Growth of the calcium carbonate polymorph vaterite in mixtures of water and ethylene glycol at conditions of gas processing

Long subsea tie-ins for transportation of moist gas and condensate require corrosion and hydrate control. The combination of alkalinity for corrosion mitigation and monoethylene glycol (MEG) for hydrate inhibition strongly affects the tolerance for produced formation water. The elevated alkalinity downstream of the injection point increases the risk of carbonate formation. Calcium carbonate is the most common precipitate at such conditions. Our previous findings (Flaten et al., 2009) [1] show that MEG governs calcium carbonate precipitation and promotes formation of the metastable polymorph vaterite. This paper describes crystal growth of vaterite in mixed MEG water solvent with 0–70 wt% MEG at temperatures of 40 and 70 °C in solutions with high calcium to carbonate ratios representative of the production conditions. Results of some experiments in solutions with stoichiometric amounts of the reactants are included for comparison. The growth rate of vaterite can be described by second-order kinetics in most of the investigated supersaturation range. The growth order is lower at high MEG contents and high calcium concentrations when the carbonate activity is reduced in order to maintain comparable supersaturation values. It is then probable that the low carbonate activity makes the reaction diffusion limited. MEG reduces the growth rate constant of vaterite when the reaction is second order. Increasing the MEG concentration from 0 to 50 wt%, decreases the growth rate constant kr from 1.9 to 0.7 nm/s at 40 °C and from 2.6 to 1.2 nm/s at 70 °C. The growth reduction can be explained by a change of either de-hydration or diffusion rate along the surface when the ions are incorporated into the crystal lattice. Further investigations into which of the two mechanisms that is rate determining is outside the scope of this work.