陶瓷膜在氢氧化铌粉体脱氟洗涤工艺的应用

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

化工进展 ›› 2023, Vol. 42 ›› Issue (12): 6218-6225.DOI: 10.16085/j.issn.1000-6613.2023-0142

• 化工过程与装备 • 上一篇

陶瓷膜在氢氧化铌粉体脱氟洗涤工艺的应用

乐剑峰¹^,²(), 王帆³, 徐楠¹(), 王永达¹, 王雨轩¹, 年佩¹, 李辉², 张伟宁², 魏逸彬¹()

^1.宁夏大学化学化工学院煤炭高效利用与绿色化工国家重点实验室，宁夏银川 750021
^2.宁夏东方钽业股份有限公司，宁夏石嘴山 753000
^3.宁夏圆惠环保科技有限公司，宁夏银川 750299

收稿日期:2023-02-06 修回日期:2023-04-07 出版日期:2023-12-25 发布日期:2024-01-08
通讯作者: 徐楠,魏逸彬
作者简介:乐剑峰（1990—），男，工程师，研究方向为钽铌湿法冶金。E-mail：121205956@qq.com。
基金资助:
宁夏重点研发项目(2022BED92038);宁夏东方钽业股份有限公司委托技术开发项目(2020019)

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

LE Jianfeng¹^,²(), WANG Fan³, XU Nan¹(), WANG Yongda¹, WANG Yuxuan¹, NIAN Pei¹, LI Hui², ZHANG Weining², WEI Yibin¹()

^1.State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering, School of Chemistry and Chemical Engineering, Ningxia University, Yinchuan 750021, Ningxia, China
^2.Ningxia Orient Tantalum Industry Co. , Ltd. , Shizuishan 753000, Ningxia, China
^3.Ningxia Yuanhui Environmental Protection Technology Co. , Ltd. , Yinchuan 750299, Ningxia, China

Received:2023-02-06 Revised:2023-04-07 Online:2023-12-25 Published:2024-01-08
Contact: XU Nan, WEI Yibin

摘要/Abstract

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

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

中图分类号:

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.

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.

