Lightening of shale oil using high-temperature supercritical CO2: An experimental study
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Abstract
This paper investigates the influence of reaction atmosphere and operation parameters of the lightening process under high temperature and high pressure on high-viscosity shale oil using an experimental approach. Two types of experiments were implemented, one involving a thermogravimetric analyzer and another using an autoclave to carry out the lightening process. By these two kinds of experiments, the effects of reaction atmosphere and operation parameters on the lightening efficiency were clarified. As for the reaction atmosphere, the effects of CO2, N2 and air were separately evaluated. As for the operation parameters, the effects of heating rate and formation rock were investigated. The results indicate that under a CO2 atmosphere, the lightening reaction is more intense than that under the other two gas phases, and it gains the highest reaction rate. Part of the minerals in the formation rock can be treated as catalyst in the shale oil lightening process. With the formation rock being present, the reaction rate increases significantly and higher contents of light components are obtained in both the lightened shale oil and gas phase. For the kinetic parameters in the lightening process, proportional relationships between the kinetic parameters and heating rates under CO2 atmosphere with and without formation rock were identified. The findings of this study can provide guidance for enhancing high-viscosity shale oil using an in-situ lightening process.
Document Type: Original article
Cited as: Zhou, X., Li, H., Zeng, F., Yu, C., Ouyang, H., Jiang, Q. Lightening of shale oil using high-temperature supercritical CO2: An experimental study. Advances in Geo-Energy Research, 2025, 16(2): 99-113. https://doi.org/10.46690/ager.2025.05.03
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Al-Harahsheh, M., Al-Ayed, O., Robinson, J., et al. Effect of demineralization and heating rate on the pyrolysis kinetics of Jordanian oil shales. Fuel Processing Technology, 2011, 92(9): 1805-1811.
Alvarez, E., Marroquín, G., Trejo, F., et al. Pyrolysis kinetics of atmospheric residue and its SARA fractions. Fuel, 2011, 90(12): 3602-3607.
Bagci, S., Kok, M. V. Combustion reaction kinetics studies of Turkish crude oils. Energy & Fuels, 2004, 18(5): 1472-1481.
Belgrave, J. D. M., Moore, R. G., Ursenbach, M. G., et al. A comprehensive approach to in-situ combustion modeling. SPE Advanced Technology Series, 1993, 1(1): 98-107.
Borrego, A. G., Prado, J. G., Fuente, E., et al. Pyrolytic behaviour of Spanish oil shales and their kerogens. Journal of Analytical and Applied Pyrolysis, 2000, 56(1): 1-21.
Chang, Z., Chu, M. The chemical composition and pyrolysis characteristics of thermal bitumen derived from pyrolyzing huadian oil shale, China. Oil Shale, 2019, 36(1): 62-75.
Chang, Z., Chu, M., Zhang, C., et al. Investigation of the effect of selected transition metal salts on the pyrolysis of Huadian oil shale, China. Oil Shale, 2017, 34(4): 354-367.
Chang, Z., Chu, M., Zhang, C., et al. Comparison of pyrolysis characteristics of two Chinese oil shales based on the migration and conversion of organic carbon. Carbon Resources Conversion, 2018, 1(3): 209-217.
Coats, A. W., Redfern, J. P. Kinetic parameters from thermo-gravimetric data. Nature, 1964, 201: 68-69.
Eletskii, P. M., Mironenko, O. O., Kukushkin, R. G., et al. Catalytic steam cracking of heavy oil feedstocks: A review. Catalysis in Industry, 2018, 10(3): 185-201.
Feng, Q., Xu, S., Xing, X., et al. Advances and challenges in shale oil development: A critical review. Advances in Geo-Energy Research, 2020, 4(4): 406-418.
Gai, R., Jin, L., Zhang, J., et al. Effect of inherent and additional pyrite on the pyrolysis behavior of oil shale. Journal of Analytical and Applied Pyrolysis, 2014, 105: 342-347.
Gao, Y., Li, Q., He, X., et al. Quantitative evaluation of shale-oil recovery during CO2 huff-n-puff at different pore scales. Energy & Fuels, 2021, 35(20): 16607-16616.
Gong, Y., Gu, Y. Miscible CO2 simultaneous water-and-gas (CO2-SWAG) injection in the Bakken formation. Energy & Fuels, 2015a, 29(9): 5655-5665.
Gong, Y., Gu, Y. Experimental study of water and CO2 f looding in the tight main pay zone and vuggy residual oil zone of a carbonate reservoir. Energy & Fuels, 2015b, 29(10): 6213-6223.
Gu, J., Deng, S., Sun, Y., et al. Pyrolysis behavior and pyrolysate characteristics of Huadian oil shale kerogen catalyzed by nickel-modified montmorillonite. Advances in Geo-Energy Research, 2024, 11(3): 168-180.
Guo, Q., Hou, L., Wang, J., et al. An evaluation method of resource potential of in-situ converted shale oil and its application. Acta Prtrolei Sinica, 2022, 43(12): 1750-1757. (in Chinese)
Guo, W., Deng, S., Sun, Y. Recent advances on shale oil and gas exploration and development technologies. Advances in Geo-Energy Research, 2024a, 11(2): 81-87.
