钕铁硼废料(NH_4)_2SO_4焙烧法回收稀土
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摘要
将钕铁硼废料与(NH_4)_2SO_4混合后焙烧,选择性回收钕铁硼废料中的稀土成分。采用单因素控制变量的方法对焙烧过程中的焙烧温度、焙烧时间、钕铁硼与(NH_4)_2SO_4混料质量比进行研究,结合稀土、铁等浸出率的影响,结果表明:焙烧温度400℃,焙烧时间120 min,钕铁硼与(NH_4)_2SO_4混料质量比1∶2,该条件下稀土可以获得较高的浸出率,约为92%,而Fe的浸出率仅为3%。通过对原料和焙烧后的产物进行热力学、扫描电镜、 X射线衍射和热重差热分析,综合分析得知钕铁硼废料中的主要成分REFeO_3, Fe_2O_3, RE_2O_3和Al_2O_3等发生硫酸化反应,生成RE_2(SO_4)_3和(NH_4)_3Fe(SO_4)_3及(NH_4)Al(SO_4)_2等。升高温度不利于REFeO_3的反应,从而抑制大部分Fe的硫酸化。经过焙烧,稀土以可溶性硫酸盐的形式存在,铁铝等杂质保持一个低的浸出率大部分留在渣中。
Rare earth elements was selectively recovered from NdFeB waste after mixed and roasted with ammonium sulfate. The single-factor controlled variable method was used to study the roasting temperature, roasting time, and the mass ratio of NdFeB mixed with ammonium sulfate, associated with the influence of rare earth and iron extraction. The results showed that under the condition of 400 ℃ roasting temperature, 120 min roasting time, 1∶2 of the NdFeB and ammonium sulfate mixing ratio, the rare earth extraction can be obtained as high as 92%, while the extraction of Fe is only 3%. By using thermal mechanical, electron microscope scanning, X-ray diffraction thermo-gravimetric and differential thermal analysis to study raw and roasting product, the comprehensive analysis showed that the main components of NdFeB wastes such as REFeO_3, Fe_2O_3, RE_2O_3 and Al_2O_3 were sulfated, and RE_2(SO_4)_3,(NH_4)_3Fe(SO_4)_3 and(NH_4)Al(SO_4)_2 were generated. The increase of temperature was not beneficial to the reaction of REFeO_3, and thus inhibited the sulfation of most Fe. After roasting, the rare earth existed in the form of soluble sulphate, and the impurities such as iron and aluminum remained a low extraction and mostly in the slag.
Rare earth elements was selectively recovered from NdFeB waste after mixed and roasted with ammonium sulfate. The single-factor controlled variable method was used to study the roasting temperature, roasting time, and the mass ratio of NdFeB mixed with ammonium sulfate, associated with the influence of rare earth and iron extraction. The results showed that under the condition of 400 ℃ roasting temperature, 120 min roasting time, 1∶2 of the NdFeB and ammonium sulfate mixing ratio, the rare earth extraction can be obtained as high as 92%, while the extraction of Fe is only 3%. By using thermal mechanical, electron microscope scanning, X-ray diffraction thermo-gravimetric and differential thermal analysis to study raw and roasting product, the comprehensive analysis showed that the main components of NdFeB wastes such as REFeO_3, Fe_2O_3, RE_2O_3 and Al_2O_3 were sulfated, and RE_2(SO_4)_3,(NH_4)_3Fe(SO_4)_3 and(NH_4)Al(SO_4)_2 were generated. The increase of temperature was not beneficial to the reaction of REFeO_3, and thus inhibited the sulfation of most Fe. After roasting, the rare earth existed in the form of soluble sulphate, and the impurities such as iron and aluminum remained a low extraction and mostly in the slag.