图/表 9

图1 陶瓷膜实验装置示意图1—料液罐；2—泵；3—流量计；4—膜组件；5—阀门；6—温度计；7—压力表

图2 不同孔径陶瓷膜对氢氧化铌浆料1在不同固含量时的渗透通量

图3 不同洗涤流程下洗涤液用量与粗氢氧化铌浆料中F-浓度的关系

图4 不同固含量氢氧化铌浆料1的渗透率随时间的变化关系

图5 压滤洗涤工艺与陶瓷膜洗涤工艺对比图

图6 氢氧化铌浆料洗涤前后的粒度分析图

图7 不同洗涤工艺最终Nb2O5产品的SEM形貌图

表1 不同洗涤工艺得到的Nb2O5产品杂质分析

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

表2 洗涤工艺比较

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

参考文献 26

1	薛冬峰, 刘美男, 贺祥珂, 等. 工业级五氧化二铌粉体物相转变技术[J]. 无机盐工业, 2005, 37(6): 23-24.
	XUE Dongfeng, LIU Meinan, HE Xiangke, et al. Material phase transitions technology of industrial grade Nb₂O₅ powders[J]. Inorganic Chemicals Industry, 2005, 37(6): 23-24.
2	ZHAO Yun, ELEY Clive, HU Jingping, et al. Shape-dependent acidity and photocatalytic activity of Nb₂O₅ nanocrystals with an active TT (001) surface[J]. Angewandte Chemie International Edition, 2012, 51(16): 3846-3849.
3	WANG Zheng, HOU Jungang, YANG Chao, et al. Template-free synthesis of 3D Nb₃O₇F hierarchical nanostructures and enhanced photocatalytic activities[J]. Physical Chemistry Chemical Physics, 2013, 15(9): 3249-3255.
4	张伟宁. 陶瓷电容器级五氧化二铌的研制与开发[D]. 长沙: 中南大学, 2001.
	ZHANG Weining. Research and development of ceramic capacitor grade niobium pentoxide[D]. Changsha: Central South University, 2001.
5	唐德胜, 晏慧娟. 钽铌氢氧化物洗水回用工艺研究[J]. 稀有金属与硬质合金, 2010, 38(4): 43-45.
	TANG Desheng, YAN Huijuan. Study of recycling process of tantalum and niobium hydroxide washing water[J]. Rare Metals and Cemented Carbides, 2010, 38(4): 43-45.
6	韩建设. 氧化铌生产工艺及装备的进展[J]. 稀有金属与硬质合金, 2003, 31(1): 35-38.
	HAN Jianshe. The progress in Nb₂O₅ production technology and equipment[J]. Rare Metals and Cemented Carbides, 2003, 31(1): 35-38.
7	韩建设, 周勇. 钽铌萃取分离工艺与设备进展[J]. 稀有金属与硬质合金, 2004, 32(2): 15-20.
	HAN Jianshe, ZHOU Yong. Development of Ta & Nb extraction and stripping technology and equipment[J]. Rare Metals and Cemented Carbides, 2004, 32(2): 15-20.
8	王常清, 易艳萍, 喻君临, 等. HF-H₂SO₄-仲辛醇体系中硝酸对高纯氧化铌生产的影响研究[J]. 稀有金属与硬质合金, 2014, 42(2): 23-25.
	WANG Changqing, YI Yanping, YU Junlin, et al. Study on effect of nitric acid in HF-H₂SO₄-2-octanol system on production of high-purity niobium oxide[J]. Rare Metals and Cemented Carbides, 2014, 42(2): 23-25.
9	幸良佐. 钽铌冶金[M]. 北京: 冶金工业出版社, 1982.
	XING Liangzuo. Tantalum niobium metallurgy[M]. Beijing: Metallurgical Industry Press, 1982.
10	中华人民共和国工业和信息化部. 五氧化二铌: [S]. 北京: 中国标准出版社, 2013.
	Ministry of Industry and Information Technology of the People’s Republic of China. Niobium pentoxide: [S]. Beijing: Standards Press of China, 2013.
11	邓小芬, 王才明. 降低Nb₂O₅中氟含量的研究[J]. 稀有金属与硬质合金, 2005, 33(1): 11-13.
	DENG Xiaofen, WANG Caiming. Research on reduction of F^- content in Nb₂O₅ [J]. Rare Metals and Cemented Carbides, 2005, 33(1): 11-13.
12	姚卫东, 曹七林, 伍尊中. 钽铌湿法冶炼含氟废水的综合利用及其治理[J]. 材料研究与应用, 2011, 5(1): 71-73.
	YAO Weidong, CAO Qilin, WU Zunzhong. Comprehensive utilization and treatment of fluorine-containing waste water arising from tantalum and niobium wet smelting[J]. Materials Research and Application, 2011, 5(1): 71-73.
13	袁宁峰, 黄道平, 董欢欢, 等. 一种钽铌氢氧化物的洗涤方法及洗涤装置: CN102807253A[P]. 2012-12-05.
	YUAN Ningfeng, HUANG Daoping, DONG Huanhuan, et al. Washing method and washing device for tantalum-niobium hydroxide: CN102807253A[P]. 2012-12-05.
14	万明远, 高潺, 李启华, 等. 氢氧化铌或氢氧化钽的洗涤设备及洗涤方法: CN1789144A[P]. 2006-06-21.
