含锗煤烟尘中锗的浸出和精提制备高品位锗精矿  

Leaching and Refining of Germanium from Coal Soot Containing Germanium to Prepare High-Grade Germanium Concentrate

作　　者：李海飞 罗波 罗志军 王绍江 龙汉生 张勇民 LI Haifei;LUO Bo;LUO Zhijun;WANG Shaojiang;LONG Hansheng;ZHANG Yongmin(School of Pharmacy,Guizhou University of Traditional Chinese Medicine,Guiyang Guizhou 550025,China;School of Food and Pharmaceutical Engineering,Guizhou Institute of Technology,Guiyang Guizhou 550025,China;Guiyang Gallochem Co.,Ltd.,Guiyang Guizhou 550214,China;School of Resources and Environmental Engineering,Guizhou Institute of Technology,Guiyang Guizhou 550025,China;Paris Institute of Molecular Chemistry,Sorbonne University,Paris 75005,France)

机构地区：[1]贵州中医药大学药学院,贵州贵阳550025 [2]贵州理工学院食品药品制造工程学院,贵州贵阳550025 [3]贵阳倍隆生物科技有限公司,贵州贵阳550214 [4]贵州理工学院资源与环境工程学院,贵州贵阳550025 [5]法国索邦大学巴黎分子化学研究所,巴黎75005

出　　处：《当代化工》2025年第3期568-574,共7页Contemporary Chemical Industry

基　　金：贵州省教育厅高校科技成果转移转化服务乡村振兴示范基地项目(项目编号:黔教技[2022]063号);贵州省科技计划项目(项目编号:黔科合服企[2020]4010号)。

摘　　要：以含锗煤烟尘为原料,通过先用NaClO_(3)氧化,再用H_(2)SO_(4)-NH_(4)F混合酸浸出,最后用单宁沉锗的工艺对锗进行富集。最佳浸出工艺条件为:含锗煤烟尘5 g,NaClO_(3)0.2 g,H_(2)O 10 mL,氧化浸提2 h,将NH_(4)F 0.4 g、H_(2)SO_(4)4 mL先混合生成HF后,将混合酸加入浸提液中,酸化浸提4 h,过滤,滤渣进行二次提取。此方法锗浸出率为97.6%。对提取液中锗的精提,用提取液中锗计算含量40倍质量比的五倍子单宁与锗形成络合物,精提锗。选用温度为50℃,恒温振荡2 h,产生沉淀,自然沉降30 min,过滤得到单宁锗。经测定,锗的沉淀率为83.3%。单宁锗氧化焙烧处理后,得到锗精矿,锗精矿的品位达到11.4%。沉锗后液中尚有10%~20%的锗未被回收,并有部分单宁在其中,将沉锗后液套用至含锗烟尘的浸出工艺中,浸出液中的锗浓度可提高20.8%。同时降低单宁用量至20倍时,锗的沉淀率可达81.9%。Using coal smoke dust containing germanium as the raw material,germanium was enriched through a process that first using NaClO_(3)for oxidation,then using H_(2)SO_(4)-NH_(4)F mixed acid for leaching,and finally using tannin to precipitate germanium.The optimal leaching process conditions were determined as follows:the amount of germanium-containing coal soot 5 g,NaClO_(3)0.2 g,water 10 mL,oxidative leaching for 2 h,NH_(4)F 0.4 g and H_(2)SO_(4)4 mL were mixed first,after HF was generated,the mixed acid was added to the extract,which was acidified and extracted for 4 h,and filtered.The filter residue was subjected to secondary extraction.The germanium leaching rate of this method was 97.6%.Refinement of germanium in the extract solution was carried out by using germanium from the extract solution at a weight ratio of 40 times that of Chinese gallotannin to form tannin complexes for germanium refinement.The temperature was 50℃,the precipitation was generated after the constant temperature oscillation for 2 h,and after the natural settlement for 30 min,the tannin germanium was filtered.The germanium immersion rate was 83.3%.After tannin germanium oxidation roasting,germanium concentrate was obtained.The germanium concentrate reached a grade of 11.4%.However,there was still 10%~20%of germanium in the solution,and some tannin in it.When the solution was applied to a leaching process containing germanium dust,the concentration of germanium in the leaching solution was increased by 20.8%.At the same time,the amount of tannin could be reduced to 20 times,and the precipitation rate of germanium could also reach about 81.9%.

关 键 词：含锗煤烟尘 五倍子单宁 单宁络合物 单宁沉锗 沉锗后液 

分 类 号：TQ016[化学工程]