Investigation of the transformation of organic matter of carbonate deposits of the Semiluksky-Mendymsky horizon under hydrothermal conditions

Abstract

The paper presents the results of studies on the transformation of the organic matter of siliceous-clayey carbonate rocks of the Semiluksko-Mendymsky horizon of the Romashkino oil field in a hydrothermal fluid for an hour (with a water-to-rock ratio of 33) at 340°C and 380°C and pressures of 17 and 20 MPa. As a result of hydrothermal treatment, at 340°C and 17 MPa, based on nitrogen porosimetry and electron microscopy data, transformations of rock-forming minerals in the rock are observed. They lead to an increase in the volume and average diameter of mesopores in it and the formation of micropores, as well, which improve its filtration properties. At the same time, the amount of kerogen in the composition of the organic matter decreases and the yield of the petroleum hydrocarbon extract increases, in which, according to the SARA analysis, the content of asphaltenes increases and the content of resins, aromatic and saturated hydrocarbons decreases. In the composition of aroatic hydrocarbons, the proportion of alkyltrimethylbenzenes and dibenzothiophenes increases, phenanthrene homologues appear, and in the composition of saturated hydrocarbons, the amount of iso-structure alkanes decreases relative to the content of linear alkanes. Raising the temperature and pressure of the hydrothermal fluid to 380°С and 20 MPa increases the degree of kerogen conversion from 12.4% to 23.6%. At the same time, changes occurring in the component composition of petroleum hydrocarbon extracts remains similar to the experiments carried out at 340°C and 17 MPa; the content of naphthalenes decreases, the content of dibenzothiophenes increases and C₁₁-C₁₇, C₁₉-C₂₂ alkyltrimethylbenzenes appear. According to IR spectroscopy, with increasing temperature and pressure of the hydrothermal fluid the intensity of the absorption bands of the aromatic ring, aliphatic fragments, and oxygen-containing groups increases in resins; the structural-group composition of asphaltenes changes little: aromaticity and the content of condensed structures slightly increase. The revealed distinctive features in the composition of organic matter after hydrothermal impact on siliceous-clayey carbonate rocks confirm the concept of staged destruction of kerogen, when large structural heteroatomic blocks (asphaltenes) are split off at the initial stages. Changes occurring in the composition of petroleum hydrocarbon extracts indicate their involvement in the process of hydrothermal transformation of organic matter of siliceous-clayey carmbonate rocks with the predominant reactions of dehydrogenation of naphthenic compounds and oxidative polycondensation of aromatic structures. The data of electron microscopy and nitrogen porosimetry of rocks after hydrothermal exposure at 380°С and 20 MPa indicate a deterioration in their reservoir properties. The most optimal thermobaric conditions of the hydrothermal fluid for the generation of petroleum hydrocarbons from kerogen of siliceous-clayey carbonate deposits of the Semiluksko-Mendymsky horizon of the Romashkino field, which improve their reservoir properties, are 340°С and 17 MPa; with implication of hard-to-recover heavy hydrocarbon resources and well-established catalytic methods of in-situ conversion.

Keywords

Carbonate deposits / Organic matter / Hydrothermal fluid / Mobile hydrocarbons

Funding

The research was conducted out of the Russian Science Foundation Grant No. 18-77-10023, https://rscf.ru/project/18-77-10023/

The investigation was conducted using equipment of the Center of Complex Program «Nanomaterials and Nanotechnologies» of the Kazan National Research Technological University.

Declaration of competing interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

References

[1] O.N. Fedyaeva, V.R. Antipenko, A.A. Vostrikov, Heavy oil upgrading at oxidation of activated carbon by supercritical water-oxygen fluid, J. Supercrit. Fluids 126 (2017) 55-64, https://doi.org/10.1016/J.SUPFLU.2017.02.016.

[2] P. Arcelus-Arrillaga, K. Hellgardt, M. Millan, Effect of process conditions on the hydrothermal partial oxidation of phenanthrene as a heavy oil model structure, Fuel 209 (2017) 434-441, https://doi.org/10.1016/J.FUEL.2017.08.005.

