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Thermodynamic Feasibility of the Black Sea CH 4 Hydrate Replacement by CO 2 Hydrate

Author

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  • Bjørn Kvamme

    (State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation, Southwest Petroleum University, Xindu Road No. 8, Chengdu 610500, China
    State Key Laboratory of Natural Gas Hydrate, Sun Palace South Street No. 6, Beijing 100027, China
    Hyzenenergy, 26701 Quail Creek, Laguna Hills, CA 92656, USA
    Strategic Carbon LLC, 7625 Rancho Vista BLVD W, Corpus Christi, TX 78414, USA)

  • Atanas Vasilev

    (Institute of Oceanology—Bulgarian Academy of Sciences, First May 40, PO Box 152, 9000 Varna, Bulgaria)

Abstract

There is an international consensus that reductions of CO 2 emissions are needed in order to reduce global warming. So far, underground aquifer storage of CO 2 is the only commercially active option, and it has been so since 1996, when STAOIL started injecting a million tons of CO 2 per year into the Utsira formation. Storage of CO 2 in the form of solid hydrate is another option that is safer. Injection of CO 2 into CH 4 hydrate-filled sediments can lead to an exchange in which the in situ CH 4 hydrate dissociates and releases CH 4 . Two types of additives are needed, however, to make this exchange feasible. The primary objective of the first additive is related to hydrodynamics and the need to increase injection gas permeability relative to injection of pure CO 2 . This type of additive is typically added in amounts resulting in concentration ranges of additive in the order of tens of percentages of CO 2 /additive mixture. These additives will, therefore, have impact on the thermodynamic properties of the CO 2 in the mixture. A second additive is added in order to reduce the blocking of pores by new hydrates created from the injection gas and free pore water. The second additive is a surfactant and is normally added in ppm amounts to the gas mixture. A typical choice for the first additive has been N 2 . The simple reasons for that are the substantial change in rheological properties for the injection gas mixture and a limited, but still significant, stabilization of the small cavities of structure I. There are, however, thermodynamic limitations related to adding N 2 to the CO 2 . In this work, we discuss a systematic and consistent method for the evaluation of the feasibility of CO 2 injection into CH 4 hydrate-filled reservoirs. The method consists of four thermodynamic criterions derived from the first and second laws of thermodynamics. An important goal is that utilization of this method can save money in experimental planning by avoiding the design of CO 2 injection mixtures that are not expected to work based on fundamental thermodynamic principles. The scheme is applied to hydrates in the Black Sea. Without compositional information and the knowledge that there is some verified H 2 S in some sites, we illustrate that the observed bottom hydrate stability limits are all with hydrate stability limits of hydrates containing from 0 to 3 mole% H 2 S. A limited number of different injection gas mixtures has been examined, and the optimum injection gas composition of 70 mole% CO 2 , 20 mole% N 2 , 5 mole% CH 4 , and 5 mole% C 2 H 6 is feasible. In addition, a surfactant mixture is needed to reduce blocking hydrate films from injection gas hydrate.

Suggested Citation

  • Bjørn Kvamme & Atanas Vasilev, 2023. "Thermodynamic Feasibility of the Black Sea CH 4 Hydrate Replacement by CO 2 Hydrate," Energies, MDPI, vol. 16(3), pages 1-29, January.
    • Handle: RePEc:gam:jeners:v:16:y:2023:i:3:p:1223-:d:1044622
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    References listed on IDEAS

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    1. Bjørn Kvamme & Jinzhou Zhao & Na Wei & Wantong Sun & Navid Saeidi & Jun Pei & Tatiana Kuznetsova, 2020. "Hydrate Production Philosophy and Thermodynamic Calculations," Energies, MDPI, vol. 13(3), pages 1-34, February.
    2. Pham, V.T.H. & Riis, F. & Gjeldvik, I.T. & Halland, E.K. & Tappel, I.M. & Aagaard, P., 2013. "Assessment of CO2 injection into the south Utsira-Skade aquifer, the North Sea, Norway," Energy, Elsevier, vol. 55(C), pages 529-540.
    3. Chadwick, R.A & Zweigel, P & Gregersen, U & Kirby, G.A & Holloway, S & Johannessen, P.N, 2004. "Geological reservoir characterization of a CO2 storage site: The Utsira Sand, Sleipner, northern North Sea," Energy, Elsevier, vol. 29(9), pages 1371-1381.
    4. Oleg Bazaluk & Kateryna Sai & Vasyl Lozynskyi & Mykhailo Petlovanyi & Pavlo Saik, 2021. "Research into Dissociation Zones of Gas Hydrate Deposits with a Heterogeneous Structure in the Black Sea," Energies, MDPI, vol. 14(5), pages 1-24, March.
    5. Bjørn Kvamme & Matthew Clarke, 2021. "Hydrate Phase Transition Kinetic Modeling for Nature and Industry–Where Are We and Where Do We Go?," Energies, MDPI, vol. 14(14), pages 1-47, July.
    6. Bjørn Kvamme, 2019. "Enthalpies of Hydrate Formation from Hydrate Formers Dissolved in Water," Energies, MDPI, vol. 12(6), pages 1-19, March.
    7. Bjørn Kvamme & Richard B. Coffin & Jinzhou Zhao & Na Wei & Shouwei Zhou & Qingping Li & Navid Saeidi & Yu-Chien Chien & Derek Dunn-Rankin & Wantong Sun & Mojdeh Zarifi, 2019. "Stages in the Dynamics of Hydrate Formation and Consequences for Design of Experiments for Hydrate Formation in Sediments," Energies, MDPI, vol. 12(17), pages 1-20, September.
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