石煤钒矿常压湿法清洁提取五氧化二钒工艺研究

万洪强; 李静; 田洪庆; 罗豪; 张丽芬; 田子瑜

doi:10.7513/j.issn.1004-7638.2025.01.004

石煤钒矿常压湿法清洁提取五氧化二钒工艺研究

doi: 10.7513/j.issn.1004-7638.2025.01.004

长沙矿冶研究院有限责任公司, 湖南长沙 410012

基金项目: 国家重点研发计划项目（2020YFC1909705）。

详细信息

作者简介:
万洪强，1984年出生，江西南昌人，正高级工程师，研究方向：有色金属冶金清洁工艺开发及工程设计，E-mail：wanhq4321@163.com

中图分类号: TF841.3
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出版历程
- 收稿日期: 2023-09-12
- 刊出日期: 2025-02-27

Study on the clean extraction process of vanadium pentoxide from vanadium ore of stone coal by atmospheric pressure wet method

Changsha Institute of Mining and Metallurgy Co., Ltd., Changsha 410012, Hunan, China

摘要

摘要: 针对目前石煤提钒环保和节能要求逐年提高的情况，开发了一种熟化水浸-萃取分离-沉钒煅烧的常压湿法清洁提取五氧化二钒工艺路线，以湖南岳阳某地石煤矿为原料，采用保温保湿浓H₂SO₄熟化浸出处理，同时对萃取、反萃和产品制备全过程进行了研究。试验结果表明，在矿物粒度100 μm占98.3%，拌水量10%，酸用量18%，熟化温度120 ℃，熟化时间8 h，水浸液固比2:1，室温下搅拌浸出2 h条件下，钒浸出率达到87.8%。采用P204进行萃取，在pH=2.2时，经过5级单级萃取，钒萃取率已达98%，反萃4级可达99%以上的反萃率，在pH=1.0进行沉钒，多钒酸盐在600 ℃下煅烧2 h，V₂O₅产品达到国家标准要求。
- 五氧化二钒 /
- 石煤钒矿 /
- 清洁提取 /
- 湿法 /
- 常压 /
- 浸出率
Abstract: In view of the increasing environmental protection and energy saving requirements of vanadium extraction from stone coal year by year, a clean process for V₂O₅ extraction by atmospheric pressure wet method including water leaching, extraction separation, vanadium precipitation and calcination was developed. A stone coal mine in Yueyang, Hunan Province was used as raw materials in this paper. Using insulated humidity-concentrated H₂SO₄ maturation leaching treatment, and also investigated the whole process of extraction, back-extraction and product preparation. The test results show that the vanadium leaching rate can reach 87.8% under the following conditions: 98.3% of mineral size under 100 μm, 10% of water mixing, 18% of acid dosage, maturation temperature of 120 ℃, maturation time of 8 h, water leaching liquid-solid ratio of 2:1 and stirring leaching for 2 h at room temperature. With P204 extraction, the vanadium extraction rate was 98% after 5 single-stage extraction at pH=2.2, and the back-extraction rate of 4 stages could reach more than 99%. At the pH of 1.0 for vanadium precipitation and then multi-vanadate was calcined at 600 ℃ for 2 h, required V₂O₅ product met the requirements of national standards.
- vanadium pentoxide /
- coal mine /
- clean extraction /
- wet process /
- atmospheric pressure /
- leaching rate

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图 1 矿石的X射线衍射矿物相分析图谱

Figure 1. X-ray diffraction mineral phase analysis profile of ore

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图 2 含钒伊利云母嵌布在石英中的扫描电镜面分析图像

（a）背散射电子像；（b）V面扫描；（c）K面扫描；（d）Al面扫描；（e）Si面扫描；（f）O面扫描；S: 伊利云母，鳞片状，含V、Si、Al、K、O；Q: 石英，基底物，Si、O密集

Figure 2. SEM surface analysis image of vanadium-containing Erie mica embedded in quartz

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图 3 石煤常压湿法清洁提取的工艺流程

Figure 3. Process flow of atmospheric pressure wet clean extraction of stone coal

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图 4 保温控湿熟化原料粒度对钒浸出率的影响

Figure 4. Influence of particle size of insulated and humidity controlled ripened raw material on vanadium leaching rate

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图 5 保温控湿熟化酸用量对钒浸出率的影响

Figure 5. Effect of holding and humidity controlled maturation acid dosage on vanadium leaching rate

