双氧水配合TRPO/TBP萃取分离钨钼的工业试验  

Industrial Test of Solvent Extraction Separation of Mo and W by H2O2-Complexation with TRPO / TBP

作　　者：关文娟[1,2] 张贵清[1,2] 肖连生[1,2] 张启修[1,2] 李晓宇 张互标 

机构地区：[1]中南大学冶金与环境学院冶金分离科学与工程实验室,湖南长沙410083 [2]中南大学难冶有色金属资源高效利用国家工程实验室,湖南长沙410083 [3]洛阳栾川钼业集团股份有限公司,河南洛阳471500

出　　处：《稀有金属》2015年第11期1030-1037,共8页Chinese Journal of Rare Metals

基　　金：国家水体污染控制与治理重大专项(2010ZX07212-008)资助

摘　　要：以双氧水(H_2O_2)为配合剂,采用混合萃取剂三烷基氧膦(TRPO)和磷酸三丁酯(TBP)从含WO3110~150 g·L^(-1)、Mo/WO_3(质量比)10%~15%的高钼钨酸铵溶液中萃取分离钨钼,负载有机相用NH_4HCO_3溶液选择性反萃Mo。在萃取-反萃取试验研究的基础上进行工业试验,利用kremser方程确定了平衡p H值、萃取级数和W,Mo萃取率之间的关系,提出了中间级加酸调p H值的2段式逆流萃取、2段式反萃取等新的工艺改进措施,在优化条件下长时间运转以考察新工艺的稳定性,并进行技术经济成本分析。结果表明:有机相组成(体积分数)为3%TRPO+70%TBP+27%磺化煤油,有机相流量为100 L·h-1,料液中含WO_3110~150 g·L^(-1),Mo/WO_3(质量比)10%~15%,优化试验条件下得到的萃余液中WO_3质量浓度为126~151 g·L^(-1),Mo质量浓度为0.0019~0.0120 g·L^(-1),Mo/WO_3质量比小于0.9×10^(-4);新工艺连续运转21个月,萃余液和反萃液质量稳定、有机相循环性能好、系统运行状况平稳;萃余液中Mo含量满足制备0级仲钨酸铵(APT)产品的需求。新工艺在处理高钼含钨溶液时,具有除Mo彻底、W收率高、Mo产品附加值高、成本低和清洁环保等优点。工业试验结果证明新工艺已具备产业化应用条件。The solvent extraction separation of molybdenum （Mo） and tungsten （W） was carried out from ammonium molybdate solution containing Mo/WO3 of 10%- 15% （ mass ratio） and WO3 110 - 150 g·L-1 using a mixture of tri-alkyl phosphine oxide （TRPO） and tributyl phosphate （TBP） as extractant and hydrogen peroxide （H2O2 ） as complex agent. The molybdenum was selectively stripped from loaded organic phase with ammonium bicarbonate （NH4HCO3 ） solution. The industrial test was carried out based on the study of extraction-stripping experiment. The relationship among equilibrium pH, extraction stages and the extraction rate of molybdenum and tungsten was defined by kremser equation. The improved measurements including methods of the process of 2-section countercurrent extraction with acid regulation in one of the middle stage and the process of 2-section stripping were proposed. The stability of the new technology was investigated by a long time-running test under the optimized conditions and the economic cost of the technology was analyzed. The result indicated that the concentration of WO3 was 126- 151 g·L - 1, the concentration of Mo was 0. 0019 - 0.0120 g·L-1, and the Mo/WO3 （mass ratio） was less than 0.9 × 10^-4 in the raffinate under the optimized conditions that the organic phase composition（ volume fraction） was 3% TRPO ＋ 70% TBP ＋ 27% sulfonated kerosene, the flow rate of organic phase was 100 L·h-1, and the concentration of WO3 was 110 - 150 g·L-1 and the Mo/WO3 （ mass ratio） was 10%- 15% in the feed solution. The industrial test was successfully and continuously running for about 21 months. The quality of raffinate and stripping liquor were stable, the cycling property of organic phase was good and the running status of the system was stable in the industrial test. The impurity Mo content in the raffinate could fully meet the requirements for producing ammonium paratungstate （APT） of the 0 grade national standards of China. The new technology provided obvious advant

关 键 词：钨 钼 萃取分离 TRPO TBP H2O2 

分 类 号：TF841.1[冶金工程—有色金属冶金]