Application of vacuum reduction and chlorinated distillation to enrich and prepare pure germanium from coal fly ash

Germanium, as strategic reserve metal, plays critical role in high-tech industry. However, a contradiction of increasing consumption and scarcity of germanium resource is becoming more and more prominent. This paper proposed an integrated process to recycle germanium from coal fly ash. This technological process mainly consisted of two procedures: vacuum reduction with the purposes of enriching germanium and chlorinated distillation with the purposes of purifying germanium. Several highlights are summarized as follows: (i) Separation principle and reaction mechanism were discussed to understand this integrated process. (ii) Optimum designs and product analysis were developed to guide industrial recycling. The appropriate parameters for vacuum reduction process on the basis of response surface methodology (RSM) were 920.53°C and 259.63Pa, with 16.64wt.% reductant, and for the chlorinated distillation process, adding 8mol/l HCl and L/S 7, 8wt.% MnO₂. The global recovery rate of germanium was 83.48±0.36% for the integrated process. (iii) This process overcomes the shortages of traditional process and shows its efficiency and environmental performance. It is significant in accordance with the "Reduce, Reuse and Recycle Principle" for solid waste and further provides a new opportunity for germanium recovery from waste by environment-friendly way.