Nano-scale pore structure and fractal dimension of organic-rich Wufeng-Longmaxi shale from Jiaoshiba area, Sichuan Basin: Investigations using FE-SEM, gas adsorption and helium pycnometry

Abstract Much attention have been recently paid to the upper Ordovician Wufeng shale (O3w) and lower Silurian Longmaxi shale (S1l) in the Jiaoshiba area of Sichuan Basin, which is now the largest producing shale gas field in China. Field emission scanning electron microscopy (FE-SEM), low pressure gas (N2 and CO2) adsorption, helium pycnometry, X-ray diffraction and geochemical analyses were performed to investigate the pore structure and fractal dimension of the pores in O3w-S1l shale formation in the Jiaoshiba area. FE-SEM images show that organic matter (OM) pores are dominant in the organic-rich samples and these pores are often irregular, bubble-like, elliptical and faveolate in shape, while in organic-poor samples, limited and isolated interparticle (interP), intraparticle (intraP) and OM pores are observed. Reversed S-shaped isotherms obtained from nitrogen adsorption are type Ⅱ, and hysteresis loops indicate that the shape of micropore in the samples is slit-or plate-like. BET surface areas and total pore volume vary from 12.2 to 27.1 m2/g and from 1.8 × 10−2 to 2.9 × 10−2 cm3/g, with an average of 19.5 m2/g and 2.3 × 10−2 cm3/g, respectively. Adsorption volume from both N2 and CO2 adsorption increases with respect to TOC contents. Porosities obtained from helium porosimetry are comparable with these from gas (CO2 and N2) adsorption in O3w-S1l shale. However, porosity determined by quantitative FE-SEM analysis is much smaller, which is mainly related to limited resolution and the small areas of investigation. Based on the Frenkel-Halsey-Hill (FHH) model of low-pressure N2 adsorption, fractal dimensions of the pores varied from 2.737 to 2.823. Relationships between pore structure parameters and TOC content, mineral composition and fractal dimension reveal that the fractal dimension is mainly associated with micropores. Samples with higher TOC content, higher quartz content and lower clay content tend to contain more heterogeneous micropores, resulting in higher fractal dimensions and more complicated pore structure in shales. Therefore, fractal dimension is an effective parameter to reflect the complexity of pore structure and the degree of micropore development in O3w-S1l shale.

[1]  Paul C. Hackley,et al.  The nature of porosity in organic-rich mudstones of the Upper Jurassic Kimmeridge Clay Formation, North Sea, offshore United Kingdom , 2012 .

[2]  Xiangliang Zeng,et al.  Characteristics of the Shale Gas Reservoir Rocks in the Lower Silurian Longmaxi Formation, East Sichuan Basin, China , 2013 .

[3]  János Urai,et al.  BIB-SEM study of the pore space morphology in early mature Posidonia Shale from the Hils area, Germany , 2012 .

[4]  R. M. Pollastro,et al.  Total petroleum system assessment of undiscovered resources in the giant Barnett Shale continuous (unconventional) gas accumulation, Fort Worth Basin, Texas , 2007 .

[5]  D. Avnir,et al.  An isotherm equation for adsorption on fractal surfaces of heterogeneous porous materials , 1989 .

[6]  R. Swanson,et al.  Digitally quantifying cerebral hemorrhage using Photoshop® and Image J , 2010, Journal of Neuroscience Methods.

[7]  R. Bustin,et al.  Geological controls on matrix permeability of Devonian Gas Shales in the Horn River and Liard basins, northeastern British Columbia, Canada , 2012 .

[8]  Jing-Hong Wu,et al.  Pore characteristics of organic-rich shales with high thermal maturity: A case study of the Longmaxi gas shale reservoirs from well Yuye-1 in southeastern Chongqing, China , 2015 .

[9]  R. Loucks,et al.  Morphology, Genesis, and Distribution of Nanometer-Scale Pores in Siliceous Mudstones of the Mississippian Barnett Shale , 2009 .