引文
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[10] 尹小文, 刘敏, 赖伟鸿, 董传博, 岳明, 索红莉. 草酸盐沉淀法回收钕铁硼废料中稀土元素的研究 [J]. 稀有金属, 2014, 38(6): 1094.Yin X W, Liu M, Lai W H, Dong C B, Yue M, Suo H L. Recycle rare earth elements from NdFeB waste with oxalate precipitation method [J]. Chinese Journal of Rare Metals, 2014, 38(6): 1094.
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[12] 刘欣伟, 冯雅丽, 李浩然, 蔡震雷, 杨志超. 硫酸铵焙烧法浸出镍磁黄铁矿中有价金属 [J]. 中国有色金属学报, 2012, 22(5): 1520.Liu X W, Feng Y L, Li H R, Cai Z L, Yang Z C. Leaching of valuable metals from nickel pyrrhotite by ammonium sulfate roasting method [J]. The Chinese Journal of Nonferrous Metals, 2012, 22(5): 1520.
[13] 彭兵, 李燕春, 柴立元, 刘恢, 闵小波, 胡明, 袁莹珍, 雷杰, 彭宁. 锌浸渣硫酸铵焙烧-选择性浸出回收锌 [J] . 中国有色金属学报, 2015, 25(9): 2596.Peng B, Li Y C, Chai L Y, Liu H, Min X B, Hu M, Yuan Y Z, Lei J, Peng N. Recovery of zinc from zinc leaching residue by ammonia sulfate roasting-selective leaching [J]. The Chinese Journal of Nonferrous Metals, 2015, 25(9): 2596.
[14] 刘科伟, 陈天朗. 硫酸铵的热分解 [J]. 化学研究与应用, 2002, 14(6): 737.Liu K W, Chen T L. Studies on the thermal decomposition of ammonium sulfate [J]. Chemical Research and Application, 2002, 14(6): 737.
[15] 范芸珠, 曹发海. 硫酸铵热分解反应动力学研究 [J]. 高校化学工程学报, 2011, 25(2): 341.Fan Y Z, Cao F H. Thermal decomposition kinetics of ammonium sulfate [J]. Journal of Chemical Engineering of Chinese Universities, 2011, 25(2): 341.
[16] 杨合, 武吉, 薛向欣, 张波, 李勇. 稀土矿硫酸铵焙烧法提取稀土 [J]. 稀土, 2017, 38(3): 16.Yang H, Wu J, Xue X X, Zhang B, Li Y. Extraction of rare earth from rare earth mine using ammonium sulfate roasting [J]. Chinese Rare Earths, 2017, 38(3): 16.
[17] 叶大伦, 胡建华. 实用无机物热力学数据手册 [M]. 北京: 冶金工业出版社, 2002.Ye D L, Hu J H. Practical Inorganic Thermodynamics Data Sheet [M]. Beijing: Metallurgical Industry Press, 2002.
[18] 林传仙, 白正华, 张哲儒. 矿物及有关化合物热力学数据手册 [M]. 北京: 科学出版社, 1985.Lin C X, Bai Z H, Zhang Z R. Minerals and Related Compounds Thermodynamic Data Sheet [M]. Beijing: Science Press, 1985.
[19] Sun Y, Shen X Y, Zhai Y C. Thermodynamics and kinetics of extracting zinc from zinc oxide ore by the ammonium sulfate roasting method [J]. Int. J. Min. Met. Mater., 2015, 22(5): 467.
[20] 杨合, 武吉, 薛向欣, 张波, 李勇. 硅酸盐稀土渣硫酸铵焙烧浸出研究 [J]. 中国稀土学报, 2015, 33(4): 440.Yang H, Wu J, Xue X X, Zhang B, Li Y. Roasting and leaching process of mixture of rare earth silicates slag and ammonium sulfate [J]. Journal of the Chinese Society of Rare Earths, 2015, 33(4): 440.
[21] Shao H M, Shen X Y, Sun Y. Reaction condition optimization and kinetic investigation of roasting zinc oxide ore using (NH_4)_2SO_4 [J]. Int. J. Min. Met. Mater., 2016, 23(10): 1133.