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图 6 18%的拌酸量保温控湿熟化时间对钒浸出率的影响

Figure 6. Effect of 18% acid mixing on the leaching rate of vanadium by holding and humidity controlled maturation time

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图 7 保温控湿熟化温度对钒浸出率的影响

Figure 7. Effect of holding and humidity controlled maturation temperature on vanadium leaching rate

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图 8 料液pH值对萃取率的影响

Figure 8. Effect of feed solution pH on extraction rate

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图 9 单级萃取级数试验

Figure 9. Single-stage extraction level test

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图 10 单级反萃级数试验

Figure 10. Single-stage back-extraction level test

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图 11 沉钒pH值与沉钒率的关系

Figure 11. Vanadium precipitation pH versus vanadium precipitation rate

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表 1 原矿的X荧光光谱半定量分析结果

Table 1. Semi-quantitative analysis of raw ore by X-fluorescence spectra %

V	Si	C	Al	Ba	Fe	K	S	O	Zr	Ti	Cr	Ni	Se	Mn	Rb	Zn	Ca	Mg	Mo	Cu	P
0.543	39.65		3.37	1.56	1.096	0.691	0.196	50.20	0.0073	0.222	0.0233	0.004	0.003		0.0039	0.003	0.031	0.242	0.0053	0.0199	0.134

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表 2 原矿化学成分定量分析结果

Table 2. Quantitative analysis of raw ore chemical composition %

V₂O₅	TFe	FeO	Fe₂O₃	SiO₂	Al₂O₃	CaO	MgO	TiO₂	Ba	P	C	S	K₂O	Na₂O	Cu
0.92	1.98	0.57	2.20	82.18	5.31	0.14	0.60	0.41	2.03	0.17	0.18	0.36	0.69	0.02	0.02

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表 3 原矿中钒物相分析结果

Table 3. Vanadium phase analysis results of raw ore

相态	V₂O₅含量/%	分布率/%
铁铝相	0.072	7.83
云母	0.835	90.76
石榴石	0.012	1.41
合计	0.92	100.00

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表 4 原矿中钒价态分析结果

Table 4. Vanadium valence analysis results in raw ore

价态	V₂O₅含量/%	分布率/%
五价钒	0.436	47.34
四价钒	0.291	31.60
三价钒	0.194	21.06
合计	0.921	100.00

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表 5 矿石中主要矿物的含量

Table 5. Content of major minerals in ore %

云母	褐铁矿	石英玉髓	蒙脱石	重晶石	角闪石	磷灰石	锐钛矿	碳质物	其它
9.2	3.0	70.8	8.0	3.5	3.0	1.0	0.5	微量	1.0

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表 6 保温控湿熟化试验用原料粒度组成

Table 6. Particle size of raw materials used in insulation and humidity-controlled ripening test

样品	占比/%
样品	$+30 \;\mu {\mathrm{m}} $	$30 \sim 60 \;\mu {\mathrm{m}} $	$60 \sim 100 \;\mu {\mathrm{m}} $	$100 \sim 150 \;\mu {\mathrm{m}} $	$-150 \;\mu {\mathrm{m}} $
样①	14.5	19.1	11.1	16.6	38.7
样②	4.5	13.2	13.7	20.6	48.0
样③	1.9	6.5	17.0	22.4	52.2
样④				1.7	98.3
样⑤					100

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表 8 煅烧试验结果

Table 8. Calcination test results

项目	钒酸铵/g	产品/g	烧成率/%	V₂O₅/%	Si/%	Fe/%	P/%	S/%	As/%	(Na₂O+K₂O)/%
一次	5	4.36	87.2	98.50	0.02	0.30	0.045	0.005	0.01	0.003
二次	5	4.39	87.80	99.23	0.03	0.28	0.05	0.004	0.0099	0.004
平均	5	4.38	87.5	98.87	0.025	0.29	0.047	0.003	0.01	0.0035

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表 7 浸出溶液主要成分分析

Table 7. Analysis of major components of leaching solution g/L

V₂O₅	V⁵⁺	Fe	Fe³⁺	Al³⁺	Mg²⁺	K⁺	SiO₂	As	Cd	Cr³⁺	Cr⁵⁺	P	Na⁺	SO₄²⁺
4.78	痕量	3.25	微量	8.21	1.42	3.15	0.07	0.0039	0.0067	痕量	0.26	0.130	0.07	81.76
注：pH=1.45。

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