硝酸-磷酸混合溶液中钨的萃取
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摘要
对比研究不同萃取体系下硝酸-磷酸混合溶液中钨的萃取-反萃行为,从萃取效率、分相程度及反萃效率等方面考虑选取仲碳伯胺萃取剂N_(1923)作为钨的萃取剂,系统研究N_(1923)对钨的萃取-反萃行为,确定了最佳的萃取/反萃工艺参数。在最优工艺参数下处理配制含有磷钨酸的硝酸-磷酸混合溶液,即在20%N_(1923)(体积分数)+磺化煤油组成的有机相体系、相比1:1、温度20℃、接触时间10 min的条件下,钨萃取率高达99.9%;反萃率条件为:温度50℃、相比2:1、氨水浓度12.5%(质量分数)、接触时间10 min,钨单级反萃率可达93.5%。在优化条件下萃取硝酸-磷酸混合溶液浸出白钨矿的实际料液,钨的萃取率达到99.9%以上,反萃时通过提高相比和氨水浓度的手段,使反萃液中WO_3浓度提高到200g/L以上,反萃率达到98%以上。
The extraction behavior of tungsten in nitric acid-phosphoric acid mixed solution was examined with different extraction agents. The results indicate that extraction agent secondary amine extractant N_(1923) has a satisfied extraction and stripping efficiency of tungsten. Then, the extracting and stripping process of tungsten by N_(1923) was investigated. During the extracting process, over 99.9% tungsten can be extracted under 20% N_(1923)(volume fraction) in organic phase system, phase ratio 1:1, temperature 20 ℃ and contact time 10 min. During the stripping process, over 93.5% tungsten loaded on organic phase is stripped with 12.5% ammonium hydroxide under the conditions of phase ratio 2:1, temperature 50 ℃ and contact time 10 min. Based on the research of extracting tungsten from simulate leach solution of scheelite concentrates, N_(1923) is used to treat the leach solution of scheelite concentrates which is digested by nitric acid phosphate mixture. The applications show that 99.9% tungsten is extracted and a relatively high concentration of ammonium tungstate solution(WO_3 is over 200 g/L) can be obtained through increasing phase ratio and ammonium hydroxide concentration with a satisfied stripping efficiency of 98%.
The extraction behavior of tungsten in nitric acid-phosphoric acid mixed solution was examined with different extraction agents. The results indicate that extraction agent secondary amine extractant N_(1923) has a satisfied extraction and stripping efficiency of tungsten. Then, the extracting and stripping process of tungsten by N_(1923) was investigated. During the extracting process, over 99.9% tungsten can be extracted under 20% N_(1923)(volume fraction) in organic phase system, phase ratio 1:1, temperature 20 ℃ and contact time 10 min. During the stripping process, over 93.5% tungsten loaded on organic phase is stripped with 12.5% ammonium hydroxide under the conditions of phase ratio 2:1, temperature 50 ℃ and contact time 10 min. Based on the research of extracting tungsten from simulate leach solution of scheelite concentrates, N_(1923) is used to treat the leach solution of scheelite concentrates which is digested by nitric acid phosphate mixture. The applications show that 99.9% tungsten is extracted and a relatively high concentration of ammonium tungstate solution(WO_3 is over 200 g/L) can be obtained through increasing phase ratio and ammonium hydroxide concentration with a satisfied stripping efficiency of 98%.
引文
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[4]MARTIN J P.Kinetics of soda ash leaching of low-grade scheelite concentrates[J].Hydrometallurgy,1996,42:221-236.
[5]LI Hong-gui.Production of high purity APT from scheelite and complex tungsten raw material with high Mo content[J].Transactions of Nonferrous Metals Society of China,2004,14(2):367-369.
[6]CHEN Min,LI Zhao,LI Xue-wei,QU Jun,ZHANG Qi-wu.Mechanochemically extracting tungsten through caustic processing of scheelite by controlling calcium dissolution[J].International Journal of Refractory Metals and Hard Materials,2016,58:211-215.
[7]万林生,邓登飞,赵立夫,李红超,徐国钻,梁勇.钨绿色冶炼工艺研究方向和技术进展[J].有色金属科学与工程,2013,4(5):15-18.WAN Lin-sheng,DENG Deng-fei,ZHAO Li-fu,LI Hong-cha,XU Guo-zuan,LIANG Yong.Research direction and technical progress of green tungsten metallurgy[J].Nonferrous Metals Science and Engineering,2013,4(5):15-18.
[8]ZHAO Zhong-wei,LI Jiang-tao,WANG Shi-bo,LI Hong-gui,LIU Mao-sheng,SUN Pei-mei,LI Yun-jiao.Extracting tungsten from scheelite concentrate with caustic soda by autoclaving process[J].Hydrometallurgy,2011,108:152-156.