[22] 晋新亮, 彭同江, 孙洪娟. 硫酸铵焙烧法提取粉煤灰中氧化铝的工艺技术研究 [J]. 非金属矿, 2013, 36(2): 59.Jin X L, Peng T J, Sun H J. Techniques of alumina extraction from coal fly ash by ammonium sulfate activation [J]. Non-Metallic Mines, 2013, 36(2): 59.
[2] 林河成. 我国烧结钕铁硼永磁材料生产应用现状及发展前景 [J]. 稀土, 1999, 20(6): 70.Lin H C. Sintered NdFeB permanent magnet materials in China [J]. Chinese Rare Earths, 1999, 20(6): 70.
[3] 肖荣晖. 钕铁硼生产中废料的回收及利用 [J]. 有色冶炼, 2001, (1): 23.Xiao R H. Recovery and Utilization of Waste from Neodymium Ferroboron Production [J]. Nonferrous Smelting, 2001, (1): 23.
[4] 黄劲松, 齐美富. 钕铁硼废料资源化利用工艺综述 [J]. 中国资源综合利用, 2008, 26(11): 4.Huang J S, Qi M F. Review on recovery technology of Nd-Fe-B waste materials [J]. China Resources Comprehensive Utilization, 2008, 26(11): 4.
[5] 王毅军, 刘宇辉, 翁国庆, 李四勇, 刘荣丽, 王素玲. 盐酸优溶法回收钕铁硼废料中稀土元素的研究与生产 [J]. 稀有金属与硬质合金, 2007, 35(2): 26.Wang Y J, Liu Y H, Weng G Q, Li S Y, Liu R L, Wang S L. Study and practice of selective dissolution with HCl for the recovery of RE elements from NdFeB scrap [J]. Rare Metals and Cemented Carbides, 2007, 35(2): 26.
[6] 许涛, 李敏, 张春新. 钕铁硼废料中钕、 镝及钴的回收 [J]. 稀土, 2004, 25(2): 31.Xu T, Li M, Zhang C X. Reclamation of Nd,Dy and Co oxides from NdFeB scrap [J]. Chinese Rare Earths, 2004, 25(2): 31.
[7] 林河成. 利用钕铁硼废料制备氧化钕 [J]. 上海有色金属, 2006, 27(3): 17.Lin H C. Preparation of neodymium oxide from waste Nd-Fe-B material [J]. Shanghai Nonferrous Metals, 2006, 27(3): 17.
[8] 郝志平. 氟化物法回收钕铁硼稀土永磁废料 [P]. 中国专利: CN1077993A.1993.Hao Z P. Fluoride Recovery of NdFeB Permanent Magnetic Permanent Scrap [P]. China Patent: CN1077993A.1993.
[9] 张礼刚. 从钕铁硼废料中提取钕的方法 [P]. 中国专利: CN1058231, 1992.Zhang L G. Method for extracting thorium from neodymium iron boron waste [P]. China Patent: CN1058231, 1992.
[10] 尹小文, 刘敏, 赖伟鸿, 董传博, 岳明, 索红莉. 草酸盐沉淀法回收钕铁硼废料中稀土元素的研究 [J]. 稀有金属, 2014, 38(6): 1094.Yin X W, Liu M, Lai W H, Dong C B, Yue M, Suo H L. Recycle rare earth elements from NdFeB waste with oxalate precipitation method [J]. Chinese Journal of Rare Metals, 2014, 38(6): 1094.
[11] 张云芳, 李金辉, 高岩, 陈志峰, 廖春发. 红土镍矿的硫酸铵焙烧过程 [J]. 中国有色金属学报, 2017, 279(1): 157.Zhang Y F, Li J H, Gao Y, Chen Z F, Liao C F. Roasting process of nickel laterite using ammonium sulfate [J]. The Chinese Journal of Nonferrous Metals, 2017, 279(1): 157.