Guo, W., Sun, Y., Li, Q., et al. Oil shale in-situ conversion technology triggered by topochemical reaction method and pilot test project in Songliao Basin. Acta Prtrolei Sinica, 2024b, 45(7): 1104-1121. (in Chinese)
Hao, J., Feng, W., Qiao, Y., et al. Thermal cracking behaviors and products distribution of oil sand bitumen by TG-FTIR and Py-GC/TOF-MS. Energy Conversion and Management, 2017, 151: 227-239.
He, L., Ma, Y., Yue, C., et al. The heating performance and kinetic behaviour of oil shale during microwave pyrolysis. Energy, 2022, 244: 123021.
Jaber, J. O., Probert, S. D. Pyrolysis and gasification kinetics of Jordanian oil-shales. Applied Energy, 1999, 63: 269-286.
Jaber, J. O., Probert, S. D., Williams, P. T., et al. Gasification potential and kinetics of Jordanian oil shales using CO2 as the reactant gas. Energy Sources, 2000, 22(6): 573-585.
Jia, B., Tsau, J. S., Barati, R. A review of the current progress of CO2 injection EOR and carbon storage in shale oil reservoirs. Fuel, 2019, 236: 404-427.
Jiang, H., Deng, S., Chen, J., et al. Effect of hydrothermal pretreatment on product distribution and characteristics of oil produced by the pyrolysis of Huadian oil shale. Energy Conversion and Management, 2017, 143: 505-512.
Jiang, H., Liu, S., Wang, J., et al. Study on evolution mechanism of the pyrolysis of chang 7 oil shale from Ordos basin in China. Energy, 2023, 272: 127097.
Jin, L., Hawthorne, S., Sorensen, J., et al. Advancing CO2 enhanced oil recovery and storage in unconventional oil play–Experimental studies on Bakken shales. Applied Energy, 2017, 208: 171-183.
Kang, Z., Zhao, Y., Yang, D. Review of oil shale in-situ conversion technology. Applied Energy, 2020, 269: 115121.
Kapadia, P. R., Wang, J., Kallos, M. S., et al. Practical process design for in situ gasification of bitumen. Applied Energy, 2013, 107: 281-296.
Kim, D. W., Lee, C. H. Efficient conversion of extra-heavy oil into distillates using tetralin/activated carbon in a continuous reactor at elevated temperatures. Journal of Analytical and Applied Pyrolysis, 2019, 140: 245-254.
Kök, M. V., Karacan, O. Pyrolysis analysis and kinetics of crude oils. Journal of Thermal Analysis and Calorimetry, 1998, 52: 781-788.
Lan, X., Luo, W., Song, Y., et al. Effect of the temperature on the characteristics of retorting products obtained by Yaojie oil shale pyrolysis. Energy & Fuels, 2015, 29(12): 7800-7806.
Liu, D., Hou, J., Luan, H., et al. Coke yield prediction model for pyrolysis and oxidation processes of low-asphaltene heavy oil. Energy & Fuels, 2019, 33(7): 6205-6214.
Liu, Z., Meng, Q., Dong, Q., et al. Characteristics and resource potential of oil shale in China. Oil Shale, 2017, 34(1): 15-41.
Maniscalco, M., Mistretta, L., Iannotta, P., et al. Experimental study of the pyrolysis of waste bitumen for oil production. Journal of the Energy Institute, 2020, 93(6): 2456-2463.
Meng, X., Bian, J., Li, J., et al. Porous aluminosilicates catalysts for low and medium matured shale oil in situ upgrading. Energy Science and Engineering, 2020, 8(8): 2859-2867.
Moine, E. C, Groune, K., El Hamidi, A., et al. Multistep process kinetics of the non-isothermal pyrolysis of Moroccan Rif oil shale. Energy, 2016, 115: 931-941.
Mozaffari, S., Järvik, O., Baird, Z. S. Effect of N2 and CO2 on shale oil from pyrolysis of Estonian oil shale. International Journal of Coal Preparation and Utilization, 2022, 42(10): 2908-2922.
Murugan, P., Mani, T., Mahinpey, N., et al. Pyrolysis kinetics of Athabasca bitumen using a TGA under the influence of reservoir sand. Canadian Journal of Chemical Engineering, 2012, 90(2): 315-319.
Ogbonnaya, O., Suriamin, F., Shiau, B., et al. Enhanced oil recovery formulations for liquid-rich shale reservoirs. Fuel, 2024, 368: 131573.
Pan, L., Dai, F., Huang, J., et al. Study of the effect of mineral matters on the thermal decomposition of Jimsar oil shale using TG-MS. Thermochimica Acta, 2016, 627-629: 31-38.
Pan, L., Dai, F., Li, G., et al. A TGA/DTA-MS investigation to the influence of process conditions on the pyrolysis of Jimsar oil shale. Energy, 2015, 86: 749-757.
