黏土钒矿直接常压活化酸浸提钒热力学分析

doi:10.16085/j.issn.1000-6613.2020-2103

摘要/Abstract

摘要：

目前黏土钒矿直接酸浸的试验以及基础性研究较少，为了进一步推动此类问题的研究进展，本项研究采用试验结合热力学计算的方法，通过试验得到了最佳浸出剂结果，运用热力学计算诠释了活化浸出钒过程的热力学行为以及其机理，同时进一步分析了不同硫元素的总量对酸浸液中各组分的影响，为从酸浸液中提钒工艺进行了溶液化学分析。结果表明：二氧化锰有能力将低价钒氧化至高价钒，从而提升钒的浸出率，升高温度对浸出率的提高以及二氧化锰的氧化均会造成不利影响，但是会抑制杂质的浸出，对杂质分离起到积极影响。硫酸的用量一方面会影响浸出过程的pH，同时会影响酸浸液中各组分的含量，低硫的酸浸体系与高硫体系中钒的离子形态存在差异。低硫体系中铁杂质的溶解度会小于高硫体系，有利于提钒过程中杂质的分离。通过分析浸出过程中溶液组分的变化，可以为后续提钒工序提供理论依据。

关键词: 浸取, 提钒, 电化学, 热力学性质：热力学过程

Abstract:

At present, there are few experiments and basic researches on direct acid leaching of clay vanadium ore. In order to further promoted the research progress of this kind of problem, the method of experiment combined with thermodynamic calculation was adopted in this study. The results of the best leaching agent were obtained through experiments. The thermodynamic behavior and mechanism of vanadium leaching process were explained by thermodynamic calculation. The influence of total amount of different sulfur elements on the components of acid leaching solution was further analyzed. The solution chemical analysis was carried out for vanadium extraction process from acid leaching solution. The results showed that manganese dioxide has the ability to oxidize low valence vanadium to high valence vanadium, so as to improve the leaching rate of vanadium. The increase of temperature will have adverse effects on the improvement of leaching rate and the oxidation of manganese dioxide, but it will inhibit the leaching of impurities and have a positive impact on the separation of impurities. The amount of sulfuric acid not only affect the pH of the leaching process, but also affect the content of each component in the acid leaching solution. The solubility of iron impurities in the low sulfur system is lower than that in the high sulfur system, which is conducive to the separation of impurities in the process of vanadium extraction. By analyzing the change of solution components in the leaching process, the theoretical basis can be provided for the subsequent vanadium extraction process.

Key words: leaching, vanadium extraction, telectrochemistry, thermodynamic propertie, hermodynamic process

中图分类号:

TF111

张豪, 叶国华, 陈子杨, 谢禹, 左琪. 黏土钒矿直接常压活化酸浸提钒热力学分析[J]. 化工进展, 2021, 40(10): 5360-5369.

ZHANG Hao, YE Guohua, CHEN Ziyang, XIE Yu, ZUO Qi. Analysis of thermodynamics of vanadium extraction from clay vanadium ore by direct atmospheric pressure activation[J]. Chemical Industry and Engineering Progress, 2021, 40(10): 5360-5369.

图/表 17

表1 黏土钒矿试样主要化学组分

成分	质量分数/%	成分	质量分数/%
V	1.20	P	0.26
Fe	1.74	S	0.01
CaO	0.14	Cr	0.11
SiO₂	81.53	K	0.98
MgO	0.74	Na	0.03
Mn	0.01	As	<0.10
Al₂O₃	6.76	TiO₂	1.75

表2 黏土钒矿中钒的价态分析结果

项目	价态质量分数/%			合计质量分数/%
项目	V（Ⅲ）	V（Ⅳ）	V（Ⅴ）	以V计	以V₂O₅计
含量	1.03	0.08	0.03	1.14	2.04
分布率	90.18	6.84	2.98	100	100

