钨湿法冶金工艺进展
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摘要
概述了钨湿法冶金中主流工艺的理论突破及其目前存在的工程技术方面的问题,综合分析我国钨矿资源、技术、环保政策等方面因素。介绍了中南大学开发的全新的钨冶金技术——白钨矿硫磷混酸协同分解技术。新技术可以解决目前钨湿法冶金所面临的这些问题,为新形势下促进我国钨工业健康发展提供了全新的思路。
The theoretical breakthrough of the mainstream technology in hydrometallurgy of tungsten and its existing problems in engineering and technology are summarized.The factors of China's tungsten resources,technology and environmental protection policies are also comprehensively analyzed.A new tungsten metallurgy technology,sulfuric-phosphoric mixed acid decomposition technology of scheelite,developed by Central South University is introduced.The new technology can solve these problems in the current tungsten hydrometallurgy.It provides a new way for promoting the healthy development of tungsten industry in China under the new situation.
The theoretical breakthrough of the mainstream technology in hydrometallurgy of tungsten and its existing problems in engineering and technology are summarized.The factors of China's tungsten resources,technology and environmental protection policies are also comprehensively analyzed.A new tungsten metallurgy technology,sulfuric-phosphoric mixed acid decomposition technology of scheelite,developed by Central South University is introduced.The new technology can solve these problems in the current tungsten hydrometallurgy.It provides a new way for promoting the healthy development of tungsten industry in China under the new situation.
引文
[1]何利华,赵中伟,杨金洪.新一代绿色钨冶金工艺——白钨硫磷混酸协同分解技术[J].中国钨业,2017,32(3):49-53.
[2]宁华.苏打压煮钨矿工艺及其发展[J].稀有金属与硬质合金,1996(4):44-48.
[3]PERLOV P M.Interaction of calcium tungstate with soda carbonate in the autoclave process[J].Obogashch Rud,1958,3(1):25-34.
[4]MARTINS J P.Soda ash leaching of scheelite concentrates:The effect of high concentration of sodium carbonate[J].Hydrometallurgy,1997,46:191-203.
[5]吴厚荣.复杂钨中矿的分解[J].中国有色冶金,1985(8):35-39.
[6]赵中伟,杨金洪.关于钨矿苏打压煮工艺几个理论问题的讨论[J].稀有金属与硬质合金,2002,30(2):1-3.
[7]AJIEKCEEB,李训诰.Na2O-CaO-CO2-H2O系中平衡过程的热力学和实验结果分析[J].轻金属,1986(1):16-19.
[8]PAYNE C M.Extraction of tungsten values from scheelite ores using a sequestering agent[J].New Zealand Journal of Science,1969,12(1):13-26.
[9]КAPOBЗГ.Регенерацияизбыточнойсодыизавтоклав-ныхщелокв[J].ЦветныеМеталлы,1989(6):94-98.
[10]URUSOVA M A,RAKOVA N N,VALYASHKO V M,et al.Na2WO4-Na2CO3-H2O system at 225℃[J].Zhurnal Neorganicheskoi Khimii,1978,23(2):553-555.
[11]赵中伟.钨冶炼的理论与应用[M].北京:清华大学出版社,2013:117-118.
[12]李洪桂,羊建高,李昆.钨冶金学[M].长沙:中南大学出版社,2010:101-102.
[13]张启修,赵秦生.钨钼冶金[M].北京:冶金工业出版社,2005:149-151.
[14]肖连生,张启修.膜电解法回收钨酸钠溶液中游离碱工业试验研究[J].膜科学与技术,2001,21(2):14-16.
[15]肖连生,王玮,张启修,等.钨酸钠溶液膜电解体系的阳极选择研究[J].膜科学与技术,2000,20(6):16-19.
[16]OSSEO-ASARE K.Solution chemistry of tungsten leaching systems[J].Metallurgical Transactions B,1992,21(1):555-564.
[17]李洪桂,刘茂盛,孙培梅,等.适应钨资源形势的变化开拓钨冶金的新工艺[J].中国钨业,1999(5):136-139.
[18]刘茂盛.碱法热球磨分解钨矿物专利技术综合介绍[J].中国钨业,1995(2):26-29.
