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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

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【作者】 关文娟张贵清肖连生张启修李晓宇张互标

【Author】 Guan Wenjuan;Zhang Guiqing;Xiao Liansheng;Zhang Qixiu;Li Xiaoyu;Zhang Hubiao;Laboratory of Metallurgical Separation Science and Engineering,School of Metallurgy and Environment,Central South University;National Engineering Laboratory for Efficient Utilization of Refractory Nonferrous Metals Resources,Central South University;China Molybdenum Co.,Ltd.;

【机构】 中南大学冶金与环境学院冶金分离科学与工程实验室中南大学难冶有色金属资源高效利用国家工程实验室洛阳栾川钼业集团股份有限公司

【摘要】 以双氧水(H2O2)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WO3110150 g·L-1、Mo/WO3(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NH4HCO3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WO3110150 g·L-1,Mo/WO3(质量比)10%15%,优化试验条件下得到的萃余液中WO3质量浓度为126151 g·L-1,Mo质量浓度为0.00190.0120 g·L-1,Mo/WO3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。

【Abstract】 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 WO3110 150 g·L-1using 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 p H,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. 0120g·L-1,and the Mo/WO3( mass ratio) was less than 0. 9 × 10- 4in 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-1and 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 advantages including deep Mo removing,high recovery of W and high added value of Mo product,low cost,clean and environmental friendliness in processing tungstate solution containing high Mo.

【关键词】 萃取分离TRPOTBPH2O2
【Key words】 tungstenmolybdenumsolvent extraction separationTRPOTBPH2O2
【基金】 国家水体污染控制与治理重大专项(2010ZX07212-008)资助
  • 【文献出处】 稀有金属 ,Chinese Journal of Rare Metals , 编辑部邮箱 ,2015年11期
  • 【分类号】TF841
  • 【被引频次】5
  • 【下载频次】410
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