Recycling of oxalic acid from rare earth oxalate leach solutions, G.L. Dyer, R.E. Browner, and R.D. Alorro

A potential new rare earth extraction process has been suggested (Lazo, et al., 2017) (Lazo, et al., 2018) based on converting the rare earth elements to solid phase rare earth oxalates in an oxalic acid leach. Oxalic acid consumption is a significant issue in the process, therefore to improve the viability of this proposed new extraction method, a process to recover oxalate from the leach solution and recycle oxalic acid is required. A review of the literature and confirmation through thermodynamic analysis of the potential options identified precipitation of calcium or ferrous oxalate as the best potential options. The use of metallic iron to both provide ferrous ions as a precipitant and reduce ferric ions in solution would provide the most economical option, however slow kinetics and unreacted iron created significant issues with this process. The direct use of ferrous ions, while faster and more efficient, produced a precipitate with relatively poor solid/liquid handling characteristics and would require an intermediate stage utilising calcium in regenerating the oxalate. Utilising calcium chloride and oxide created very similar precipitates with better physical properties than the ferrous oxalate and that a reasonable proportion of the oxalate could be recovered before neutralisation of the solution induced precipitation of other phases such as iron oxy-hydroxides and calcium phosphate. The produced calcium oxalate was easily converted to oxalic acid and gypsum via immersion in sulphuric acid. It was also found that there is a significant loss of oxalic acid due to factors other than rare earth oxalate precipitation during leaching. This leads to a maximum oxalate recovery in the range of 50 %.