-140(in Chinese with English abstract).
[10]Lu X C,Li F C,Watson A T.Adsorption measurements in Devonian shales[J].Fuel,1995,74(4):599-603.
[11]Chalmers G R L,Bustin R M,Power I M.Characterization of gas shale pore systems by porosimetry,pycnometry,surface area,and field emission scanning electron microscopy/transmission electron microscopy image analyses:Examples from the Barnett,Woodford,Haynesville?Marcellus,and Doig units[J].AAPG Bulletin,2012,96(6):1099-1119.
[12]Chalmers G R L,Bustin R M.The organic matter distribution and methane capacity of the lower Cretaceous strata of northeastern British Columbia,Canada[J].Int J Coal Geol,2007,70(1):223-239.
[13]Chalmers G R L,Bustin R M.Lower Cretaceous gas shales in northeastern British Columbia,Part I:Geological controls on methane sorption capacity[J].Bull Can Pet Geol,2008,56(1):1-21.
[14]Ross D J K,Bustin R M.Shale gas potential of the Lower Jurassic Gordondale Member,northeastern British Columbia,Canada[J].Bull Can Pet Geol,2007,55(2):176-177.
[15]Ross D J K,Bustin R M.The importance of shale composition and pore structure upon gas storage potential of shale gas reservoirs[J].Mar Pet Geol,2009,26(6):916-927.
[16]Zhang T W,Ellis G S,Ruppel S Cs Milliken K?Yang R.Effect of organic-matter type and thermal maturity on methane adsorption in shale-gas systems[J].Org Geochem,2012,47:120-131.
[17]Wang S B,Song Z G,Cao T T,Song X.The methane sorption capacity of Paleozoic shales from the Sichuan Basin,China[J].Mar Pet Geol,2013,44:112-119.
[18]张小东,秦勇,桑树勋.不同煤级煤及其萃余物吸附性能的研究[J].地球化学,2006,35(5):567-574.Zhang Xiao-dong,Qin Yong,Sang Shu-xun.Adsorption capacity of different metamorphism coals and their residues[J].Geochimica,2006,35(5):567-574(in Chinese with English abstract).
[19]Jarvie D M,Hill R J,Ruble T E,Pollastro R M.Unconventional shale-gas systems:The Mississippian Barnett Shale of north-central Texas as one model for thermogenic shale-gas assessment[J].AAPG Bulletin,2007,91(4):475-499.
[20]Valenza J J,Drenzek N,Marques F,Pagels M,Mastalerz M.Geochemical controls on shale microstructure[J].Geology,2013,41(5):611-614.
[21]Gregg S,Sing K S.Adsorption,Surface Area and Porosity[M].New York:Academic Press,1983:1-303.
[22]Brunauer SEmmett P H,Teller E.Adsorption of gases in multimolecular layers[J].J Am Chem Soc,1938,60(2):309-319.
[23]Barrett E P,Joyner L G,Halenda P P.The determination of pore volume and area distributions in porous substances.I.Computations from nitrogen isotherms[J].J Am Chem Soc,1951,73(1):373-380.
[24]Brunauer SDeming L S,Deming W E,Teller E.On a theory of the van der Waals adsorption of gases[J].J Am Chem Soc,1940,62(7):1723-1732.
[25]Chalmers G R,Bustin R M,Power I M.Characterization of gas shale pore systems by porosimetry,pycnometry,surface area,and field emission scanning electron microscopy/transmission electron microscopy image analyses:Examples from the Barnett,Woodford,Haynesville,Marcellus,and Doig units[J].AAPG Bulletin,2012,96(6):1099-1119.
[26]Curtis M E,Sondergeld C H,Ambrose R J,Rai C S.Microstructural investigation of gas shales in two and three dimensions using nanometer-scale resolution imaging[J].AAPG Bulletin,2012,96(4):665-677.
[27]Loucks R G,Reed R M,Ruppel S C,Jarvie D M.Morphology,genesis,and distribution of nanometer-scale pores in siliceous muds tones of the Mississippian Barnett Shale[J].J Sediment Res,2009,79(12):848-861.
[28]吉利明,邱军利,夏燕青,张同伟.常见黏土矿物电镜扫描微孔隙特征与甲烷吸附性[J].石油学报,2012,33(2):249-256.Ji Li-ming?Qiu Jun-li,Xia Yan-qing,Zhang Tong-wei.Micro-pore characteristics and methane adsorption properties of common clay minerals by electron microscope scanning[J].Acta Pet Sin,2012,33(2):249-256(in Chinese with English abstract).