Pu, W., Gong, X., Chen, Y., et al. Non-isothermal pyrolysis and combustion kinetics of heavy oil and its low temperature oxidation products by thermal analyses. Petroleum Science and Technology, 2020, 38(4): 398-404.
Quan, H., Xing, L. The effect of hydrogen bonds between f low improvers with asphaltene for heavy crude oil. Fuel, 2019, 237: 276-282.
Raja, M. A., Zhao, Y., Zhang, X., et al. Practices for modeling oil shale pyrolysis and kinetics. Reviews in Chemical Engineering, 2017, 34(1): 21-42.
Ren, Y., Freitag, N. P., Mahinpey, N. A simple kinetic model for coke combustion during an in situ combustion (ISC) process. Journal of Canadian Petroleum Technology, 2007, 46(4): 47-52.
Ren, Y., Wei, B., Ji, B., et al. Pore-scale probing CO2 huff-n-puff in extracting shale oil from different types of pores using online T1-T2 nuclear magnetic resonance spectroscopy. Petroleum Science, 2024, 21(6): 4119-4129.
Shabib-Asl, A., Plaksina, T., Moradi, B. Evaluation of nanopore confinement during CO2 huff and puff pro cess in liquid-rich shale formations. Computational Geo-sciences, 2020, 24(3): 1163-1178.
Syed, S., Qudaih, R., Talab, I., et al. Kinetics of pyrolysis and combustion of oil shale sample from thermogravimetric data. Fuel, 2011, 90: 1631-1637.
Tang, L., Yan, Y., Meng, Y., et al. CO2 gasification and pyrolysis reactivity evaluation of oil shale. Energy Procedia, 2019, 158: 1694-1699.
Wang, L., Gao, C., Xiong, R., et al. Development review and the prospect of oil shale in-situ catalysis conversion technology. Petroleum Science, 2024, 21(2): 1385-1395.
Williams, P. T., Ahmad, N. Investigation of oil-shale pyrolysis processing conditions using thermogravimetric analysis. Applied Energy, 2000, 66(2): 113-133.
Xie, F., Wang, Z., Lin, W., et al. Study on thermal conversion of huadian oil shale under N2 and CO2 atmospheres. Oil Shale, 2010, 27(4): 309-320.
Yang, Q., Zhang, X., Xu, S., et al. Low-temperature cocurrent oxidizing pyrolysis of oil shale: Study on the physicochemical properties, reactivity and exothermic characters of semi-coke as heat generation donor. Jour nal of Petroleum Science and Engineering, 2022a, 216: 110726.
Yang, S., Huang, S., Jiang, Q., et al. Experimental study of hydrogen generation from in-situ heavy oil gasification. Fuel, 2022b, 313: 122640.
Yuan, C., Emelianov, D. A., Varfolomeev, M. A. Oxidation behavior and kinetics of light, medium, and heavy crude oils characterized by thermogravimetry coupled with fourier transform infrared spectroscopy. Energy & Fuels, 2018, 32(4): 5571-5580.
Yu, H., Xu, H., Fu, W., et al. Extraction of shale oil with supercritical CO2: Effects of number of fractures and injection pressure. Fuel, 2021, 285: 118977.
Zhang, C., Xu, T., Shi, H., et al. Physicochemical and pyrolysis properties of SARA fractions separated from asphalt binder. Journal of Thermal Analysis and Calorimetry, 2015, 122(1): 241-249.
Zhao, Q., Dong, Y., Zheng, L., et al. Sub- and supercritical water conversion of organic-rich shale with low-maturity for oil and gas generation: Using Chang 7 shale as an example. Sustainable Energy and Fuels, 2022, 7(1): 155-163.
Zhao, S., Lü, X., Li, Q., et al. Thermal-fluid coupling analysis of oil shale pyrolysis and displacement by heat-carrying supercritical carbon dioxide. Chemical Engineering Journal, 2020, 394: 125037.
Zhao, W., Guan, M., Liu, W., et al. Low-to-medium maturity lacustrine shale oil resource and in-situ conversion process technology: Recent advances and challenges. Advances in Geo-Energy Research, 2024, 12(2): 81-88. Zhao, W., Hu, S., Hou, L. Connotation and strategic role of in-situ conversion processing of shale oil underground in the onshore China. Petroleum Exploration and Development, 2018, 45(4): 563-572.
Zhao, X., Sang, Q., Li, Y., et al. CO2-kerogen interaction dominated CO2-oil counter-current diffusion and its effect on ad-/absorbed oil recovery and CO2 sequestration in shale. Fuel, 2021, 294: 120500.
Zhou, J., Yang, K., Zhou, L., et al. Microstructure and mechanical properties alterations in shale treated via CO2/CO2-water exposure. Journal of Petroleum Science and Engineering, 2021, 196: 108088.
Zhou, X., Li, X., Shen, D., et al. CO2 huff-n-puff process to enhance heavy oil recovery and CO2 storage: An integration study. Energy, 2022, 239: 122003.
DOI: https://doi.org/10.46690/ager.2025.05.03
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