[19]李洪桂,刘茂盛,思泽金,等.白钨精矿与黑白钨混合矿碱分解方法及设备:CN85100350A[P].1986-08-27.
[20]李洪桂,刘茂盛,孙培梅,等.白钨精矿与黑白钨混合矿碱分解的方法与设备[J].中国科学基金,1997(3):210-212.
[21]ZHAO Z,LI J,WANG S,et al.Extracting tungsten from scheelite concentrate with caustic soda by autoclaving process[J].Hydrometallurgy,2011,108(1):152-156.
[22]ZHAO Z,LI H.Thermodynamics for leaching of scheelite—Pseudo-ternary-system phase diagram and its application[J].Metallurgical&Materials Transactions B,2008,39(4):519-523.
[23]吴建国,柯家骏.白钨矿添加磷酸盐苛性碱浸取的热力学分析[J].过程工程学报,1987(3):1-6.
[24]李洪桂,孙培梅,刘茂盛,等.Na2WO4在NaOH-H2O系中的溶解度研究[J].中南矿冶学院学报,1991(6):644-649.
[25]彭泽田.高钙黑钨精矿的低压高碱浸取[J].中国钨业,1996(10):16-19.
[26]张启修,赵秦生.钨钼冶金[M].北京:冶金工业出版社,2005:127-129.
[27]罗军,袁喜振.溶剂萃取法提取钨研究现状[J].中国钨业,2017,32(2):56-59.
[28]张贵清,关文娟,张启修,等.从钨矿苏打浸出液中直接萃取钨的连续运转试验[J].中国钨业,2009,24(5):49-52.
[29]ВEPEBKИHГВ,杨阳.试论处理低品钨原料的合理工艺[J].中国钨业,1990(5):27-29.
[30]张贵清,张启修,张斌,等.从含钨物料苏打浸出液中离心萃取制取钨酸铵溶液的方法:CN101445275[P].2009-06-03.
[31]ZHANG G,GUAN W,XIAO L,et al.A novel process for tungsten hydrometallurgy based on direct solvent extraction in alkaline medium[J].Hydrometallurgy,2016,165:233-237.
[32]张贵清,张启修.一种钨湿法冶金清洁生产工艺[J].稀有金属,2003,27(2):254-257.
[33]廖春发,张启修.从钨矿苛性钠浸出液直接萃取钨时杂质锡行为的考察[J].江西理工大学学报,2001,22(4):239-242.
[34]胡兆瑞.离子交换法冶炼钨工艺的诞生和发展[J].中国钨业,1997(Z1):42-44.
[35]胡兆瑞,邬盛华,袁衍球.离子交换法在钨冶炼工业中的应用[J].中国有色冶金,1981(6):11-17,37.
[36]李会强,唐忠阳,何利华,等.离子交换技术在钨冶金中的应用与进展[J].中国钨业,2014(5):34-39.
[37]何传冰.提高201树脂对钨的交换容量的措施[J].稀有金属与硬质合金,1989(2):33-35.
[38]姜萍,徐迎春.离子交换解吸工艺的改进与实践[J].稀有金属与硬质合金,2001,1(1):47-49.
[39]徐迎春,姜萍.关于提高201×7型树脂对钨交换容量的研究[J].中国钨业,2000,15(3):36-37.
[40]马升灯.强碱性阴离子交换树脂在水中的热稳定性[J].浙江师范大学学报(自然科学版),1998(3):65-67.
[41]余腾海,王心灵,童长仁.离子交换法提取钨工艺的改进[J].有色金属(冶炼部分),1988(3):27-28.
[42]赵中伟.用于处理高浓度钨酸钠溶液的离子交换新工艺[J].中国钨业,2005,20(1):33-35.
[43]华宇闻.新标准为氯碱行业污染物排放套上紧箍咒[J].上海化工,2016,41(11):43.
[44]张鑫.中国政策环境对氯碱行业发展的影响分析[J].中国氯碱,2014(6):1-5.
[45]WOLOCHOW D.The manufacture of tungstic acid from scheelite[D].California:California Institute of Technology,1924:4-7.
