The recovery and recycling of metals that generate toxic ions in the environment is of particular importance, especially when these are tungsten and, in particular, thorium. The radioactive element thorium has unexpectedly accessible domestic applications (filaments of light bulbs and electronic tubes, welding electrodes, and working alloys containing aluminum and magnesium), which lead to its appearance in electrical and electronic waste from municipal waste management platforms. The current paper proposes the simultaneous recovery of waste containing tungsten and thorium from welding electrodes. Simultaneous recovery is achieved by applying a hybrid membrane electrolysis technology coupled with nanofiltration. An electrolysis cell with sulphonated polyether-ether-ketone membranes (sPEEK) and a nanofiltration module with chitosan-polypropylene membranes (C-PHF-M) are used to carry out the hybrid process. The analysis of welding electrodes led to a composition of W (tungsten) 89.4%; Th 7.1%; O2 2.5%; and Al 1.1%. Thus, the parameters of the electrolysis process were chosen according to the speciation of the three metals suggested by the superimposed Pourbaix diagrams. At a constant potential of 20.0 V and an electrolysis current of 1.0 A, the pH is varied and the possible composition of the solution in the anodic workspace is analyzed. Favorable conditions for both electrolysis and nanofiltration were obtained at pH from 6 to 9, when the soluble tungstate ion, the aluminum hydroxide, and solid thorium dioxide were formed. Through the first nanofiltration, the tungstate ion is obtained in the permeate, and thorium dioxide and aluminum hydroxide in the concentrate. By adding a pH 13 solution over the two precipitates, the aluminum is solubilized as sodium aluminate, which will be found after the second nanofiltration in the permeate, with the thorium dioxide remaining integrally (within an error of ±0.1 ppm) on the C-PHF-M membrane.
Keywords: Pourbaix diagrams; membrane electrolysis; membrane processes; nanofiltration; thorium recovery; thorium recycling; wolfram recovery; wolfram recycling.