[10]  Christine E. Krohn,et al.  Fractal measurements of sandstones, shales, and carbonates , 1988 .

[11]  M. Curtis,et al.  Development of organic porosity in the Woodford Shale with increasing thermal maturity , 2012 .

[12]  Zheling Zhang,et al.  Theoretical and practical discussion of measurement accuracy for physisorption with micro- and mesoporous materials , 2013 .

[13]  R. Marc Bustin,et al.  Lower Cretaceous gas shales in northeastern British Columbia, Part I: geological controls on methane sorption capacity , 2008 .

[14]  J. Urai,et al.  A comparative study of representative 2D microstructures in Shaly and Sandy facies of Opalinus Clay (Mont Terri, Switzerland) inferred form BIB-SEM and MIP methods , 2014 .

[15]  Fang Yuan-fang Mesozoic Intra-Continental Progressive Deformation in Western Hunan-Hubei-Eastern Sichuan Provinces of China:Evidence from Apatite Fission Track and Balanced Cross-Section , 2010 .

[16]  R. Angulo,et al.  Fractal Dimensions from Mercury Intrusion Capillary Tests , 1992 .

[17]  Gerhard Gerold,et al.  The surface fractal dimension of the soil–pore interface as measured by image analysis , 2001 .

[18]  A. V. Shishkov,et al.  Production of ultraheavy hydrogen isotopes in absorption of pi- mesons by Li-6, Li-7 nuclei , 1990 .

[19]  J. Urai,et al.  Pore morphology and distribution in the Shaly facies of Opalinus Clay (Mont Terri, Switzerland): Insights from representative 2D BIB–SEM investigations on mm to nm scale , 2013 .

[20]  Wu,et al.  Multilayer adsorption on a fractally rough surface. , 1989, Physical review letters.

[21]  R. Marc Bustin,et al.  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 , 2012 .

[22]  M. Thommes,et al.  Quenched solid density functional theory and pore size analysis of micro-mesoporous carbons , 2009 .

[23]  A. Neimark,et al.  Density functional theory model of adsorption on amorphous and microporous silica materials. , 2006, Langmuir : the ACS journal of surfaces and colloids.

[24]  J. Urai,et al.  Variations in the morphology of porosity in the Boom Clay Formation: insights from 2D high resolution BIB-SEM imaging and Mercury injection Porosimetry , 2013, Netherlands Journal of Geosciences - Geologie en Mijnbouw.

[25]  Hu Lin Classification of pore structures in shale gas reservoir at the Longmaxi Formation in the south of Sichuan Basin , 2013 .

[26]  Xiangjun Liu,et al.  Experimental study on crack propagation in shale formations considering hydration and wettability , 2015 .

[27]  Christopher R. Clarkson,et al.  Pore structure characterization of North American shale gas reservoirs using USANS/SANS, gas adsorption, and mercury intrusion , 2013 .

[28]  Wang Shufan Biogenic Silica of Organic-Rich Shale in Sichuan Basin and Its Significance for Shale Gas , 2014 .

[29]  Benoit B. Mandelbrot,et al.  Fractal Geometry of Nature , 1984 .

[30]  K. Thomas,et al.  High-pressure methane adsorption and characterization of pores in Posidonia shales and isolated kerogens. , 2014 .

[31]  Xusheng Guo,et al.  The Puguang gas field: New giant discovery in the mature Sichuan Basin, southwest China , 2007 .

[32]  J. Bernal,et al.  Fractal geometry and mercury porosimetry: Comparison and application of proposed models on building stones , 2001 .

[33]  R. Slatt,et al.  Pore types in the Barnett and Woodford gas shales: Contribution to understanding gas storage and migration pathways in fine-grained rocks , 2011 .

[34]  Ruobing Liu,et al.  Geological Features and Reservoiring Mode of Shale Gas Reservoirs in Longmaxi Formation of the Jiaoshiba Area , 2014 .

