Comparison of calcium-removal options in the treatment of minewater reclamation retentates, H.R. Heydenrych, J. Chivavava, M. Shaw, E. Glass, and A.E. Lewis

The removal of calcium from the retentates of reverse osmosis (RO) treated minewater is desirable since it allows the recovery of both additional potable water (through RO) and higher-purity salts (in downstream processing). This, in turn, reduces the need for costly and unsustainable evaporation ponds and enhances the economics and operability of potential zero-liquid discharge downstream processes, e.g. evaporative-, cooling- and eutectic freeze-crystallisation. For this study, a multi-component retentate high in sodium content was considered, typical of those emanating from minewater reclamation plants in Mpumalanga, South Africa. Four technologies were evaluated to remove calcium: gypsum precipitation by addition of lime; calcium carbonate precipitation by addition of soda-ash; heating crystallisation of calcium sulphate anhydrite; and cooling crystallisation of gypsum. Full processes were developed and simulated using electrolyte thermodynamics. Using the results of these simulations, capital- and operating costs, as well as revenues were calculated and used in economic comparisons of the processes. Sensitivities to key purchasing and selling prices were also investigated to understand the impact of changes in these variables. For the case of a low magnesium-to-sodium ratio in the feed, gypsum precipitation through lime addition was found to have the lowest operating and total annualised costs; but, if revenue could be derived from the sale of sodium sulphate, calcium carbonate precipitation through soda-ash addition was favoured. Keywords: Calcium removal, gypsum precipitation, calcium carbonate precipitation, heating crystallsation, cooling crystallisation, economic comparison