[46]HE G,ZHAO Z,WANG X,et al.Leaching kinetics of scheelite in hydrochloric acid solution containing hydrogen peroxide as complexing agent[J].Hydrometallurgy,2014,144-145(4):140-147.
[47]ZHANG Wenjuan,YANG Jinhong,ZHAO Zhongwei,et al.Coordination leaching of tungsten from scheelite concentrate with phosphorus in nitric acid[J].Journal of Central South University,2016,23(6):1 312-1 317.
[48]XUIN G H,YU D Y,SU Y F.Leaching of scheelite by hydrochloric acid in the presence of phosphate[J].Hydrometallurgy,1986,16(1):27-40.
[49]赵中伟,李江涛.一种分解白钨矿的方法:CN102080157A[P].2011-06-01.
[50]ZHAO Zhongwei,LI Jiangtao.Method for extracting tungsten from scheelite:US8771617[P].2014-07-08.
[2]宁华.苏打压煮钨矿工艺及其发展[J].稀有金属与硬质合金,1996(4):44-48.
[3]PERLOV P M.Interaction of calcium tungstate with soda carbonate in the autoclave process[J].Obogashch Rud,1958,3(1):25-34.
[4]MARTINS J P.Soda ash leaching of scheelite concentrates:The effect of high concentration of sodium carbonate[J].Hydrometallurgy,1997,46:191-203.
[5]吴厚荣.复杂钨中矿的分解[J].中国有色冶金,1985(8):35-39.
[6]赵中伟,杨金洪.关于钨矿苏打压煮工艺几个理论问题的讨论[J].稀有金属与硬质合金,2002,30(2):1-3.
[7]AJIEKCEEB,李训诰.Na2O-CaO-CO2-H2O系中平衡过程的热力学和实验结果分析[J].轻金属,1986(1):16-19.
[8]PAYNE C M.Extraction of tungsten values from scheelite ores using a sequestering agent[J].New Zealand Journal of Science,1969,12(1):13-26.
[9]КAPOBЗГ.Регенерацияизбыточнойсодыизавтоклав-ныхщелокв[J].ЦветныеМеталлы,1989(6):94-98.
[10]URUSOVA M A,RAKOVA N N,VALYASHKO V M,et al.Na2WO4-Na2CO3-H2O system at 225℃[J].Zhurnal Neorganicheskoi Khimii,1978,23(2):553-555.
[11]赵中伟.钨冶炼的理论与应用[M].北京:清华大学出版社,2013:117-118.
[12]李洪桂,羊建高,李昆.钨冶金学[M].长沙:中南大学出版社,2010:101-102.
[13]张启修,赵秦生.钨钼冶金[M].北京:冶金工业出版社,2005:149-151.
[14]肖连生,张启修.膜电解法回收钨酸钠溶液中游离碱工业试验研究[J].膜科学与技术,2001,21(2):14-16.
[15]肖连生,王玮,张启修,等.钨酸钠溶液膜电解体系的阳极选择研究[J].膜科学与技术,2000,20(6):16-19.
[16]OSSEO-ASARE K.Solution chemistry of tungsten leaching systems[J].Metallurgical Transactions B,1992,21(1):555-564.
[17]李洪桂,刘茂盛,孙培梅,等.适应钨资源形势的变化开拓钨冶金的新工艺[J].中国钨业,1999(5):136-139.
[18]刘茂盛.碱法热球磨分解钨矿物专利技术综合介绍[J].中国钨业,1995(2):26-29.
[19]李洪桂,刘茂盛,思泽金,等.白钨精矿与黑白钨混合矿碱分解方法及设备:CN85100350A[P].1986-08-27.
[20]李洪桂,刘茂盛,孙培梅,等.白钨精矿与黑白钨混合矿碱分解的方法与设备[J].中国科学基金,1997(3):210-212.
[21]ZHAO Z,LI J,WANG S,et al.Extracting tungsten from scheelite concentrate with caustic soda by autoclaving process[J].Hydrometallurgy,2011,108(1):152-156.
[22]ZHAO Z,LI H.Thermodynamics for leaching of scheelite—Pseudo-ternary-system phase diagram and its application[J].Metallurgical&Materials Transactions B,2008,39(4):519-523.
