氧压酸浸炼锌流程中置换渣提取锗镓铟  

Recovery of Ge /Ga /In from Replacement Slag in Pressure Oxidation Leaching Process of Zinc Sulfide Concentrate

作　　者：王继民[1] 曹洪杨[1] 陈少纯[1] 徐毅 张登凯 

机构地区：[1]广州有色金属研究院稀有金属研究所,广东广州510650 [2]深圳市中金岭南有色金属股份有限公司丹霞冶炼厂,广东绍关512024

出　　处：《稀有金属》2014年第3期471-479,共9页Chinese Journal of Rare Metals

摘　　要：为从锌精矿氧压酸浸炼锌工艺的置换渣中提取锗镓铟元素，对二段浸出-萃取分离锗镓铟铜工艺进行研究，锌电积废液用于一段浸出，H2S04-HF混酸用于一段浸出渣的二段浸出；一段浸出液分别采用二（2-乙基已基）磷酸（P204），C3～5氧肟酸＋二（2-乙基已基）（P204）磷酸及5-壬基水杨醛肟（CP150）分别萃取铟，锗镓及铜；二段浸出液用C3-5氧肟酸萃取提锗，萃余液加入氟化钠沉淀氟硅酸钠。试验结果显示，一段浸出用酸度为3．1N的湿法炼锌电积废液，液固比4：1，初始氧分压0．4MPa，150℃，经3h的二级浸出后，浸出渣率约为15％，铟镓铜锌4个元素的浸出率都达到98％，而锗浸出率约为80％；一段浸出残渣用H2SO4-HF混酸浸出，其氟／硅摩尔比4．2：1．0，硫酸浓度为2N温度80℃，液固比3：1，浸出时间为5h，一段浸出残渣中锗几乎完全浸出；一段浸出液在pH2．0～2．2，30％二（2-乙基已基）磷酸萃取，部分铁与几乎所有的铟被萃取，用2N盐酸反萃，铟、铁的反萃率分别为98．28％和2．79％，可达到铟铁的分离；萃铟余液用3％的氧肟酸＋10％二（2-乙基已基）磷酸-煤油协萃锗、镓，铁也发生共萃，锗、镓和铁的单级萃取率均在90％以上，采用次氯酸钠反萃，锗反萃率近100％，且Ge／Ga和Ge／Fe的反萃分离系数分别为10836和318．7。用3mol·L^-1的硫酸，相比（W／O）1：2反萃镓，镓的一次反萃率达97．5％。二段浸出液采用10％C3～5氧肟酸-煤油萃取，相比（O／W）为1．2：1．0，锗的单级萃取率达到98．31％。经30％次氯酸钠溶液反萃，锗的一次反萃率达到98．83％，萃余液加入氟化钠，氟硅化物的沉淀率为90％左右。沉硅滤液经补充氢氟酸后返回二段沉出，锗的浸出仍可达到较完全的浸出。该工艺无废液排放，并且通过与湿法炼锌流程的物料交换而变得简化。To effectively recover geImanium/gallium and indium from the replacement slag in the pressure oxidation leaching process of zinc sulfide concentrate, two-steps leaching-solvent extraction process was investigated. The first leaching was for the waste electro- lyte from electro-deposition of zinc, and the second was for the residue slag from the first leaching with the solution of H2 SO4-HF, and elements were extracted with bis （2-ethylhexyl）hydrogen phosphate （P204） for indium, with C3 -5 hydroximic acids ＋ bis （2-ethylhexyl） hydrogen phosphate for germanium and gallium, and with 5-nonyl salicylaldoxime （ CPl05 ） for copper from the first leaching solution, with C3 -5 hydroximic acids for germanium from the second leaching solution sodium fluoride. The experimental results showed that by the first leaching the elements such as zinc, copper, gallium and indium completely（98% ）, germanium of about 80%, were dissolved from the cementation slag with the waste electrolyte acidity of 3.1 N, the ratio of liquid to solid 4： 1, initial oxygen partial pressure of 0.4 MPa, two times leaching at 150 ℃ for 3 h, with about 15% mass of residue slag to the original cementation slag. By the second leaching process, the germanium remained in the first leaching residue slag was completely dissolved with the H2SO4-HF under the condition of the F/Si mole ratio of 4.2： 1.0, the liquid-solid ratio of 3： 1, and 2 N sulfuric acid for 5 h at 80 ℃. Almost all of the indium and part of iron were extracted with 30% bis（2-ethylhexyl）hydrogen phosphate-kerosene from the first leaching solution at pH 2.0 2.2, and stripping with 2 N hydrochloric acid from the loaded organic phase, 98.28% of indium and 2.79% of iron were stripped , the separation of indium from iron was realized. And then extracting with the organic phase of 3 % hydroximic acids ＋ 10% bis （2-ethylhexyl） hydrogen phosphate-kerosene from the raffinate of indium-extraction, above 90% of germanium, gallium and iron were extracted for one tim

关 键 词：锗镓提取 置换渣 二氧化硅基体中锗的溶出 锗镓溶剂萃取 

分 类 号：O614.37[理学—无机化学]