图1 试验装置

表3 V-H2O体系主要电化学反应以及标准电位

序号	方程式	298K标准电位/V
1	VOH²⁺ $? ? ???????? ?$ VO⁺+H⁺	3.52
2	V³⁺+H₂O $? ? ???????? ?$ V（OH）²⁺+H⁺	2.92
3	2VO²⁺+3H₂O $? ? ???????? ?$ HV₂O $5 -$ +5H⁺	4.02
4	2VO $2 +$ +3H₂O $? ? ???????? ?$ H₃V₂O $7 -$ +3H⁺	1.03
5	H₃V₂O $7 -$ +H₂O $? ? ???????? ?$ 2H₂VO $4 -$ +2H⁺	7.38
6	H₂VO $4 -$ $? ? ???????? ?$ HVO $4 2 -$ +H⁺	9.52
7	HVO $4 2 -$ $? ? ???????? ?$ VO $4 3 -$ +H⁺	11.5
8	V³⁺+e^- $? ? ???????? ?$ V²⁺	-0.26
9	VO⁺ $? ? ???????? ?$ VO²⁺+e^-	-0.04
10	V²⁺+H₂O $? ? ???????? ?$ V（OH）²⁺+H⁺+e^-	-0.08
11	V²⁺+H₂O $? ? ???????? ?$ VO⁺+2H⁺+e^-	0.13
12	VOH²⁺ $? ? ???????? ?$ VO²⁺+H⁺+e^-	0.16
13	2VO⁺+3H₂O $? ? ???????? ?$ HV₂O $5 -$ +5H⁺+2e^-	0.55
14	2VO²⁺+5H₂O $? ? ???????? ?$ H₃V₂O $7 -$ +7H⁺+2e^-	1.10
15	HV₂O $5 -$ +2H₂O $? ? ???????? ?$ H₃V₂O $7 -$ +2H⁺+2e^-	0.50
16	HV₂O $5 -$ +3H₂O $? ? ???????? ?$ 2H₂VO $4 -$ +3H⁺+2e^-	0.72
17	HV₂O $5 -$ +3H₂O $? ? ???????? ?$ 2HVO $4 2 -$ +5H⁺+2e^-	1.28
18	HV₂O $5 -$ +3H₂O $? ? ???????? ?$ 2VO $4 3 -$ +7H⁺+2e^-	1.96

表3 V-H2O体系主要电化学反应以及标准电位

序号	方程式	298K标准电位/V
1	VOH²⁺ $? ? ???????? ?$ VO⁺+H⁺	3.52
2	V³⁺+H₂O $? ? ???????? ?$ V（OH）²⁺+H⁺	2.92
3	2VO²⁺+3H₂O $? ? ???????? ?$ HV₂O $5 -$ +5H⁺	4.02
4	2VO $2 +$ +3H₂O $? ? ???????? ?$ H₃V₂O $7 -$ +3H⁺	1.03
5	H₃V₂O $7 -$ +H₂O $? ? ???????? ?$ 2H₂VO $4 -$ +2H⁺	7.38
6	H₂VO $4 -$ $? ? ???????? ?$ HVO $4 2 -$ +H⁺	9.52
7	HVO $4 2 -$ $? ? ???????? ?$ VO $4 3 -$ +H⁺	11.5
8	V³⁺+e^- $? ? ???????? ?$ V²⁺	-0.26
9	VO⁺ $? ? ???????? ?$ VO²⁺+e^-	-0.04
10	V²⁺+H₂O $? ? ???????? ?$ V（OH）²⁺+H⁺+e^-	-0.08
11	V²⁺+H₂O $? ? ???????? ?$ VO⁺+2H⁺+e^-	0.13
12	VOH²⁺ $? ? ???????? ?$ VO²⁺+H⁺+e^-	0.16
13	2VO⁺+3H₂O $? ? ???????? ?$ HV₂O $5 -$ +5H⁺+2e^-	0.55
14	2VO²⁺+5H₂O $? ? ???????? ?$ H₃V₂O $7 -$ +7H⁺+2e^-	1.10
15	HV₂O $5 -$ +2H₂O $? ? ???????? ?$ H₃V₂O $7 -$ +2H⁺+2e^-	0.50
16	HV₂O $5 -$ +3H₂O $? ? ???????? ?$ 2H₂VO $4 -$ +3H⁺+2e^-	0.72
17	HV₂O $5 -$ +3H₂O $? ? ???????? ?$ 2HVO $4 2 -$ +5H⁺+2e^-	1.28
18	HV₂O $5 -$ +3H₂O $? ? ???????? ?$ 2VO $4 3 -$ +7H⁺+2e^-	1.96

