Phase Equilibria of Acid-Gas Aqueous Systems (CO2, H2S, CH4, Water) and In-Situ pH Measurements in Application to Top-of-Line Corrosion

Summary We present thermodynamic modeling and pH measurements of fluid systems containing acid-gases (e.g., CO2 and H2S), water, and hydrocarbons—replicating the production and shutdown conditions in sour fields—for the purpose of evaluating top-of-line corrosion (TLC) and wellbore integrity and screening/selection of the proper wellbore materials. In particular: An equation of state (EOS) model using Peng-Robinson EOS in combination with the Huron-Vidal (HV) mixing rule for an aqueous subsystem is developed. In the model, subject EOS parameters are calibrated against existing thermodynamic data (saturation data for pure components and solubility data for binary systems) in literature. New in-situ pH measurement data are presented for a model system corresponding to a sour field. It was found that the wellbore can be subjected to pH levels as low as 2.7 with reservoir fluid containing 12 mol% CO2 and 88 mol% CH4 with downhole flowing conditions of 200 bar and 150°C and wellhead shut-in conditions of 300 bar and 4°C, as observed from the experiments. A modeling workflow is developed to estimate pH of the condensed water as a function of temperature and composition of the aqueous phase. The comparison between prediction and experimental measurement shows a very good match between the two (within pH ±0.1). Such studies (pH measurements and prediction) are not available in the literature but play important roles in material screening and assuring wellbore integrity for sour fields. More importantly, sensitivity analysis can be performed to investigate the effects of various factors (such as reservoir temperature/pressure, shutdown conditions, and compositions or extent of souring) on pH prediction. Furthermore, the methodologies developed through this work can also be extended to reservoir facilities, pipelines, sour gas disposal/handling units, and downstream systems such as water utilities, reactor plants, and refineries. The work can also support regulation/licensing for these sour systems.