P507萃取纯化V(Ⅳ)制备草酸氧钒及其物化性能

doi:10.7503/cjcu20180528

高等学校化学学报 ›› 2019, Vol. 40 ›› Issue (4): 740.doi: 10.7503/cjcu20180528

P507萃取纯化V(Ⅳ)制备草酸氧钒及其物化性能

张健^1,², 朱兆武^1,²(), 雷泽³, 王丽娜^1,², 陈德胜^1,², 易爱飞^1,², 苏慧^1,², 齐涛^1,²()

1. 中国科学院过程工程研究所, 湿法冶金清洁生产技术国家工程实验室, 2. 绿色过程与工程重点实验室, 北京 100190
2. 绿色过程与工程重点实验室, 北京 100190
3. 中国矿业大学(北京)化学与环境工程学院, 北京 100083

收稿日期:2018-07-27 出版日期:2019-04-03 发布日期:2018-10-08
作者简介:
联系人简介: 朱兆武, 男, 博士, 研究员, 博士生导师, 主要从事湿法冶金方面的研究. E-mail: zhwzhu@ipe.ac.cn;齐涛, 男, 博士, 研究员, 博士生导师, 主要从事湿法冶金方面的研究. E-mail: tqi@ipe.ac.cn
基金资助:
国家自然科学基金(批准号: 21506233, 21606241, 51774260)、中国科学院前沿科学重点研究项目(批准号: QYZDJ-SSW-JSC021)和中国科学院创新交叉团队项目资助.

Preparation of Vanadium Oxalate by Solvent Extraction and Purification with P507 and Its Physicochemical Properties^†

ZHANG Jian^1,², ZHU Zhaowu^1,^2,^*(), LEI Ze³, WANG Lina^1,², CHEN Desheng^1,², YI Aifei^1,², SU Hui^1,², QI Tao^1,^2,^*()

1. National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology, 2. Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Science, Beijing 100910, China
2. Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Science, Beijing 100910, China
3. School of Chemical & Environmental Engineering, China University of Mining & Technology-Beijing, Beijing 100083, China;

Received:2018-07-27 Online:2019-04-03 Published:2018-10-08
Contact: ZHU Zhaowu,QI Tao E-mail:zhwzhu@ipe.ac.cn;tqi@ipe.ac.cn
Supported by:
† Supported by the National Natural Science Foundation of China(Nos.21506233, 21606241, 51774260), the Key Research Program of Frontier Sciences of Chinese Academy of Sciences(No.QYZDJ-SSW-JSC021) and the Foundation of Interdisciplinary Innovation Team of Chinese Academy of Sciences.

摘要/Abstract

摘要：

从钒渣钠化焙烧后的含钒浸液中, 采用2-乙基己基磷酸单-2-乙基己酯(P507)萃取-草酸反萃取-蒸发结晶新工艺制备了草酸氧钒, 优化了草酸反萃取工艺的条件. 研究结果表明, 采用2.0 mol/L草酸溶液, 在水相与有机相体积比V(A):V(O)为1:5时, 于50 ℃下经过三级(理论)反萃取, 钒的反萃取率可达到99.98%, 反萃取液中VOC₂O₄浓度可达290.0 g/L以上. 负载的反萃取液经膜过滤除去残留有机物后, 再经蒸发结晶得到草酸氧钒. 采用X射线衍射、 X射线能谱、热场发射扫描电子显微镜及同步热分析等手段表征了草酸氧钒的物化性能, 结果表明, 草酸氧钒的结构为VOC₂O₄·2H₂O, 粒度分布均匀, 结晶度高.