[12] 刘欣伟, 冯雅丽, 李浩然, 蔡震雷, 杨志超. 硫酸铵焙烧法浸出镍磁黄铁矿中有价金属 [J]. 中国有色金属学报, 2012, 22(5): 1520.Liu X W, Feng Y L, Li H R, Cai Z L, Yang Z C. Leaching of valuable metals from nickel pyrrhotite by ammonium sulfate roasting method [J]. The Chinese Journal of Nonferrous Metals, 2012, 22(5): 1520.
[13] 彭兵, 李燕春, 柴立元, 刘恢, 闵小波, 胡明, 袁莹珍, 雷杰, 彭宁. 锌浸渣硫酸铵焙烧-选择性浸出回收锌 [J] . 中国有色金属学报, 2015, 25(9): 2596.Peng B, Li Y C, Chai L Y, Liu H, Min X B, Hu M, Yuan Y Z, Lei J, Peng N. Recovery of zinc from zinc leaching residue by ammonia sulfate roasting-selective leaching [J]. The Chinese Journal of Nonferrous Metals, 2015, 25(9): 2596.
[14] 刘科伟, 陈天朗. 硫酸铵的热分解 [J]. 化学研究与应用, 2002, 14(6): 737.Liu K W, Chen T L. Studies on the thermal decomposition of ammonium sulfate [J]. Chemical Research and Application, 2002, 14(6): 737.
[15] 范芸珠, 曹发海. 硫酸铵热分解反应动力学研究 [J]. 高校化学工程学报, 2011, 25(2): 341.Fan Y Z, Cao F H. Thermal decomposition kinetics of ammonium sulfate [J]. Journal of Chemical Engineering of Chinese Universities, 2011, 25(2): 341.
[16] 杨合, 武吉, 薛向欣, 张波, 李勇. 稀土矿硫酸铵焙烧法提取稀土 [J]. 稀土, 2017, 38(3): 16.Yang H, Wu J, Xue X X, Zhang B, Li Y. Extraction of rare earth from rare earth mine using ammonium sulfate roasting [J]. Chinese Rare Earths, 2017, 38(3): 16.
[17] 叶大伦, 胡建华. 实用无机物热力学数据手册 [M]. 北京: 冶金工业出版社, 2002.Ye D L, Hu J H. Practical Inorganic Thermodynamics Data Sheet [M]. Beijing: Metallurgical Industry Press, 2002.
[18] 林传仙, 白正华, 张哲儒. 矿物及有关化合物热力学数据手册 [M]. 北京: 科学出版社, 1985.Lin C X, Bai Z H, Zhang Z R. Minerals and Related Compounds Thermodynamic Data Sheet [M]. Beijing: Science Press, 1985.
[19] Sun Y, Shen X Y, Zhai Y C. Thermodynamics and kinetics of extracting zinc from zinc oxide ore by the ammonium sulfate roasting method [J]. Int. J. Min. Met. Mater., 2015, 22(5): 467.
[20] 杨合, 武吉, 薛向欣, 张波, 李勇. 硅酸盐稀土渣硫酸铵焙烧浸出研究 [J]. 中国稀土学报, 2015, 33(4): 440.Yang H, Wu J, Xue X X, Zhang B, Li Y. Roasting and leaching process of mixture of rare earth silicates slag and ammonium sulfate [J]. Journal of the Chinese Society of Rare Earths, 2015, 33(4): 440.
[21] Shao H M, Shen X Y, Sun Y. Reaction condition optimization and kinetic investigation of roasting zinc oxide ore using (NH_4)_2SO_4 [J]. Int. J. Min. Met. Mater., 2016, 23(10): 1133.
[22] 晋新亮, 彭同江, 孙洪娟. 硫酸铵焙烧法提取粉煤灰中氧化铝的工艺技术研究 [J]. 非金属矿, 2013, 36(2): 59.Jin X L, Peng T J, Sun H J. Techniques of alumina extraction from coal fly ash by ammonium sulfate activation [J]. Non-Metallic Mines, 2013, 36(2): 59.
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