[3] P. Crawford, K. Biglarbigi, A. Dammer, E. Knaus, Advances in World oil-shale production technologies, in: Proc -SPE Annu Tech Conf Exhib, vol. 6, 2008, pp. 4101-4111, https://doi.org/10.2118/116570-MS.

[4] Z. Nasyrova, A. Aliev, S. Petrov, A. Safiulina, I. Mukhamatdinov, The catalytic effects of carbonate minerals on characteristics of heavy oil in hydrothermal reactions, Petrol. Sci. Technol. 36 (2018) 1439-1445, https://doi.org/10.1080/10916466.2018.1484767.

[5] A.G. Safiulina, D.A. Ibragimova, L.R. Baibekova, R.R. Soldatova, S.M. Petrov, N.Y. Bashkirtseva, Modeling of paraffin wax deposition process in poorly extractable hydrocarbon stock, Chem. Technol. Fuels Oils 53 (2018) 897-904, https://doi.org/10.1007/s10553-018-0879-x.

[6] Z. Liu, Q. Meng, Q. Dong, J. Zhu, W. Guo, S. Ye, et al., Characteristics and resource potential of oil shale in China, Oil Shale 34 (2017) 15-41, https://doi.org/10.3176/OIL.2017.1.02.

[7] P. Johnston, Arctic energy resources: security and environmental implications, J. Strat. Secur. 5 (2012), https://doi.org/10.5038/1944-0472.5.3.2.

[8] R.S. Khisamov, V.G. Bazarevskaya, T.I. Tarasova, O.V. Mikhailova, S.N. Mikhailov, Geochemical evidence for petroleum potential of Domanic deposits in the Republic of Tatarstan (Russian), in: Neft Khozyaystvo -Oil Ind 2016, 2016, pp. 10-13.

[9] Y.M. Ganeeva, E.S. Okhotnikova, E.E. Barskaya, T.N. Yusupova, L.E. Foss, O.C. Sotnikov, et al., The composition of organic matter of Domanic deposit of the Bavly field, Petrol. Sci. Technol. 37 (2018) 317-322, https://doi.org/10.1080/10916466.2018.1542445.

[10] A.N. Mikhailova, G.P. Kayukova, A.V. Vakhin, A.A. Eskin, Vandyukova II, Composition features of hydrocarbons and rocks of Domanic deposits of different oil fields in the Tatarstan territory, Petrol. Sci. Technol. 37 (2019) 374-381, https://doi.org/10.1080/10916466.2018.1547757.

[11] G.P. Kayukova, A.N. Mikhailova, N.M. Khasanova, V.P. Morozov, A.V. Vakhin, N.A. Nazimov, et al., Influence of hydrothermal and pyrolysis processes on the transformation of organic matter of dense low-permeability rocks from domanic formations of the Romashkino oil field, Geofluids 8 (2018) 1-14, https://doi.org/10.1155/2018/9730642.

[12] D.A. Bushnev, N.S. Burdel’naya, O.V. Valyaeva, A.A. Derevesnikova, Geochemistry of late Devonian oils of the Timan-Pechora basin, Russ. Geol. Geophys. 58 (2017) 332-342, https://doi.org/10.1016/J.RGG.2016.09.009.

[13] R.K. Muslimov, I.N. Plotnikova, The main problems of developing deposits of unconventional hydrocarbons in ultra-low-permeable and shale sediments, Georesursy 20 (2018) 198-205, https://doi.org/10.18599/GRS.2018.3.198-205.

[14] I.N. Zaidullin, A.N. Pitsenko, A.G. Safiulina, A.I. Lakhova, S.N. Petrov, N.Y. Bashkirtseva, Composition and property changes in oil dispersions after hydrothermal treatment of rock-forming minerals with hydrocarbon solvents, Chem. Technol. Fuels Oils 54 (2018) 550-556, https://doi.org/10.1007/s10553-018-0958-z.

