Wang Yang, Qin Yong, Zhang Rui, He Lilin, Anovitz Lawrence M, Bleuel Markus, Mildner David F R, Liu Shimin, Zhu Yanming
Key Laboratory of Coalbed Methane Resources and Reservoir Formation Process, China University of Mining and Technology, Xuzhou, Jiangsu 221008, China.
School of Resources and Earth Science, China University of Mining and Technology, Xuzhou, Jiangsu 221116, China.
Energy Fuels. 2018;32(12). doi: 10.1021/acs.energyfuels.8b03437.
The Lower Cambrian Niutitang and Lower Silurian Longmaxi shales in the Upper Yangtze Platform (UYP) are the most promising strata for shale gas exploration in China. Knowledge of the nanoscale pore structure may improve the prediction of the gas production potential in Chinese marine shales. A systematic investigation of the pore accessibility and its impact on methane adsorption capacity has been conducted on shale samples using various techniques including geochemical and mineralogical analyses, field-emission scanning electron microscopy (FE-SEM), small-angle neutron scattering (SANS), helium porosimetry, and methane adsorption. The results show that organic matter (OM) pores with various shapes dominate the pore systems of these shales. OM tended to mix with clay minerals and converted to organoclay complexes, developing plentiful micro- and mesopores. A unified fit model with two pore structures, fractal pores and finite pores, was used to model the SANS data to characterize the pore structure of the shales. Both mass and surface fractals are identified for each pore structure. The total porosity estimated by the Porod invariant method ranges between 2.35 and 16.40%, of which the porosity for finite pores ranges between 0.35 and 6.36%, and the porosity for the fractal pores ranges between 2.07 and 8.51%. The fraction of open pores was evaluated by comparing the porosities estimated by He porosimetry and SANS. We find that the fraction of open pores is higher than 64% for most of these shales. Correlation analyses suggest that clay and total organic carbon (TOC) have opposite effects on pore structure and methane adsorption capacity. Samples with higher clay contents have higher pore accessibility and lower total porosity, surface area, and maximum methane adsorption, whereas samples with higher TOC content show the inverse relationships. The high percentage of open pores may reduce methane adsorption capacity in these shales, whereas low pore accessibility may reduce methane production at specific pressure differences. Thus, both TOC and pore accessibility may be essential controlling factors in methane production from shale gas reservoirs.
上扬子地台(UYP)的下寒武统牛蹄塘组和下志留统龙马溪组页岩是中国页岩气勘探最具潜力的地层。了解纳米级孔隙结构有助于提高对中国海相页岩气产量潜力的预测。利用地球化学和矿物学分析、场发射扫描电子显微镜(FE-SEM)、小角中子散射(SANS)、氦孔隙率测定法和甲烷吸附等多种技术,对页岩样品的孔隙可及性及其对甲烷吸附能力的影响进行了系统研究。结果表明,各种形状的有机质(OM)孔隙在这些页岩的孔隙系统中占主导地位。OM倾向于与粘土矿物混合并转化为有机粘土复合体,形成大量的微孔和介孔。采用具有分形孔隙和有限孔隙两种孔隙结构的统一拟合模型对SANS数据进行建模,以表征页岩的孔隙结构。每种孔隙结构都识别出了质量分形和表面分形。用Porod不变量法估算的总孔隙率在2.35%至16.40%之间,其中有限孔隙的孔隙率在0.35%至6.36%之间,分形孔隙的孔隙率在2.07%至8.51%之间。通过比较氦孔隙率测定法和SANS估算的孔隙率来评估开孔率。我们发现,这些页岩中的大多数开孔率都高于64%。相关性分析表明,粘土和总有机碳(TOC)对孔隙结构和甲烷吸附能力有相反的影响。粘土含量较高的样品具有较高的孔隙可及性,但总孔隙率、表面积和最大甲烷吸附量较低,而TOC含量较高的样品则呈现相反的关系。开孔率高可能会降低这些页岩中的甲烷吸附能力,而孔隙可及性低可能会在特定压差下降低甲烷产量。因此,TOC和孔隙可及性可能都是页岩气藏甲烷生产的关键控制因素。