[23]吴建国,柯家骏.白钨矿添加磷酸盐苛性碱浸取的热力学分析[J].过程工程学报,1987(3):1-6.
[24]李洪桂,孙培梅,刘茂盛,等.Na2WO4在NaOH-H2O系中的溶解度研究[J].中南矿冶学院学报,1991(6):644-649.
[25]彭泽田.高钙黑钨精矿的低压高碱浸取[J].中国钨业,1996(10):16-19.
[26]张启修,赵秦生.钨钼冶金[M].北京:冶金工业出版社,2005:127-129.
[27]罗军,袁喜振.溶剂萃取法提取钨研究现状[J].中国钨业,2017,32(2):56-59.
[28]张贵清,关文娟,张启修,等.从钨矿苏打浸出液中直接萃取钨的连续运转试验[J].中国钨业,2009,24(5):49-52.
[29]ВEPEBKИHГВ,杨阳.试论处理低品钨原料的合理工艺[J].中国钨业,1990(5):27-29.
[30]张贵清,张启修,张斌,等.从含钨物料苏打浸出液中离心萃取制取钨酸铵溶液的方法:CN101445275[P].2009-06-03.
[31]ZHANG G,GUAN W,XIAO L,et al.A novel process for tungsten hydrometallurgy based on direct solvent extraction in alkaline medium[J].Hydrometallurgy,2016,165:233-237.
[32]张贵清,张启修.一种钨湿法冶金清洁生产工艺[J].稀有金属,2003,27(2):254-257.
[33]廖春发,张启修.从钨矿苛性钠浸出液直接萃取钨时杂质锡行为的考察[J].江西理工大学学报,2001,22(4):239-242.
[34]胡兆瑞.离子交换法冶炼钨工艺的诞生和发展[J].中国钨业,1997(Z1):42-44.
[35]胡兆瑞,邬盛华,袁衍球.离子交换法在钨冶炼工业中的应用[J].中国有色冶金,1981(6):11-17,37.
[36]李会强,唐忠阳,何利华,等.离子交换技术在钨冶金中的应用与进展[J].中国钨业,2014(5):34-39.
[37]何传冰.提高201树脂对钨的交换容量的措施[J].稀有金属与硬质合金,1989(2):33-35.
[38]姜萍,徐迎春.离子交换解吸工艺的改进与实践[J].稀有金属与硬质合金,2001,1(1):47-49.
[39]徐迎春,姜萍.关于提高201×7型树脂对钨交换容量的研究[J].中国钨业,2000,15(3):36-37.
[40]马升灯.强碱性阴离子交换树脂在水中的热稳定性[J].浙江师范大学学报(自然科学版),1998(3):65-67.
[41]余腾海,王心灵,童长仁.离子交换法提取钨工艺的改进[J].有色金属(冶炼部分),1988(3):27-28.
[42]赵中伟.用于处理高浓度钨酸钠溶液的离子交换新工艺[J].中国钨业,2005,20(1):33-35.
[43]华宇闻.新标准为氯碱行业污染物排放套上紧箍咒[J].上海化工,2016,41(11):43.
[44]张鑫.中国政策环境对氯碱行业发展的影响分析[J].中国氯碱,2014(6):1-5.
[45]WOLOCHOW D.The manufacture of tungstic acid from scheelite[D].California:California Institute of Technology,1924:4-7.
[46]HE G,ZHAO Z,WANG X,et al.Leaching kinetics of scheelite in hydrochloric acid solution containing hydrogen peroxide as complexing agent[J].Hydrometallurgy,2014,144-145(4):140-147.
[47]ZHANG Wenjuan,YANG Jinhong,ZHAO Zhongwei,et al.Coordination leaching of tungsten from scheelite concentrate with phosphorus in nitric acid[J].Journal of Central South University,2016,23(6):1 312-1 317.
[48]XUIN G H,YU D Y,SU Y F.Leaching of scheelite by hydrochloric acid in the presence of phosphate[J].Hydrometallurgy,1986,16(1):27-40.
[49]赵中伟,李江涛.一种分解白钨矿的方法:CN102080157A[P].2011-06-01.
[50]ZHAO Zhongwei,LI Jiangtao.Method for extracting tungsten from scheelite:US8771617[P].2014-07-08.