关键词: 钒浸出液, 反萃取, 结晶, 草酸氧钒, 物化性能

Abstract:

Vanadium oxalate is an ideal precursor used for the preparation of vanadium containing catalysts, advanced phase change material of VO₂, high performance VN and other vanadium based chemical products. Currently, few research on the preparation of VOC₂O₄ was found to be reported. In this study, highly pure vanadium oxalate was prepared through “extraction-stripping-evaporative crystallization” method using 2-ethylhexyl dihydrogen phosphate(P507) as the extractant and H₂C₂O₄ as the stripping reagent from a vanadium leach solution obtained by sodium roasting and water leaching of vanadium titano-magnetite slags. V(Ⅳ) stripping from the loaded P507 solution with H₂C₂O₄ was emphatically studied and the stripping conditions were optimized. The result showed that vanadium could be almost completely(99.98%) stripped at an A/O ratio of 1:5 and 50 ℃ using 2.0 mol/L oxalic acid solution in three stages(theoretical). The concentration of VOC₂O₄ would reach 290 g/L in the loaded strip liquor. The vanadium oxalate was characterized by X-ray diffraction(XRD), energy dispersive spectrometer(EDS), field emission scanning electron microscope(SEM) and synchronous thermal analyzer(TGA-DSC). The result showed that vanadium oxalate was VOC₂O₄·2H₂O and it had high purity, good crystallinity and average particle size distribution.

Key words: Vanadium leach solution, Stripping, Crystallization, VOC₂O₄, Physicochemical characterization

中图分类号:

O627
TG110.6

TrendMD:

张健, 朱兆武, 雷泽, 王丽娜, 陈德胜, 易爱飞, 苏慧, 齐涛. P507萃取纯化V(Ⅳ)制备草酸氧钒及其物化性能. 高等学校化学学报, 2019, 40(4): 740.

ZHANG Jian,ZHU Zhaowu,LEI Ze,WANG Lina,CHEN Desheng,YI Aifei,SU Hui,QI Tao. Preparation of Vanadium Oxalate by Solvent Extraction and Purification with P507 and Its Physicochemical Properties^†. Chem. J. Chinese Universities, 2019, 40(4): 740.

图/表 11

Fig.1 Effect of oxalic acid concentration on the vanadium stripping at 25 ℃(a), 40 ℃(b) and 50 ℃(c)

Fig.2 Effect of temperature on the vanadium stripping

Fig.3 Relationship of lgDV(Ⅳ) and T-1

Fig.4 Effect of V(A):V(O) ratio on the vanadium stripping

Table 1 Vanadium concentration and residual oxalic acid in the loaded strip liquor(LSL) under various V(A):V(O)

V(A):V(O)	Vanadium concentration/ (g·L^-1)	Oxalic concentration/ (mol·L^-1)	V(A):V(O)	Vanadium concentration/ (g·L^-1)	Oxalic concentration/ (mol·L^-1)
1:1	20.75	1.59	1:4	76.31	0.50
1:2	38.77	1.24	1:5	81.61	0.40
1:3	58.70	0.85	1:10	105.37	0

Fig.5 McCabe Thiele diagram for the determination of V(Ⅳ) stripping stage

Fig.6 Effect of stripping time on the V(Ⅳ) stripping

Fig.7 XRD pattern of the vanadyl oxalate sample

Fig.8 EDS analysis of vanadyl oxalate sampleSpots 1, 2 and 3 represent sample points seleeted during EDS point analysis; area 4 represents a sample area selected during EDS area analysis.

Table 2 EDS elemental composition analysis of vanadyl oxalate in Fig.8

Selected area	w(%)				m(V):m(C)
Selected area	C	O	V	Total	m(V):m(C)
Theoretical value	15.48	51.61	32.91	100.00	2.12
Spot 1	17.81	48.45	33.74	100.00	2.24
Spot 2	16.11	51.70	32.19	100.00	2.13
Spot 3	18.03	47.45	34.52	100.00	2.22
Area 4	17.93	45.08	37.28	100.00	2.04

Fig.9 Appearance(A), SEM image(B), TGA(a) and DSC(b) curves(C) of the vanadyl oxalate sample

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P507萃取纯化V(Ⅳ)制备草酸氧钒及其物化性能

Preparation of Vanadium Oxalate by Solvent Extraction and Purification with P507 and Its Physicochemical Properties^†

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P507萃取纯化V(Ⅳ)制备草酸氧钒及其物化性能

Preparation of Vanadium Oxalate by Solvent Extraction and Purification with P507 and Its Physicochemical Properties†

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Preparation of Vanadium Oxalate by Solvent Extraction and Purification with P507 and Its Physicochemical Properties^†