[15] S.M. Petrov, A.G. Safiulina, N.Y. Bashkirtseva, A.I. Lakhova, G.G. Islamova, Influence of metal oxides and their precursors on the composition of final products of aquathermolysis of raw Ashalchin oil, Processes 9 (2021) 256, https://doi.org/10.3390/pr9020256.

[16] A. Lakhova, R. Soldatova, S. Petrov, A. Nosova, A. Safiulina, Transformation of heavy oil in hydrothermal impact, Petrol. Sci. Technol. 37 (2019) 611-616, https://doi.org/10.1080/10916466.2018.1560319.

[17] M.D. Lewan, J.C. Winters, J.H. McDonald, Generation of oil-like pyrolyzates from organic-rich shales, Science (80-) 203 (1979) 897-899, https://doi.org/10.1126/SCIENCE.203.4383.897.

[18] L.C. Price, Aqueous solubility of crude oil to 400 °C and 2,000 bars pressure in the presence of gas*, J. Petrol. Geol. 4 (1981) 195-223, https://doi.org/10.1111/J.1747-5457.1981.TB00535.X.

[19] J.C. Winters, A laboratory study of petroleum generation by hydrouspyrolysis, Adv. Org. Geochem. (1981 1983)524-533.

[20] L.C. Price, Aqueous solubility of methane at elevated pressures and temperatures, Am. Assoc. Petrol. Geol. Bull. 63 (1979) 1527-1533, https://doi.org/10.1306/2F9185E0-16CE-11D7-8645000102C1865D.

[21] T.I. Eglinton, S.J. Rowland, C.D. Curtis, A.G. Douglas, Kerogen-mineral reactions at raised temperatures in the presence of water, Org. Geochem. 10 (1986) 1041-1052, https://doi.org/10.1016/S0146-6380(86)80043-2.

[22] Y.V. Onishchenko, A.V. Vakhin, B.I. Gareev, G.A. Batalin, V.P. Morozov, A.A. Eskin, The material balance of organic matter of Domanic shale formation after thermal treatment, Petrol. Sci. Technol. 37 (2019) 756-762, https://doi.org/10.1080/10916466.2018.1558247.

[23] G. Kayukova, A. Mikhailova, Z. Nasurova, O. Sotnikov, E. Nazimov,Temperature influence on the composition of high-carbonic Domanic rocks organic matter during hydrothermal treatment in CO2 atmosphere, IOP Conf. Ser. Earth Environ. Sci. 282 (2019) 012005, https://doi.org/10.1088/1755-1315/282/1/012005.

[24] T. Bondarenko, A. Cheremisin, E. Kozlova, I. Zvereva, M. Chislov, M. Myshenkov, et al., Experimental investigation of thermal decomposition of Bazhenov formation kerogen: mechanism and application for thermal enhanced oil recovery, J. Pet. Sci. Eng. 150 (2017) 288-296, https://doi.org/10.1016/J.PETROL.2016.12.011.

[25] A.V. Stupakova, G.A. Kalmykov, N.P. Fadeeva, A.K. Bogomolov, T.A. Kiryukhina, N.I. Korobova, et al., On the estimation of shale-oil resources and reserves, Moscow Univ. Geol. Bull. 70 (2015) 183-190, https://doi.org/10.3103/S0145875215030096.

[26] E.L. Shock, P. Canovas, Z. Yang, G. Boyer, K. Johnson, K. Robinson, et al., Thermodynamics of organic transformations in hydrothermal fluids, Rev. Mineral. Geochem. 76 (2013) 311-350, https://doi.org/10.2138/RMG.2013.76.9.

[27] G. Brunner, Processing of fuel materials with hydrothermal and supercritical water, Supercrit. Fluid Sci. Technol. 5 (2014) 361-394, https://doi.org/10.1016/B978-0-444-59413-6.00007-8.

[28] Z. Chen, Z. Chen, F. Yin, G. Wang, H. Chen, C. He, et al., Supercritical water oxidation of oil-based drill cuttings, J. Hazard Mater. 332 (2017) 205-213, https://doi.org/10.1016/J.JHAZMAT.2017.03.001.

