Phase Stability and Inhibition of Calcium Sulfate in the System NaCl/Monoethylene Glycol/H2O

Abstract

Summary Calcium sulfate is one of the major mineral scales in oil and gas production. Hemihydrate (CaSO4·0.5H2O) and anhydrite (CaSO4) are the predominant sulfate scales formed at high temperature, while gypsum (CaSO4·2H2O) scale may form at low temperatures (<~45°C). However, it has been shown in this study that anhydrite can form at low temperature in the presence of excess amounts of monoethylene glycol (MEG), and this may occur during offshore production with long tie-backs. The prediction and prevention of calcium sulfate scales requires knowledge of the phase behavior of the three major phases of calcium sulfate. The phase behavior of different calcium sulfate phases is related to the supersaturation state, temperature, and fugacity of water. In this study, the effect of a common hydrate inhibitor, MEG, on calcium sulfate solubility and phase behavior was investigated. This study was run with NaCl/CaSO4/MEG/H2O solutions at 0–6 molality (M) NaCl and 0–95 wt% MEG at 4–70°C. Three approaches were taken to determine the kinetics of calcium sulfate phase transition at various temperatures, ionic strengths, and MEG concentrations: (1) dissolution of gypsum, (2) dissolution of anhydrite, and (3) nucleation and precipitation of calcium sulfate by mixing calcium- and sulfate-containing solutions. The effect of scale inhibitors on phase transition was also evaluated. Phase transition of gypsum to anhydrite was observed in the presence of high concentrations of NaCl and MEG, regardless of the experimental approach. The transition boundary of temperature and concentrations of NaCl and MEG can be estimated from solubility of calcium sulfate and the fugacity of water. The inhibition mechanism of hexamethylene diamine tetra (methylene phosphonic acid) (HDTMP), one of the most effective inhibitors for calcium sulfate scale, was also tested by investigating the kinetics of precipitation and inhibition of calcium sulfate.