[9]ZHANG Wen-juan,YANG Jin-hong,ZHAO Zhong-wei,WANGWen-qiang,LI Jiang-tao.Coordination leaching of tungsten from scheelite concentrate with phosphorus in nitric acid[J].J Cent South Univ,2016,23:1312-1317.
[10]ZHANG Wen-juan,LI Jiang-tao,ZHAO Zhong-wei.Leaching kinetics of scheelite with nitric acid and phosphoric acid[J].International Journal of Refractory Metals and Hard Materials,2015,52:78-84.
[11]ZHAO Zhong-wei,HU Fang,HU Yu-jie,WANG Shi-bo,SUNPei-mei,HUO Guang-sheng,LI Hong-gui.Adsorption behaviour of WO42-onto 201×7 resin in highly concentrated tungstate solutions[J].International Journal of Refractory Metals and Hard Materials,2010,28(5):633-637.
[12]李洪桂,羊建高,李昆.钨冶金学[M].长沙:中南大学出版社,2010:155-200.LI Hong-gui,YANG Jian-gao,LI Kun.Tungsten metallurgy[M].Changsha:Central South University Industry Press,2010:155-200.
[13]关文娟,张贵清.用季铵盐从模拟钨矿苏打浸出液中直接萃取钨[J].中国有色金属学报,2011,21(7):1757-1762.GUAN Wen-juan,ZHANG Gui-qing.Extraction of tungsten from simulated autoclave-soda leaching liquor of scheelite with quaternary ammonium salt[J].The Chinese Journal of Nonferrous Metals,2011,21(7):1757-1762.
[14]陈世梁,张贵清,肖连生,关文娟.采用HCO3--CO32-混合型季铵盐从模拟钨矿苏打高压浸出液中萃取钨[J].中国有色金属学报,2014,24(12):3155-3160.CHEN Shi-liang,ZHANG Gui-qing,XIAO Lian-sheng,GUANWen-juan.Extraction of tungsten from simulated autoclave-soda leaching liquor of tungsten ore with quaternary ammonium salt of bicarbonate and carbonate[J].The Chinese Journal of Nonferrous Metals,2014,24(12):3155-3160.
[15]YANG Yue,XIE Bo-yi,WANG Rui-xiang,XU Sheng-ming,WANG Jian-long,XU Zheng-he.Extraction and separation of tungsten from acidic high-phosphorus solution[J].Hydrometallurgy,2016,164:97-102.
[16]LIAO Yu-long,ZHAO Zhong-wei.Effects of phosphoric acid and ageing time on solvent extraction behavior of phosphotungstic acid[J].Hydrometallurgy,2017,169:515-519.
[17]廖宇龙.高钼白钨中矿酸性化学选矿浸出液的钨钼萃取研究[D].长沙:中南大学,2011:35-37.LIAO Yu-long.Solvent extraction of tungsten and molybdenum from chemical beneficiation acid leach solution of scheelite middling with high content of molybdenum[D].Changsha:Central South University,2011:35-37.
[18]张启修,张贵清,唐瑞仁.萃取冶金原理与实践[M].长沙:中南大学出版社,2014:294-295.ZHANG Qi-xiu,ZHANG Gui-qing,TANG Rui-ren.Fundamentals and practice of solvent extraction in hydrometallurgy[M].Changsha:Central South University Press,2014:294-295.
[19]柯兆华,张贵清,关文娟,尚广浩.季铵盐从碱性钨酸钠溶液中萃取钨的研究[J].稀有金属与硬质合金,2012,40(6):1-4.KE Zhao-hua,ZHANG Gui-qing,GUAN Wen-juan,SHANGGuang-hao.Research on tungsten extraction from alkali sodium tungstate solution with quaternary ammonium salt[J].Rare Metals and Cemented Carbides,2012,40(6):1-4.
[2]赵中伟.钨冶炼的理论与应用[M].北京:清华大学出版社,2013:10-20.ZHAO Zhong-wei.Tungsten metallurgy:Fundamentals and applications[M].Beijing:Tsinghua University Press,2013:10-20.
[3]RAJ P S.Modern hydrometallurgical production methods for tungsten[J].JOM,2006,58:45-49.
[4]MARTIN J P.Kinetics of soda ash leaching of low-grade scheelite concentrates[J].Hydrometallurgy,1996,42:221-236.
[5]LI Hong-gui.Production of high purity APT from scheelite and complex tungsten raw material with high Mo content[J].Transactions of Nonferrous Metals Society of China,2004,14(2):367-369.
[6]CHEN Min,LI Zhao,LI Xue-wei,QU Jun,ZHANG Qi-wu.Mechanochemically extracting tungsten through caustic processing of scheelite by controlling calcium dissolution[J].International Journal of Refractory Metals and Hard Materials,2016,58:211-215.