[29] Z.R. Nasyrova, G.P. Kayukova, Y.V. Onishchenko, V.P. Morozov, A.V. Vakhin, Conversion of high-carbon domanic shale in sub-and supercritical waters, Energy Fuel. 34 (2020) 1329-1336, https://doi.org/10.1021/acs.energyfuels.9b03130.

[30] I.S. Khusnutdinov, A.G. Safiulina, R.R. Zabbarov, O.A. Dubovikov, S.I. Khusnutdinov, N.K. Khaldarov, Influence of physicochemical properties of highly organized oil disperse systems on efficiency of thermomechanical dehydration, Chem. Technol. Fuels Oils 52 (2017) 779-784, https://doi.org/10.1007/s10553-017-0773-y.

[31] A. Lakhova, S. Petrov, D. Ibragimova, G. Kayukova, A. Safiulina, A. Shinkarev, et al., Aquathermolysis of heavy oil using nano oxides of metals, J. Pet. Sci. Eng. 153 (2017) 385-390, https://doi.org/10.1016/J.PETROL.2017.02.015.

[32] S.М. Petrov, D.A. Ibragimova, A.G. Safiulina, B. Tohidi Kalorazi, A.V. Vakhin, R.C. Okekwe, et al., Conversion of organic matter in the carbonaceous medium in the supercritical water, J. Pet. Sci. Eng. 159 (2017) 497-505, https://doi.org/10.1016/J.PETROL.2017.09.060.

[33] G.P. Kayukova, A.M. Kiyamova, A.N. Mikhailova, I.P. Kosachev, S.M. Petrov, G.V. Romanov, et al., Generation of hydrocarbons by hydrothermal transformation of organic matter of Domanik rocks, Chem. Technol. Fuels Oils 52 (2016) 149-161, https://doi.org/10.1007/s10553-016-0685-2.

[34] G.P. Kayukova, A.N. Mikhailov, I.P. Kosachev, V.P. Morozov, A.V. Vakhin, Hydrothermal transformations of organic matter of carbon-rich Domanik rock in carbon dioxide environment at different temperatures, Petrol. Chem. 60 (2020) 278-290, https://doi.org/10.1134/S0965544120030093/METRICS.

[35] G.P. Kayukova, N.M. Khasanova, D.T. Gabdrakhmanov, A.N. Mikhaylova, N.A. Nazimov, O.S. Sotnikov, et al., Changes of the oil-generation potential of the Domanik rocks in the conditions of hydrothermal and pyrolytic exposure, Actual Probl. Oil Gas 4 (2017) 1-17, https://doi.org/10.29222/ipng.2078-5712.2017-19.art3.

[36] D.D. Valeshina, G.P. Kayukova, D.A. Feoktistov, V.P. Morozov, A.I. Lakhova, Evaluation of the relationship between the content of organic matter in the rocks and the group composition of extracts from the rocks of the Permian deposits of the Ashalchinskoye field, Bull. Technol. Univ. 20 (2017) 38-42.

[37] Z.R. Nasyrova, G.P. Kayukova, A.N. Mukhamadyarova, R. Jimasbe, B.I. Gareev, A.V. Vakhin, Hydrocarbon composition of products formed by transformation of the organic matter of rocks from Tatarstan Domanik deposits in supercritical water, Petrol. Chem. 62 (2022) 199-213, https://doi.org/10.1134/S0965544122060081/METRICS.

[38] Z.R. Nasyrova, G.P. Kayukova, B.I. Gareev, V.P. Morozov, A.V. Vakhin, The effect of supercritical water on conversion of resins, asphaltenes and kerogens in rocks of different lithofacies of Domanic deposits of Tatarstan, Fuel 329 (2022) 125429, https://doi.org/10.1016/J.FUEL.2022.125429.

[39] N.S. Burdelnaya, Modeling of the Chemical Structure of Kerogen and its Transformation during the Catagenesis of the Middle Volgian and Domanik Carbonaceous Rocks of the East European Platform, 2017.

[40] Т.N. Yusupova, Y.M. Ganeeva, G.V. Romanov, E.E. Barskaya, Physical and Chemical Processes in Productive Oil Reservoirs, 2015