A robust and efficient numerical method for multiphase equilibrium calculations: Application to CO2–brine–rock systems at high temperatures, pressures and salinities

• Published in: Advances in water resources Vol. 62; pp. 409 - 430
• Main Authors: Leal, Allan M.M., Blunt, Martin J., LaForce, Tara C.
• Format: Journal Article
• Language: English
• Published: Elsevier Ltd 01-12-2013
• Subjects: Aquifers; Carbon storage; Chemical equilibrium; Convergence; Customizing; Geochemistry; Mathematical analysis; Mathematical models; Multiphase; Multiphase system; Saline; Salinity; Multiphase system; Geochemistry; Chemical equilibrium; Carbon storage
• ISSN: 0309-1708; 1872-9657
• DOI: 10.1016/j.advwatres.2013.02.006

► We develop a method for chemical equilibrium calculations in multiphase systems. ► We show that the method is capable of determining the stable phase assemblage. ► A general approach for specifying equilibrium constraints is developed. ► The method is applied to solve equilibrium problems relevant to carbon storage. ► We demonstrate its potential to be integrated in reactive transport simulators.
We present a robust and efficient method for calculating chemical equilibria of general multiphase systems. The method is based on a stoichiometric approach, which uses Newton’s method to solve a system of mass-action equations coupled with a system of equilibrium constraints. A stabilisation procedure is developed to promote convergence of the calculation when a presupposed phase in the chemical system is absent in the equilibrium state. The formulation of the chemical equilibrium problem is developed by presuming no specific details of the involved phases and species. As a consequence, the method is flexible and general enough so that the calculation can be customised with a combination of thermodynamic models that are appropriate for the problem of interest. Finally, we show the use of the method to solve relevant geochemical equilibrium problems for modelling carbon storage in highly saline aquifers.