Kerogen Swelling and Confinement: Its implication on Fluid Thermodynamic Properties in Shales

Type I kerogen was isolated from Green River Shale and characterized using SEM, TGA, DSC, and nitrogen adsorption. The swelling behavior of this kerogen with decane was analyzed using traditional test-tube swelling experiment and Dynamic Light Scattering. The TGA and DSC were used to analyze the thermodynamic behavior of decane that was sorbed in the kerogen and show that kerogen suppresses the boiling point of decane due to the effect of confinement. However, the suppression is larger when oil (a multicomponent mixture) was used, possibly due to the combined effect of differential uptake of components by kerogen (kerogen prefers and sorbs polars and aromatics more than saturates, leading to splitting of oil into a sorbed and a free phase) and confinement in nano pores. Test-tube swelling, TGA, and DSC experiments were also performed on pyridine(polar-aromatic)-swelled kerogen. The combined and individual contributions from the two effects (the effect of confinement and differential uptake of hydrocarbon components) on properties of liquid in contact with kerogen, are studied in this work. Molecular Dynamics (MD) simulations revealed the variation in the swelling of type II kerogen in the presence of same amount of different liquids (differential swelling of kerogen).

[1]  K. Gubbins,et al.  Phase separation in confined systems , 1999 .

[2]  J. Larsen,et al.  Changes in the Macromolecular Structure of a Type I Kerogen during Maturation , 1997 .

[3]  Marcus D. Hanwell,et al.  Avogadro: an advanced semantic chemical editor, visualization, and analysis platform , 2012, Journal of Cheminformatics.

[4]  E. Barrett,et al.  The Determination of Pore Volume and Area Distributions in Porous Substances. II. Comparison between Nitrogen Isotherm and Mercury Porosimeter Methods , 1951 .

[5]  M. Sahimi,et al.  Adsorption-induced swelling of porous media , 2017 .

[6]  J. Larsen,et al.  An initial comparison of the interactions of Type I and III kerogens with organic liquids , 1997 .

[7]  M. Deo,et al.  Effect of the presence of organic matter on bubble points of oils in shales , 2017 .

[8]  Holger Gohlke,et al.  The Amber biomolecular simulation programs , 2005, J. Comput. Chem..

[9]  N. Savest,et al.  Interaction of Estonian kukersite with organic solvents : A volumetric swelling and molecular simulation study , 2007 .

[10]  Joan-Emma Shea,et al.  Moltemplate a Coarse-Grained Model Assembly Tool , 2013 .

[11]  F. Pinto,et al.  Effect of coal pre-treatment with swelling solvents on coal liquefaction , 1999 .

[12]  L. Ballice Solvent swelling studies of Göynük (Kerogen Type-I) and Beypazarı oil shales (Kerogen Type-II)☆ ☆ , 2003 .

[13]  M. Sahimi,et al.  Three-Dimensional Stochastic Characterization of Shale SEM Images , 2015, Transport in Porous Media.

[14]  U. Ritter Solubility of petroleum compounds in kerogen: implications for petroleum expulsion , 2003 .

[15]  K Schulten,et al.  VMD: visual molecular dynamics. , 1996, Journal of molecular graphics.

[16]  J. Gasteiger,et al.  ITERATIVE PARTIAL EQUALIZATION OF ORBITAL ELECTRONEGATIVITY – A RAPID ACCESS TO ATOMIC CHARGES , 1980 .

[17]  Xiangfang Li,et al.  Molecular simulation of adsorption and thermodynamic properties on type II kerogen: Influence of maturity and moisture content , 2017 .

[18]  N. Savest,et al.  SOLVENT SWELLING OF DICTYONEMA OIL SHALE , 2010 .

[19]  Shuangfang Lu,et al.  The Research Progress on the Occurrence Mechanism of Detained Hydrocarbon , 2015 .

[20]  E. Barrett,et al.  (CONTRIBUTION FROM THE MULTIPLE FELLOWSHIP OF BAUGH AND SONS COMPANY, MELLOX INSTITUTE) The Determination of Pore Volume and Area Distributions in Porous Substances. I. Computations from Nitrogen Isotherms , 1951 .

[21]  Jodie L. Lutkenhaus,et al.  Effect of confinement on the bubble points of hydrocarbons in nanoporous media , 2016 .

[22]  V. A. Kuz,et al.  Critical shift of a confined fluid in a nanopore , 2004 .

[23]  E. Suuberg,et al.  Kukersite oil shale kerogen solvent swelling in binary mixtures , 2013 .

[24]  Yifeng Wang,et al.  Nanostructural control of methane release in kerogen and its implications to wellbore production decline , 2016, Scientific Reports.

[25]  P. Ungerer,et al.  Molecular Simulation of Bulk Organic Matter in Type II Shales in the Middle of the Oil Formation Window , 2014 .

[26]  N. Nagarajan,et al.  Critical Role of Rock and Fluid - Impact on Reservoir Performance on Unconventional Shale Reservoirs , 2013 .

