Thermodynamic of thermochemical sulphate reduction

Abstract Hydrogen sulphide is likely to become more common in produced hydrocarbon fluids, as the exploitation of deep reservoirs increases and unconventional resources get recovered significantly, such as heavy oils or bitumen. Hydrogen sulphide presence in produced oil and gas results in operational, environmental and treatment problems. Therefore, understanding the origin and the amount of hydrogen sulphide in petroleum reservoirs has great importance for petroleum engineers. Three natural processes are set forth to explain the generation of H 2 S in reservoirs: bacterial sulphate reduction, thermal cracking and thermochemical sulphate reduction (TSR). It is the TSR that leads to the largest amount of H 2 S. This phenomenon involves hydrocarbon oxidation and sulphate reduction and produces as by-products, hydrogen sulphide, carbon dioxide, carbonate minerals and heavy organo-sulphur compounds. The reaction mechanisms of TSR, as well as its kinetics, are not yet fully understood. In this paper, we checked the thermodynamic feasibility of TSR, at temperatures prevailing in the reservoirs where TSR is encountered. Firstly, we calculated the Gibbs energy of the reactions proposed by Worden and Smalley (Worden R.H. and Smalley P.C., 1996, H 2 S producing reactions in deep carbonate gas reservoirs: Khuff Formation, Abu Dhabi, Chem. Geol., 133, p. 157–171). We concluded that they are thermodynamically possible from 25 °C, confirming thermodynamic data published by Anisimov (Anisimov L., 1978, Conditions of abiogenic reduction of sulfates in oil and gas bearing basins, Geochem. Int., 15, p. 63) and Yue and co-workers (Yue C., Li S., Ding K., Zhong N., 2003, Study of thermodynamics and kinetics of CH4–CaSO 4 and H 2 S–Fe 2 O 3 systems, Chinese J. chem. Eng., 11, (6), p.696–700., Yue C., Li S., Ding K., Zhong N., 2006, Thermodynamics and kinetics of reaction between C1–C3 hydrocarbons and calcium sulfate in deep carbonate reservoirs, Geochem. J., 40, 87–94). Secondly, we used a non-stoichiometric approach without any pre-requisite chemical scheme this time. We calculated the Gibbs Energy of chemical systems composed by hydrocarbons, sulphur, anhydrite and water. The minimization of the Gibbs Energy lead to find the most probable chemical systems at steady state. Our theoretical results are consistent with the chemical schemes set forth for TSR by Orr (Orr W., 1977, Changes in Sulfur Content and Isotopic Ratios of Sulfur during Petroleum Maturation — study of Big Horn Basin Paleozoic Oils, in R. Campo and J. Goni Eds, Advances in onorganic geochemistry, Madrid Spain, Enadimsa, p. 571–595), by Worden and Smalley (Worden R.H. and Smalley P.C., 1996, H 2 S producing reactions in deep carbonate gas reservoirs: Khuff Formation, Abu Dhabi, Chem. Geol., 133, p. 157–171) and by Machel (Machel H.G., 2001, Bacterial and thermochemical sulfate reduction in diagenetic settings — old and new insights, Sedimentary Geology, 140, p. 143–175). Moreover, they are in concordance with some in-situ observations: anhydrite and hydrocarbon consumption with simultaneous formation of calcite, hydrogen sulphide and water. Our results showed as well that the larger the number of the carbon atoms in the reactant hydrocarbons, the more irreversible the reaction is.