盐酸蒸馏-磷酸三丁酯萃取法从锗煤烟尘中综合回收锗和镓  

Comprehensive Recovery of Germanium and Gallium from Gemanium Coal Dust through Hydrochloric Acid Distillation-Tributyl Phosphate Extraction Process

作　　者：普世坤[1,2] 兰尧中[1,3] 刀才付 

机构地区：[1]上海大学,上海200072 [2]云南临沧鑫圆锗业股份有限公司,云南临沧677000 [3]云南大学矿产开发与循环经济研究所,云南昆明650091 [4]新平第一中学,云南玉溪653400

出　　处：《稀有金属材料与工程》2014年第3期752-756,共5页Rare Metal Materials and Engineering

基　　金：国家自然科学基金(U1037603)

摘　　要：先采用二氧化锰氧化-盐酸蒸馏提取煤烟尘中的锗，经提纯后制备得到高纯二氧化锗，同时煤烟尘中的镓在蒸馏过程中充分溶解到了锗蒸馏残渣液中，过滤后镓和蒸馏后残留的锗进入到了蒸馏残液中，调节蒸馏残液的酸度至5．6mol／L，采用磷酸三丁酯的260“溶剂油溶液对镓进行萃取，蒸馏残液中的少量锗亦被同时萃取进入到有机相中，用氢氧化钠溶液进行反萃取，反萃取完后调节pH至6．5～6．7，升温至85～95℃水解，得到氢氧化镓沉淀和二氧化锗沉淀，经过滤烘干后得到含锗镓精矿。锗的蒸馏回收率可达到92.37％以上，残液中锗的萃取率可达到86．18％以上；镓的盐酸浸出率可达81．23％以上，镓的磷酸三丁酯萃取率可达98.81％以上，反萃取率可达99．11％以上，中和沉淀直收率可达93．20％以上；工艺方法具有工艺流程简短、设备简单、过程易于控制，所用生产辅料较少，是一种从煤烟尘中综合回收锗和镓的高效且经济的方法。Germanium was extracted from coal dust by manganese dioxide oxidation-hydrochloric acid distillation, and then germanium dioxide with high purity was obtained via purification process. Meanwhile, gallium in the coal dust dissolved fully into germanium distillation residual liquid. After the filtering process, gallium and residual germanium got into the vinasse. The vinasse acidity was adjusted to 5.6 mol/L to extract gallium by 260# solvent oil solution of tributyl phosphate （TBP）. A small amount of germanium in the vinasse was extracted as well, and subsequently went into the organic phase. Then sodium hydroxide solution was taken to conduct re-extraction. Afterwards, its pH was adjusted to 6.5-6.7 and it was heated up to 85-95℃ to hydrolyze gallium and germanium. As a result, hydrogen gallium oxide precipitation and germanium dioxide precipitation were produced. Finally germanium and gallium concentrates were obtained via filtering and drying process. By taking the above procedures, the distillation recovery rate of germanium is as high as 92.37%, and the recovery rate of germanium in the vinasse is 86.18%. Hydrochloric acid leaching rate of gallium is above 81.23% and tributyl phosphate recovery rate and re-extraction rate of gallium is 98.81% and 99.11%, respectively. And the neutralized precipitation straight yield rate is 93.20%. Thus, the hydrochloric acid distillation-tributyl phosphate extraction process is a kind of economic and efficient extraction method, enjoying the qualities of short procedures, easier process control, high recovery rate, less time and less assumption of material.

关 键 词：锗煤烟尘 盐酸 TBP 锗 镓 回收中图法 

分 类 号：TF84[冶金工程—有色金属冶金]