[27]  Janet E. Jones On the determination of molecular fields. —II. From the equation of state of a gas , 1924 .

[28]  M. Deo,et al.  The effect of kerogen-hydrocarbons interaction on the PVT properties in liquid rich shale plays , 2015 .

[29]  J. Kovac,et al.  A rapid and convenient method for measuring the swelling of coals by solvents , 1984 .

[30]  E. Salmon,et al.  Molecular characterization of Type I kerogen from the Green River Formation using advanced NMR techniques in combination with electrospray ionization/ultrahigh resolution mass spectrometry , 2011 .

[31]  Junmei Wang,et al.  Development and testing of a general amber force field , 2004, J. Comput. Chem..

[32]  G. Moridis,et al.  Effect of Confinement on Pressure/Volume/Temperature Properties of Hydrocarbons in Shale Reservoirs , 2016 .

[33]  Palash Panja,et al.  Unusual behavior of produced gas oil ratio in low permeability fractured reservoirs , 2016 .

[34]  J. Larsen,et al.  Solvent swelling studies of green river kerogen , 1994 .

[35]  Kenneth S. Okiongbo,et al.  Changes in Type II Kerogen Density as a Function of Maturity: Evidence from the Kimmeridge Clay Formation , 2005 .

[36]  G. L. Salmon,et al.  Density gradient centrifugation: Application to the separation of macerals of type I, II, and III sedimentary organic matter , 1994 .

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

[38]  Jayant K. Singh,et al.  Vapor-Liquid Phase Coexistence, Critical Properties, and Surface Tension of Confined Alkanes , 2009 .

[39]  Deniz Ertas,et al.  Petroleum Expulsion Part 2. Organic Matter Type and Maturity Effects on Kerogen Swelling by Solvents and Thermodynamic Parameters for Kerogen from Regular Solution Theory , 2006 .

[40]  Deniz Ertas,et al.  Petroleum Expulsion Part 1. Theory of Kerogen Swelling in Multicomponent Solvents , 2006 .

[41]  E. Suuberg,et al.  SOLVENT SWELLING OF KUKERSITE OIL SHALE MACROMOLECULAR ORGANIC MATTER IN BINARY MIXTURES: IMPACT OF SPECIFICALLY INTERACTING SOLVENTS , 2014 .

[42]  Pejman Tahmasebi,et al.  Stochastic shale permeability matching: Three-dimensional characterization and modeling , 2016 .

[43]  Pejman Tahmasebi,et al.  Multiscale and multiresolution modeling of shales and their flow and morphological properties , 2015, Scientific Reports.

[44]  Erdal Ozkan,et al.  Experimental Study and Modeling of the Effect of Nanoconfinement on Hydrocarbon Phase Behavior in Unconventional Reservoirs , 2014 .

[45]  H. A. Lorentz Ueber die Anwendung des Satzes vom Virial in der kinetischen Theorie der Gase , 1881 .

[46]  K. Marfurt,et al.  Current Workflows for Shale Gas Reservoir Characterization , 2013 .

[47]  R. Reimert,et al.  Effect of solvent swelling on pyrolysis of kerogen (type-I) isolated from Göynük oil shale (Turkey) , 2009 .

[48]  Pejman Tahmasebi,et al.  Multiscale study for stochastic characterization of shale samples , 2016 .

[49]  Howard Rosenbaum,et al.  Effects of reading proficiency on embedded stem priming in primary school children , 2021 .

[50]  G. Moridis,et al.  Effect of Confinement on PVT Properties of Hydrocarbons in Shale Reservoirs , 2014 .

[51]  Sugata P. Tan,et al.  A review on capillary condensation in nanoporous media: Implications for hydrocarbon recovery from tight reservoirs , 2016 .

[52]  A. V. Kiselev Non-specific and specific interactions of molecules of different electronic structures with solid surfaces , 1965 .

[53]  Steve Plimpton,et al.  Fast parallel algorithms for short-range molecular dynamics , 1993 .

[54]  P. Ungerer,et al.  Molecular Modeling of the Volumetric and Thermodynamic Properties of Kerogen: Influence of Organic Type and Maturity , 2015 .

[55]  J. Larsen,et al.  Kerogen chemistry 5. Anhydride formation in, solvent swelling of, and loss of organics on demineralization of Kimmeridge shales , 2008 .

[56]  Zhangxin Chen,et al.  Phase Equilibria of Confined Fluids in Nanopores of Tight and Shale Rocks Considering the Effect of Capillary Pressure and Adsorption Film , 2016 .

[57]  Milind Deo,et al.  Experimental and Molecular Modeling Study of Bubble Points of Hydrocarbon Mixtures in Nanoporous Media , 2017 .

[58]  A. Firoozabadi,et al.  Flow of methane in shale nanopores at low and high pressure by molecular dynamics simulations. , 2015, The Journal of chemical physics.

[59]  V. Strezov,et al.  Thermo-swelling behavior of Kukersite oil shale , 2015, Journal of Thermal Analysis and Calorimetry.