[35]  Michael D. Abràmoff,et al.  Image processing with ImageJ , 2004 .

[36]  N. Seaton,et al.  A new analysis method for the determination of the pore size distribution of porous carbons from nitrogen adsorption measurements , 1989 .

[37]  D. Jarvie,et al.  Unconventional shale-gas systems: The Mississippian Barnett Shale of north-central Texas as one model for thermogenic shale-gas assessment , 2007 .

[38]  K. Rademann,et al.  Electronic Energy Transfer on Fractals , 1984 .

[39]  Keyu Liu,et al.  Organic matter/clay mineral intergranular pores in the Lower Cambrian Lujiaping Shale in the north-eastern part of the upper Yangtze area, China: A possible microscopic mechanism for gas preservation , 2015 .

[40]  T. Topór,et al.  Nano-scale texture and porosity of organic matter and clay minerals in organic-rich mudrocks , 2014 .

[41]  Feng Yang,et al.  Fractal characteristics of shales from a shale gas reservoir in the Sichuan Basin, China , 2014 .

[42]  B. Horsfield,et al.  Geochemical evolution of organic-rich shales with increasing maturity: A STXM and TEM study of the Posidonia Shale (Lower Toarcian, northern Germany) , 2012 .

[43]  R. Littke,et al.  Polyphase thermal evolution in the Infra-Cambrian Ara Group (South Oman Salt Basin) as deduced by maturity of solid reservoir bitumen , 2007 .

[44]  M. Jaroniec Evaluation of the Fractal Dimension from a Single Adsorption Isotherm , 1995 .

[45]  Xiong Jian,et al.  Investigation of pore structure and fractal characteristics of organic-rich Yanchang formation shale in central China by nitrogen adsorption/desorption analysis , 2015 .

[46]  Jinliang Huang,et al.  Geochemistry of the extremely high thermal maturity Longmaxi shale gas, southern Sichuan Basin , 2014 .

[47]  János Urai,et al.  BIB-SEM characterization of pore space morphology and distribution in postmature to overmature samples from the Haynesville and Bossier Shales , 2015 .

[48]  Zhang Hai-qua Late Ordovician- Early Silurian sedimentary facies and palaeogeographic evolution and its bearings on the black shales in the Middle-Upper Yangtze area , 2013 .

[49]  E. Teller,et al.  On a Theory of the van der Waals Adsorption of Gases , 1940 .

[50]  R. Marc Bustin,et al.  The importance of shale composition and pore structure upon gas storage potential of shale gas reservoirs , 2009 .

[51]  K. Sing Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity (Recommendations 1984) , 1985 .

[52]  János Urai,et al.  Morphology of the pore space in claystones - evidence from BIB/FIB ion beam sectioning and cryo-SEM observations , 2009 .

[53]  T. Guo,et al.  Evaluation of highly thermally mature shale-gas reservoirs in complex structural parts of the Sichuan Basin , 2013, Journal of Earth Science.

[54]  Ruobing Liu,et al.  Characteristics and controlling factors of micropore structures of the Longmaxi Shale in the Jiaoshiba area, Sichuan Basin , 2014 .

[55]  Yong Qin,et al.  Reservoir evaluation of the Lower Silurian Longmaxi Formation shale gas in the southern Sichuan Basin of China , 2014 .

[56]  D. Avnir,et al.  Recommendations for the characterization of porous solids (Technical Report) , 1994 .

[57]  Hanrong Zhang,et al.  Formation and enrichment mode of Jiaoshiba shale gas field, Sichuan Basin , 2014 .

[58]  Jiang Wen-li The present situation of oil & gas resources exploration and strategic selection of potential area in China , 2011 .

[59]  Feiyu Wang,et al.  Evolution of overmature marine shale porosity and implication to the free gas volume , 2013 .

