Application of ceramic membranes in the defluorination washing process of niobium hydroxide powders

doi:10.16085/j.issn.1000-6613.2023-0142

Abstract

Abstract:

To address the problems of intensive water consumption and high production of ammonia-containing wastewater in the defluorination washing process of niobium hydroxide powders, a ceramic membrane-based technology and process for niobium hydroxide powder washing was developed. The effects of membrane pore size, washing sequence and washing liquid usage on the removal of F^- impurities from niobium hydroxide slurry were investigated. The final product purity and economic efficiency were compared between the ceramic membrane-based and the traditional pressure filter-based methods. The results showed that constant volume diafiltration washing was the best way for removing F^- in niobium hydroxide slurry. When the ratio of material to washing liquid was 1∶60kg/L, the F^- content in normal niobium hydroxide slurry reached the standard by using the α-Al₂O₃ ceramic membrane with a pore size of 200nm. The α-Al₂O₃ ceramic membrane with a pore size of 50nm could efficiently wash the ultra-fine niobium hydroxide powder. Both ceramic membranes indicated good stability in the application of niobium hydroxide powder washing. The ceramic membrane-based washing method showed excellent purification effect on niobium hydroxide as well as the final product Nb₂O₅. The method was obviously better than the pressure filter-based method in terms of removal impurities and saving operation cost. Therefore, the ceramic membrane-based washing process offered high technical and economic feasibility for promoting the green development of tantalum-niobium hydrometallurgy.

Key words: alumina, ceramic membrane, niobium hydroxide, powders, washing

摘要：

针对氢氧化铌粉体脱氟洗涤过程耗水量大、含氨废水产量高的问题，本文开发了基于陶瓷膜的氢氧化铌粉体洗涤技术与工艺。考察了膜孔径、洗涤方式、洗涤液用量等参数对氢氧化铌浆料脱氟（F^-）效果的影响；在最终五氧化二铌（Nb₂O₅）产品纯度以及经济性方面对比了陶瓷膜法与传统压滤法洗涤氢氧化铌粉体工艺的不同。结果表明，恒体积渗滤洗涤方式对于去除氢氧化铌浆料中F^-效果最好。采用200nm膜孔径的α-Al₂O₃陶瓷膜，当料液比为1∶60kg/L时，常规氢氧化铌浆料中F^-含量达标，50nm孔径的α-Al₂O₃陶瓷膜可以对超细氢氧化铌粉体实现高效洗涤，两种膜在氢氧化铌粉体洗涤应用中均展现出较好的稳定性。陶瓷膜洗涤法对氢氧化铌及其最终产品Nb₂O₅的除杂效果显著，且在降低成本方面均明显优于压滤洗涤法。因此，基于陶瓷膜的洗涤工艺具有较高的技术与经济可行性，将有力促进我国钽铌湿法冶金绿色化发展。

关键词: 氧化铝, 陶瓷膜, 氢氧化铌, 粉体, 洗涤

CLC Number:

LE Jianfeng, WANG Fan, XU Nan, WANG Yongda, WANG Yuxuan, NIAN Pei, LI Hui, ZHANG Weining, WEI Yibin. Application of ceramic membranes in the defluorination washing process of niobium hydroxide powders[J]. Chemical Industry and Engineering Progress, 2023, 42(12): 6218-6225.

乐剑峰, 王帆, 徐楠, 王永达, 王雨轩, 年佩, 李辉, 张伟宁, 魏逸彬. 陶瓷膜在氢氧化铌粉体脱氟洗涤工艺的应用[J]. 化工进展, 2023, 42(12): 6218-6225.

Figures/Tables 9

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杂质	陶瓷膜洗涤/mg·L^-1	压滤洗涤/mg·L^-1
Ta	100	100
Fe	12	5
Cr	<3	<3
Ni	<3	<3
Si	33	19
Ti	<3	<3
Al	10	<3
Mn	<3	<3
Mo	<10	<10
Cu	<3	<3
Zr	<3	<3
Ca	5	5
Mg	10	3
Sn	<3	<3
As	10	10
Sb	40	41
Bi	3	3
Pb	<3	<3
F	100	220

杂质	陶瓷膜洗涤/mg·L^-1	压滤洗涤/mg·L^-1
Ta	100	100
Fe	12	5
Cr	<3	<3
Ni	<3	<3
Si	33	19
Ti	<3	<3
Al	10	<3
Mn	<3	<3
Mo	<10	<10
Cu	<3	<3
Zr	<3	<3
Ca	5	5
Mg	10	3
Sn	<3	<3
As	10	10
Sb	40	41
Bi	3	3
Pb	<3	<3
F	100	220

洗涤方法	浆料	膜孔径 /nm	料液比 /kg·L^-1	氢氧化铌F^-质量分数/%	洗涤时间/h	是否合格
压滤法	浆料1	—	1∶180	0.026	3.5	是
陶瓷膜法1	浆料1	200	1∶40	0.17	3.5	否
陶瓷膜法2	浆料1	200	1∶60	0.034	4	是
陶瓷膜法3	浆料1	200	1∶80	0.031	4.5	是
陶瓷膜法4	浆料2	50	1∶60	0.045	4	是

洗涤方法	浆料	膜孔径 /nm	料液比 /kg·L^-1	氢氧化铌F^-质量分数/%	洗涤时间/h	是否合格
压滤法	浆料1	—	1∶180	0.026	3.5	是
陶瓷膜法1	浆料1	200	1∶40	0.17	3.5	否
陶瓷膜法2	浆料1	200	1∶60	0.034	4	是
陶瓷膜法3	浆料1	200	1∶80	0.031	4.5	是
陶瓷膜法4	浆料2	50	1∶60	0.045	4	是

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