CO₂ injection in oil reservoirs provides the dual benefit of increasing oil recovery as well as sequestration. Compositional simulations using phase behavior calculations are used to model miscibility and estimate oil recovery. The injected CO₂, however, is known to react with brine. The precipitation and dissolution reactions, especially with carbonate rocks, can have undesirable consequences. The geochemical reactions can also change the mole numbers of components and impact the phase behavior of hydrocarbons. A Gibbs free energy framework that integrates phase equilibrium computations and geochemical reactions is presented in this dissertation. This framework uses the Gibbs free energy function to unify different phase descriptions - Equation of State (EOS) for hydrocarbon components and activity coefficient model for aqueous phase components. A Gibbs free energy minimization model was developed to obtain the equilibrium composition for a system with not just phase equilibrium (no reactions) but also phase and chemical equilibrium (with reactions). This model is adaptable to different reservoirs and can be incorporated in compositional simulators. The Gibbs free energy model is used for two batch calculation applications. In the first application, solubility models are developed for acid gases (CO₂ /H2 S) in water as well as brine at high pressures (0.1 - 80 MPa) and high temperatures (298-393 K). The solubility models are useful for formulating acid gas injection schemes to ensure continuous production from contaminated gas fields as well as for CO₂ sequestration. In the second application, the Gibbs free energy approach is used to predict the phase behavior of hydrocarbon mixtures - CO₂ -nC₁₄ H₃₀ and CH₄ -CO₂. The Gibbs free energy model is also used to predict the impact of geochemical reactions on the phase behavior of these two hydrocarbon mixtures. The Gibbs free energy model is integrated with flow using operator splitting to model an application of cation exchange reactions between aqueous phase and the solid surface. A 1-D numerical model to predict effluent concentration for a system with three cations using the Gibbs free energy minimization approach was observed to be faster than an equivalent stoichiometric approach. Analytical solutions were also developed for this system using the hyperbolic theory of conservation laws and are compared with experimental results available at laboratory and field scales. / text
| Identifer | oai:union.ndltd.org:UTEXAS/oai:repositories.lib.utexas.edu:2152/24828 |
| Date | 25 June 2014 |
| Creators | Venkatraman, Ashwin |
| Source Sets | University of Texas |
| Language | English |
| Detected Language | English |
| Type | Thesis |
| Format | application/pdf |
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