[60]  Yanbin Yao,et al.  Fractal characterization of adsorption-pores of coals from North China: An investigation on CH4 adsorption capacity of coals , 2008 .

[61]  A. Schimmelmann,et al.  Porosity of Devonian and Mississippian New Albany Shale across a maturation gradient: Insights from organic petrology, gas adsorption, and mercury intrusion , 2013 .

[62]  Peter Pfeifer,et al.  Chemistry in noninteger dimensions between two and three. I. Fractal theory of heterogeneous surfaces , 1983 .

[63]  Peter Pfeifer,et al.  Fractal Analysis and Surface Roughness of Nonporous Carbon Fibers and Carbon Blacks , 1994 .

[64]  M. Mahamud,et al.  The use of fractal analysis in the textural characterization of coals , 2008 .

[65]  J. Curtis Fractured shale-gas systems , 2002 .

[66]  Chun Liu,et al.  The characterization and quantitative analysis of nanopores in unconventional gas reservoirs utilizing FESEM–FIB and image processing: An example from the lower Silurian Longmaxi Shale, upper Yangtze region, China , 2014 .

[67]  A. Erdem-Senatalar,et al.  Method to Evaluate the Fractal Dimensions of Solid Adsorbents , 1999 .

[68]  N. Harris,et al.  Porosity characteristics of the Devonian Horn River shale, Canada: Insights from lithofacies classification and shale composition , 2015 .

[69]  K. Gubbins,et al.  Pore size distribution analysis of microporous carbons: a density functional theory approach , 1993 .

[70]  M. D. Rudnicki,et al.  Organic matter–hosted pore system, Marcellus Formation (Devonian), Pennsylvania , 2013 .

[71]  E. Teller,et al.  ADSORPTION OF GASES IN MULTIMOLECULAR LAYERS , 1938 .

[72]  Mingzhen Wei,et al.  Rock characterization of Fayetteville shale gas plays , 2013 .

[73]  Xiong Jian,et al.  Experimental study on the pore structure characteristics of the Upper Ordovician Wufeng Formation shale in the southwest portion of the Sichuan Basin, China , 2015 .

[74]  Wong,et al.  Surface roughening and the fractal nature of rocks. , 1986, Physical review letters.

[75]  M. Prasad,et al.  Porosity evolution in oil-prone source rocks , 2014 .

[76]  S. J. Gregg,et al.  Adsorption Surface Area and Porosity , 1967 .

[77]  Andrew C. Aplin,et al.  Mudstone diversity: Origin and implications for source, seal, and reservoir properties in petroleum systems , 2011 .

[78]  Fang Hao,et al.  Mechanisms of shale gas storage: Implications for shale gas exploration in China , 2013 .

[79]  D. Mccarty,et al.  Influence of Mechanical Compaction and Clay Mineral Diagenesis on the Microfabric and Pore-Scale Properties of Deep-Water Gulf of Mexico Mudstones , 2006 .

[80]  Liu Yingjie,et al.  Effects of composition and pore structure on the reservoir gas capacity of Carboniferous shale from Qaidam Basin, China , 2015 .

[81]  H. Jacob Classification, structure, genesis and practical importance of natural solid oil bitumen (“migrabitumen”) , 1989 .

[82]  Leonard H. Cohan,et al.  Sorption Hysteresis and the Vapor Pressure of Concave Surfaces , 1938 .

[83]  Junhua Fang,et al.  Shale gas reservoir characterisation: A typical case in the southern Sichuan Basin of China , 2011 .

[84]  T. Guo,et al.  Evidence for multiple stages of oil cracking and thermochemical sulfate reduction in the Puguang gas field, Sichuan Basin, China , 2008 .

[85]  Stephen C. Ruppel,et al.  Spectrum of pore types and networks in mudrocks and a descriptive classification for matrix-related mudrock pores , 2012 .

[86]  John J. Valenza,et al.  Geochemical controls on shale microstructure , 2013 .