Abstract
Adsorption characteristics and thermodynamic properties of organic matter are the basis for investigating gas storage and transport mechanisms. In this work, a realistic molecular model of organic matter in Chinese Silurian shale was constructed based on experimental data. The fluid distribution and thermodynamic properties were computed using the molecular dynamics simulations, while the adsorption isotherms and the isosteric heat for methane under different temperatures were simulated with the grand canonical Monte Carlo method. Results show that water molecules aggregate into small clusters in the lower density regions; carbon dioxide molecules are located closer to the oxygen groups, while nitrogen molecules and methane molecules are closer to the sulfur groups and nitrogen groups. The adsorption capacity of methane decreases with increasing temperature. The isosteric heat decreases in the beginning and then increases as the adsorption proceeds. This observation suggests that methane molecules are preferably adsorbed on the high-energy adsorption sites of the energetically heterogeneous surface. The later increase of isosteric heat is because of the increasing contribution of adsorbate–adsorbate interaction to adsorption enthalpy. The developed molecular model of organic matter can serve as a starting point for further theoretical investigations of the Silurian organic matter at molecular scale.
Copyright 2017, Shaanxi Petroleum Society.
This paper was prepared for presentation at the 2017 International Field Exploration and Development Conference in Chengdu, China, 21–22 September 2017.
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References
Li SY, Yue CT (2003) Study of pyrolysis kinetics of oil shale. Fuel 82(3):337–342
Wei ZB, Gao XX, Zhang DJ, Da J (2005) Assessment of thermal evolution of kerogen geopolymers with their structural parameters measured by solid-state 13C NMR spectroscopy. Energy Fuel 19(1):240–250
Zeng Y, Wu C (2007) Raman and infrared spectroscopic study of kerogen treated at elevated temperatures and pressures. Fuel 86(7):1192–1200
Ru X, Cheng ZQ, Song LH, Wang HY, Li JF (2012) Experimental and computational studies on the average molecular structure of Chinese Huadian oil shale kerogen. J Mol Struct 1030:10–18
Collell J, Ungerer P, Galliero G, Yiannourakou M, Montel F, Pujol M (2014) Molecular simulation of bulk organic matter in type II shales in the middle of the oil formation window. Energy Fuel 28(12):7457–7466
Zhou B, Xu R, Jiang P (2016) Novel molecular simulation process design of adsorption in realistic shale kerogen spherical pores. Fuel 180:718–726
Zhang DG (2015) Characteristics of the Organic-rich Shales of the Wufeng-Longmaxi Group in Wulong, Southeastern Sichuan. Master thesis, Chengdu University of Technology
Feng ZQ, Liu D, Huang SP, Wu W, Dong DZ, Peng WL, Han EX (2016) Carbon isotopic composition of shale gas in the Silurian Longmaxi Formation of the Changning area, Sichuan Basin. Petrol Explor Dev 43(5):769–777
Kelemen SR, Afeworki M, Gorbaty ML, Sansone M, Kwiatek PJ, Walters CC, Freund H, Siskin M (2007) Direct characterization of kerogen by X-ray and solid-state 13C nuclear magnetic resonance methods. Energy Fuel 21(3):1548–1561
Yen TF (1979) Structural difference between petroleum and coal-derived asphaltenes. Div Pet Chem Am Chem Soc 24(4):901–909
Ungerer P, Collell J, Yiannourakou M (2015) Molecular modeling of the volumetric and thermodynamic properties of kerogen: Influence of organic type and maturity. Energy Fuel 29(1):91–105
Lagache M, Ungerer P, Boutin A, Fuchs AH (2001) Prediction of thermodynamic derivative properties of fluids by Monte Carlo simulation. Phys Chem Chem Phys 3(19):4333–4339
Sui H, Yao J (2016) Effect of surface chemistry for CH4/CO2 adsorption in kerogen: a molecular simulation study. J Nat Gas Sci Eng 31:738–746
Pan H, Ritter JA, Balbuena PB (1998) Examination of the approximations used in determining the isosteric heat of adsorption from the Clausius-Clapeyron equation. Langmuir 14(21):6323–6327
Jarvie DM, Claxton BL, Henk F, Breyer JT (2001) Oil and shale gas from the Barnett shale, Ft. Worth Basin, Texas, In: AAPG Annual Meet Program, 2001, 10, A100
Huang L, Ning Z, Wang Q, Qi R, Li J, Zeng Y, Ye H, Qin H (2017) Thermodynamic and structural characterization of bulk organic matter in Chinese Silurian shale: experimental and molecular modeling studies. Energy Fuel. https://doi.org/10.1021/acs.energyfuels.7b00132
Fu XD, Qiu NS, Qin JZ, Tenger, Liu WH, Wang XF (2013) Content distribution and isotopic composition characteristics of sulfur in marine source rocks in Middle-Upper Yangtze region. Pet Geol. Exper 35:545–551
Gao B (2015) Geochemical characteristics of shale gas from Lower Silurian Longmaxi Formation in the Sichuan Basin and its geological significance. Nat Gas Geosci 26:1173–1182
Okiongbo KS, Aplin AC, Larter SR (2005) Changes in type II kerogen density as a function of maturity: evidence from the Kimmeridge Clay Formation. Energy Fuel 19(6):2495–2499
Ahmadov R, Vanorio T, Mavko G (2009) Confocal laser scanning and atomic-force microscopy in estimation of elastic properties of the organic-rich Bazhenov Formation. Lead Edge 28(1):18–23
Hu H (2014) Methane adsorption comparison of different thermal maturity kerogens in shale gas system. Chin J Geochem 33(4):425–430
Himeno S, Komatsu T, Fujita S (2005) High-pressure adsorption equilibria of methane and carbon dioxide on several activated carbons. J Chem Eng Data 50(2):369–376
Acknowledgements
We acknowledge the financial support of the National Natural Science Foundation of China (Grant No. 51504265) and the Science Foundation for the Excellent Youth Scholars of China University of Petroleum (Beijing) (Grant No.2462015YQ0223).
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Huang, L. et al. (2019). Molecular Simulation of Adsorption and Thermodynamic Properties of Organic Matter in Silurian Shale of Sichuan Basin, China. In: Qu, Z., Lin, J. (eds) Proceedings of the International Field Exploration and Development Conference 2017. Springer Series in Geomechanics and Geoengineering. Springer, Singapore. https://doi.org/10.1007/978-981-10-7560-5_139
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DOI: https://doi.org/10.1007/978-981-10-7560-5_139
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