[7]万林生,邓登飞,赵立夫,李红超,徐国钻,梁勇.钨绿色冶炼工艺研究方向和技术进展[J].有色金属科学与工程,2013,4(5):15-18.WAN Lin-sheng,DENG Deng-fei,ZHAO Li-fu,LI Hong-cha,XU Guo-zuan,LIANG Yong.Research direction and technical progress of green tungsten metallurgy[J].Nonferrous Metals Science and Engineering,2013,4(5):15-18.
[8]ZHAO Zhong-wei,LI Jiang-tao,WANG Shi-bo,LI Hong-gui,LIU Mao-sheng,SUN Pei-mei,LI Yun-jiao.Extracting tungsten from scheelite concentrate with caustic soda by autoclaving process[J].Hydrometallurgy,2011,108:152-156.
[9]ZHANG Wen-juan,YANG Jin-hong,ZHAO Zhong-wei,WANGWen-qiang,LI Jiang-tao.Coordination leaching of tungsten from scheelite concentrate with phosphorus in nitric acid[J].J Cent South Univ,2016,23:1312-1317.
[10]ZHANG Wen-juan,LI Jiang-tao,ZHAO Zhong-wei.Leaching kinetics of scheelite with nitric acid and phosphoric acid[J].International Journal of Refractory Metals and Hard Materials,2015,52:78-84.
[11]ZHAO Zhong-wei,HU Fang,HU Yu-jie,WANG Shi-bo,SUNPei-mei,HUO Guang-sheng,LI Hong-gui.Adsorption behaviour of WO42-onto 201×7 resin in highly concentrated tungstate solutions[J].International Journal of Refractory Metals and Hard Materials,2010,28(5):633-637.
[12]李洪桂,羊建高,李昆.钨冶金学[M].长沙:中南大学出版社,2010:155-200.LI Hong-gui,YANG Jian-gao,LI Kun.Tungsten metallurgy[M].Changsha:Central South University Industry Press,2010:155-200.
[13]关文娟,张贵清.用季铵盐从模拟钨矿苏打浸出液中直接萃取钨[J].中国有色金属学报,2011,21(7):1757-1762.GUAN Wen-juan,ZHANG Gui-qing.Extraction of tungsten from simulated autoclave-soda leaching liquor of scheelite with quaternary ammonium salt[J].The Chinese Journal of Nonferrous Metals,2011,21(7):1757-1762.
[14]陈世梁,张贵清,肖连生,关文娟.采用HCO3--CO32-混合型季铵盐从模拟钨矿苏打高压浸出液中萃取钨[J].中国有色金属学报,2014,24(12):3155-3160.CHEN Shi-liang,ZHANG Gui-qing,XIAO Lian-sheng,GUANWen-juan.Extraction of tungsten from simulated autoclave-soda leaching liquor of tungsten ore with quaternary ammonium salt of bicarbonate and carbonate[J].The Chinese Journal of Nonferrous Metals,2014,24(12):3155-3160.
[15]YANG Yue,XIE Bo-yi,WANG Rui-xiang,XU Sheng-ming,WANG Jian-long,XU Zheng-he.Extraction and separation of tungsten from acidic high-phosphorus solution[J].Hydrometallurgy,2016,164:97-102.
[16]LIAO Yu-long,ZHAO Zhong-wei.Effects of phosphoric acid and ageing time on solvent extraction behavior of phosphotungstic acid[J].Hydrometallurgy,2017,169:515-519.
[17]廖宇龙.高钼白钨中矿酸性化学选矿浸出液的钨钼萃取研究[D].长沙:中南大学,2011:35-37.LIAO Yu-long.Solvent extraction of tungsten and molybdenum from chemical beneficiation acid leach solution of scheelite middling with high content of molybdenum[D].Changsha:Central South University,2011:35-37.
[18]张启修,张贵清,唐瑞仁.萃取冶金原理与实践[M].长沙:中南大学出版社,2014:294-295.ZHANG Qi-xiu,ZHANG Gui-qing,TANG Rui-ren.Fundamentals and practice of solvent extraction in hydrometallurgy[M].Changsha:Central South University Press,2014:294-295.
[19]柯兆华,张贵清,关文娟,尚广浩.季铵盐从碱性钨酸钠溶液中萃取钨的研究[J].稀有金属与硬质合金,2012,40(6):1-4.KE Zhao-hua,ZHANG Gui-qing,GUAN Wen-juan,SHANGGuang-hao.Research on tungsten extraction from alkali sodium tungstate solution with quaternary ammonium salt[J].Rare Metals and Cemented Carbides,2012,40(6):1-4.