	WAN Mingyuan, GAO Chan, LI Qihua, et al. Equipment and method for washing niobium hydroxide or tantalum hydroxide: CN1789144A[P]. 2006-06-21.
15	张伟宁, 陈飞, 鲁东, 等. 钽铌湿法冶金技术设备的发展与展望[J]. 冶金与材料, 2018, 38(6): 96-97.
	ZHANG Weining, CHEN Fei, LU Dong, et al. Development and prospect of tantalum-niobium hydrometallurgy technology and equipment[J]. Metallurgy and Materials, 2018, 38(6): 96-97.
16	董强, 季兆全, 廖翔, 等. 湿化学法制备纳米陶瓷粉体中膜清洗工艺基础研究[J]. 硅酸盐学报, 2002, 30(S1): 18-21.
	DONG Qiang, JI Zhaoquan, LIAO Xiang, et al. Study on nanometer ceramic powders preparation by washing process of ceramic membrane separation technique[J]. Journal of the Chinese Ceramic Society, 2002, 30(S1): 18-21.
17	徐南平. 无机膜的发展现状与展望[J]. 化工进展, 2000, 19(4): 5-9.
	XU Nanping. Recent developmet of inorganic membrane[J]. Chemical Industry and Engineering Progress, 2000, 19(4): 5-9.
18	徐南平, 李卫星, 仲兆祥, 等. 固液分离中陶瓷膜微结构设计方法与应用[C]//2007全国无机硅化物行业年会论文集, 上海, 2007: 38-44.
	XU Nanping, LI Weixing, ZHONG Zhaoxiang, et al. Design methods and applications of ceramic membrane microstructures in solid-liquid separation[C]//Proceedings of the 2007 national inorganic silicides industry annual meeting, Shanghai, 2007: 38-44.
19	李波, 万小朋, 赵美英. 孔隙率对复合材料单向板横向力学性能的影响[J]. 玻璃钢/复合材料, 2017(6): 33-38.
	LI Bo, WAN Xiaopeng, ZHAO Meiying. The influence of void contents on transverse mechanical properties of unidirectional composites[J]. Fiber Reinforced Plastics/Composites, 2017(6): 33-38.
20	杨晓明, 彭文博, 吴正雷, 等. 硅铝粉体陶瓷膜分离过程分析及膜清洗方法探讨[J]. 广东化工, 2018, 45(11): 99-101.
	YANG Xiaoming, PENG Wenbo, WU Zhenglei, et al. Silicon aluminum powder liquid ceramic membrane separation process and membrane cleaning method discussed[J]. Guangdong Chemical Industry, 2018, 45(11): 99-101.
21	樊江, 汪唯, 蔡佳浩, 等. 二维膜的精密构筑和结构调控策略综述[J]. 化工进展, 2020, 39(12): 4823-4836.
	FAN Jiang, WANG Wei, CAI Jiahao, et al. A review of structural design and tuning methods of two-dimensional membranes[J]. Chemical Industry and Engineering Progress, 2020, 39(12): 4823-4836.
22	徐南平, 赵静, 刘公平. “双碳”目标下膜技术发展的思考[J]. 化工进展, 2022, 41(3): 1091-1096.
	XU Nanping, ZHAO Jing, LIU Gongping. Thinking of membrane technology development towards “carbon emission peak” and “carbon neutrality” targets[J]. Chemical Industry and Engineering Progress, 2022, 41(3): 1091-1096.
23	董强, 廖翔, 季兆全, 等. 陶瓷微滤膜洗涤碱法制备Al(OH)₃中杂质Na⁺的研究[J]. 膜科学与技术, 2004, 24(5): 29-32.
	DONG Qiang, LIAO Xiang, JI Zhaoquan, et al. Study on ceramic membrane washing process of the Na⁺ in Al(OH)₃ powders by alkaline method[J]. Membrane Science and Technology, 2004, 24(5): 29-32.
24	李卫星, 邢卫红, 徐南平. 超细粉体洗涤陶瓷膜过程研究[C]//第二届全国膜技术在冶金中应用研讨会论文集, 南京, 2006: 180-183.
	LI Weixing, XING Weihong, XU Nanping. Research on ceramic membrane process of ultrafine powder washing[C]//Proceedings of the 2nd national symposium on application of membrane technology in metallurgy, Nanjing, 2006: 180-183.
25	DONG Qiang, LIU Xingqin, ZHANG Tianshu. Ceramic membrane separation technique for washing nano-sized ceramic powder precursors[J]. Particuology, 2011, 9(5): 492-496.
26	崔鹏, 王凤来, 熊伟, 等. 超声场强化膜分离过程研究与应用进展[J]. 化工进展, 2011, 30(7): 1391-1398.
	CUI Peng, WANG Fenglai, XIONG Wei, et al. Research and application of ultrasound-enhanced membrane filtration[J]. Chemical Industry and Engineering Progress, 2011, 30(7): 1391-1398.

