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

doi:10.7503/cjcu20180528

Abstract

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

CLC Number:

O627
TG110.6

TrendMD:

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^†[J]. Chem. J. Chinese Universities, 2019, 40(4): 740.

Figures/Tables 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

References 24

[1]	Yang S. L., Peng F. C., Pan F. S., Gao S. Z., Mater.Rev.,2008, 22(4), 53—56
	(杨绍利, 彭富昌, 潘复生, 高仕忠. 材料导报, 2008, 22(4), 53—56)
[2]	Gao Z. M., Zhang Y. F., Wang Q. S., Zhen J. Q., J. Chin. Ele. Micro. Soc.,2017, 36(2), 103—112
	(高占明, 张依福, 王秋实, 郑吉祺. 电子显微学报, 2017, 36(2), 103—112)
[3]	Cao Y. L., Jia D. Z., Liu L., Xiao D. Q., Xin X. Q., Chem. Res. Chinese Universities,2005, 21(2), 134—136
[4]	Lin H., Zou J., Li Q., Iron Steel Vanadium Titanium,2006, 27(1), 55—58, 63
	(林华, 邹建, 李庆. 钢铁钒钛, 2006, 27(1), 55—58, 63)
[5]	Hao Q. L., Shao Q., Liu Q. Y., Mod. Chem.Ind.,2014, 34(11), 51—54
	(郝巧兰, 邵谦, 刘青云. 现代化工, 2014, 34(11), 51—54)
[6]	Ren Z.Z., Huang W. G., J. Funct. Mater., 2007, 8, 2112—2113
	(任哲峥, 黄维刚功能材料, 2007, 8 , 2112—2113)
[7]	Wang A. R., Yuan J. F., Chin. J. Process Eng.,2017, 17(3), 558—564
	(王安仁, 袁吉峰. 过程工程学报, 2017, 17(3), 558—564)
[8]	Li Z.T., Synthesis, Characterization and Electrochemical Performance of Vanadium-Based Materials, South China University of Technology, Guangzhou, 2015
	(栗志同. 钒基材料的合成、表征及其电化学性能研究, 广州: 华南理工大学, 2015)
[9]	(栗志同, 王素清. 多孔五氧化二钒的制备及其电化学性能研究, 中国科技论文在线,
[10]	Ren D. X., Cao Y. Z., Chen C., Ying Y. H., Chem. Res. Chinese Universities,2012, 28(5), 768—774
[11]	Huang W. G., Lin H., Tu M. J.,J. Funct.Mater.,2006, 3(37), 440—442
	(黄维刚, 林华, 涂铭旌. 功能材料, 2006, 3(37), 440—442)
[12]	Wan L. F., Iron Steel Vanadium Titanium, 2016, 37(3), 56—60
	(万龙飞. 钢铁钒钛, 2016, 37(3), 56—60)
[13]	Hao C. Z., Kong X. F., Yu M. A., A Method to Prepare Highly Pure Vanadyl Oxalate Solid Product, CP 201710340156.8,2017-08-18
	(郝承志, 孔祥风, 于明爱. 一种高纯草酸氧钒固体产品的制备方法, CP 201710340156.8, 2017-08-18)
[14]	Cao P., Wan L. F., Shen B., Sun Z. H., Li Q. W., Pen Y., Hu L., A Method to Prepare Vanadyl Oxalate, CP 201200079205.4,2013-09-25
	(曹鹏, 万隆飞, 申彪, 孙朝晖, 李千文, 彭毅, 胡力. 一种草酸氧钒的制备方法,CP 201200079205.4, 2013-09-25)
[15]	Bruyère V. I. E., Morando P. J., Blesa M. A., J. Colloid. Interf.Sci.,1999, 209, 207—214
[16]	Bruyère V. I. E., Rodenas L. A. G., Morando P. J., Blesa M. A., J. Chem. Soc.Dalton.2001, 24(24), 3593—3597
[17]	Zhang J., Zhu Z. W., Chen D. S., Wang L. N., Wang W. J., Lei Z., Chinese Journal of Rare Metals,2018, 43(3), 303—311
	(张健, 朱兆武, 陈德胜, 王丽娜, 王伟菁, 雷泽. 稀有金属, 2018, 43(3), 303—311)
[18]	Li L. J., Chang F. Z., Wang H. X., Bai R. G., Zhou X., Yan H., A Method to Prepare Vanadyl Oxalate, CP 201610775992.4,2017-02-08
	(李兰杰, 常福增, 王海旭, 白瑞国, 周欣, 闫浩. 一种草酸氧钒的制备方法, CP 201610775992.4, 2017-02-08)
[19]	Zhang Y., Zhang T. A., Dreisinger D., Lv G. Z., Can. Metall.Quart.,2017, 56(5), 1—13
[20]	Liu Y. H., Yang C., Hydrometallurgy of China,2010, 29(4), 263—266
	(刘彦华, 杨超. 湿法冶金,2010, 29(4), 263—266)
[21]	Li X. B., Wei C., Wu J. N., Li C. X., Li M. T., Deng Z. G., Xu H. S., T. Nonferr. Metal.Soc.,2015, 25(10), 461—466
[22]	Mehdi N., Fereshteh R., Ataollah B., Ehsan V., Sep. Purif.Technol.,2014, 136, 125—128
[23]	Zhang G.Z., Study on the Recovery of V, Cr, and Fe form the Chloride Solution by Solvent Extraction, the University of Chinese Academy of Sciences, Beijing, 2017
	(张国之. 酸性氯化物体系钒、铬、铁萃取分离基础研究,北京: 中国科学院大学, 2017)
[24]	Li D., Preparation of Vanadyl Sulfate with High Purity form Vanadium Hydrochloride Solutions in Shorter Process, The University of Chinese Academy of Sciences, Beijing, 2017
	(李丹. 含钒氯化物溶液短流程制备高纯硫酸氧钒研究,,北京: 中国科学院大学, 2017)