Phase Equilibria Relevant to Acid Gas Injection, Part 1-Non-Aqueous Phase Behaviour

Abstract

The design of an acid gas injection scheme requires a significant amount of information regarding phase equilibria. The purpose of this paper is to review the literature for the available experimental data, and survey methods for calculations of the non-aqueous equilibria. This study will be limited to the following components: hydrogen sulfide, carbon dioxide, methane, ethane, propane, and, to some extent, water. It is demonstrated that the widely available Peng-Robinson equation of state is adequate for predicting the non-aqueous phase equilibria in these mixtures. However, the design engineer should be cognizant of the capabilities of the model selected to perform the calculations. If uncertain, it is wise to verify the software package, and more importantly the chosen model, by comparing it with experimental data. Available data are compiled as a part of this paper. ACID GAS INJECTION Acid gas injection has become the environmentally friendly way to deal with the unwanted by-product of the sweetening of natural gas. In the future it may become a means of dealing with carbon dioxide from other sources as well. In a basic acid gas injection scheme, the acid gas off the amine regenerator tower is compressed and transported via pipeline to an injection well. From there, it is injected into a suitable formation for disposal. The formation is selected based on geological criteria such as the size of the disposal reservoir, and the containment of the injected acid gas. In an acid gas injection scheme, pressures can range from near atmospheric up to 30 MPa or more; the upper limit is dictated by the selected reservoir. The temperature can range from about 30 °C up to as much as 200 °C; again the upper limit is being the reservoir conditions. The design of the injection scheme requires a thorough knowledge of the phase equilibria encountered in wet acid gas mixtures. This paper reviews the experimental investigations into the relevant systems. This study is limited to the following components: hydrogen sulfide, carbon dioxide, methane, ethane, propane, and water. Even so, an interesting variety of phase equilibria will be presented. The design engineer is advised to be aware of all of the various phenomena encountered in mixtures of these components, as they will have a significant effect on the design. Experimental Investigations In this section, experimental investigations important to acid gas injection will be reviewed. Typically, in acid gas injection schemes, we are not concerned with hydrocarbons heavier than propane. So, for this study, only equilibrium between the acid gas components and methane, ethane, and propane will be considered. Hydrogen Sulfide +Carbon Dioxide The most important non-aqueous system involved in acid gas injection is the binary mixture hydrogen sulfide +carbon dioxide, since acid gas is composed almost exclusively of these components. Two early studies of the phase equilibrium in the system hydrogen sulfide +carbon dioxide were Bierlein and Kay(1) and Sobocinski and Kurata(2).

Evaluation of Cubic, SAFT, and PC-SAFT Equations of State for the Vapor–Liquid Equilibrium Modeling of CO2 Mixtures with Other Gases

“…As far as thermodynamic modeling of CCS technologies is concerned, several approaches have been reported in the literature that vary with respect to components, methods and conditions investigated. Caroll studied the vapor–liquid equilibria (VLE) of CO 2 mixtures with CH 4 and H 2 S using PR and SRK EoS. Li and Yan studied the VLE of CO 2 mixtures with a wide range of gases using different cubic EoS.…”

Hydrogen sulphide

“…For simplicity and economic reasons, wellhead injection temperatures and pressures are usually aligned with that of the compressed gas's transportation conditions [90] although temperatures can range between 30°C all through to 200°C and pressures from 1 to 30 MPa, with both temperature and pressure ceiling usually determined by the reservoir's state [91], and the acid gas injection strategy delineated to take advantage of system thermodynamics, including importantly, use of the phase envelope [92]. Storage is usually implemented in deep saline aquifers, depleted oil and gas reservoirs, clastic and basaltic formations, unmineable coal seams [93], and unconventional oil and gas reservoirs [94].…”

Mathematical modeling of thermophysical properties and phase equilibria of pure carbon dioxide and multicomponent mixtures

“…Carroll [68] used the PR and SRK EoS to study the vapor-liquid equilibria (VLE) behavior of CO2 mixtures with CH4 and H2S, proving that these tools are quite accurate for the prediction of the complex phase equilibria exhibited by these systems.…”