[1]	于志庆, 黄文斌, 王晓晗, 邓开鑫, 魏强, 周亚松, 姜鹏. B掺杂Al₂O₃@C负载CoMo型加氢脱硫催化剂性能[J]. 化工进展, 2023, 42(7): 3550-3560.
[2]	张乐乐, 钱运东, 朱华曈, 冯思龙, 杨秀娜, 于颖, 杨强, 卢浩. 加氢原料煤焦油脱水除盐预处理工艺优化限值[J]. 化工进展, 2023, 42(5): 2298-2305.
[3]	王嘉, 彭冲, 唐磊, 陆安慧. 渣油加氢催化剂活性相结构调控及对反应性能影响[J]. 化工进展, 2023, 42(4): 1811-1821.
[4]	范旭阳, 陈延信, 赵博, 张蕾蕾. 气体硫黄还原磷石膏制酸新工艺预还原数值模拟[J]. 化工进展, 2023, 42(10): 5414-5426.
[5]	邓权龙, 丁厚成, 徐远迪, 蒋仲安, 杨岚, 孙雪霏. 表面活性雾滴联合金属网栅增效除尘[J]. 化工进展, 2023, 42(1): 546-552.
[6]	曹正凯, 米晓斌, 吴子明, 孙士可, 曹均丰, 彭德强, 梁相程. 煤合成气净化除尘装置压降问题分析及应用优化[J]. 化工进展, 2022, 41(S1): 15-21.
[7]	郭凡辉, 武建军, 张海军, 郭旸, 刘虎, 张一昕. 煤气化细渣陶瓷膜真空脱水试验与数值模拟[J]. 化工进展, 2022, 41(8): 4047-4056.
[8]	宋绍彤, 李天舒, 鞠雅娜, 吕忠武, 吴培, 孙长宇, 段爱军. 不同类型氧化铝对FCC轻汽油芳构化性能影响[J]. 化工进展, 2022, 41(5): 2460-2467.
[9]	张喻, 高宁博, 全翠, 王凤超. 低阶煤热解高温油气除尘技术进展[J]. 化工进展, 2022, 41(4): 1814-1824.
[10]	任可欣, 鲁军辉, 王随林, 唐进京. 低湿CO₂/H₂O混合气体吸附特性实验[J]. 化工进展, 2022, 41(12): 6698-6710.
[11]	苏洋, 罗振敏, 王涛. CO₂/海泡石抑爆剂对氢气/甲烷爆炸特性参数的影响[J]. 化工进展, 2022, 41(11): 5731-5736.
[12]	张永祥, 王德龙, 郭晓燕, 邵怀启. CrO _x /Ti-Al₂O₃催化剂结构及其催化丙烷脱氢性能[J]. 化工进展, 2022, 41(11): 5879-5886.
[13]	邹星宇, 赵文霞, 刘勇, 许瑞梅. 炭化叶脉网络生长MOFs材料制备透明超级电容器[J]. 化工进展, 2022, 41(1): 350-358.
[14]	靳元勋, 霍地, 孙旭东. 液相法制备棒状Al₂O₃及Al₂O₃-ZrO₂陶瓷复合粉体[J]. 化工进展, 2021, 40(S2): 309-314.
[15]	张军保, 王忠凯, 刘彪, 张晓晖, 刘冠美. 大颗粒尿素造粒尾气冷却洗涤器技术应用进展[J]. 化工进展, 2021, 40(S2): 15-19.

陶瓷膜在氢氧化铌粉体脱氟洗涤工艺的应用

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

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 9

参考文献 26

相关文章 15

编辑推荐

Metrics

本文评价

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

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

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