表4 Mn-V-H2O体系主要电化学反应以及不同温度下的热力学数据

序号	方程式	ΔS	比热容/J·K^-1		电势/V
序号	方程式	ΔS	333K	373K	298K	333K	373K
19	MnO+2H⁺ $? ? ???????? ?$ Mn²⁺+H₂O	-105.55	36.00	98.33	7.65	6.56	5.62
20	Mn²⁺+2e^- $? ? ???????? ?$ Mn	17.13	-19.97	-20.51	-1.18	-1.18	-1.17
21	MnO+2H⁺+2e^- $? ? ???????? ?$ Mn+H₂O	-88.42	13.85	15.10	-0.73	-0.74	-0.76
22	Mn₃O₄+2H⁺+2e^- $? ? ???????? ?$ 3MnO+H₂O	-37.19	17.72	19.63	0.46	0.46	0.45
23	Mn₃O₄+8H⁺+2e^- $? ? ???????? ?$ 3Mn²⁺+4H₂O	-353.31	119.18	126.25	1.82	1.76	1.68
24	Mn₂O₃+6H⁺+2e^- $? ? ???????? ?$ 2Mn²⁺+3H₂O	-262.91	89.56	93.59	1.44	1.40	1.34
25	3Mn₂O₃+2H⁺+2e^- $? ? ???????? ?$ 2Mn₃O₄+H₂O	-81.02	30.32	28.28	0.69	0.67	0.66
26	MnO₂+4H++2e^- $? ? ???????? ?$ Mn²⁺+2H₂O	-159.61	54.81	56.95	1.23	1.20	1.17
27	2MnO₂+2H++2e^- $? ? ???????? ?$ Mn₂O₃+H2O	-56.32	20.07	20.30	1.02	1.00	0.99
28	2MnO₂+2H⁺+2e^- $? ? ???????? ?$ Mn₂O₃+H₂O	-432.00	230.80	131.90	1.69	1.64	1.58
29	MnO^4-+4H+3e^- $? ? ???????? ?$ MnO₂+2H₂O	76.68	-53.11	-57.13	-0.44	-0.43	-0.41
30	Fe²⁺+2e^- $? ? ???????? ?$ Fe	269.23	-14.23	-11.61	0.77	0.82	0.88
31	Fe³⁺+e^- $? ? ???????? ?$ Fe²⁺	-128.41	75.29	80.46	6.57	5.54	4.62
32	Fe（OH）₂+2H⁺ $? ? ???????? ?$ Fe²⁺+2H₂O	-277.31	121.81	124.94	1.53	0.87	0.32
33	Fe（OH）₃+3H⁺ $? ? ???????? ?$ Fe³⁺+3H₂O	435.68	-116.71	-158.32	1.06	1.01	0.95
34	Fe（OH）₃+3H⁺ $? ? ???????? ?$ Fe³⁺+3H₂O	-51.72	22.18	23.33	-0.05	-0.06	-0.07
35	Fe（OH）₂+2H⁺+2e^- $? ? ???????? ?$ Fe+2H₂O	-28.56	78.82	77.35	0.27	0.27	0.26
36	Fe（OH）₃+H⁺+e^- $? ? ???????? ?$ Fe（OH）₂+H₂O	-200.91	9.42	-2.33	0.34	0.32	0.30
37	V³⁺+H₂O $? ? ???????? ?$ VO²⁺+2H⁺+e^-	367.08	1.58	8.21	1.04	1.01	0.99
38	VO²⁺+H₂O $? ? ???????? ?$ VO $2 +$ +2H⁺+e^-	-281.24	55.14	15.04	0.96	0.93	0.90
39	V₂O₅+6H⁺+2e^- $? ? ???????? ?$ 2VO²⁺+3H₂O	-65.27	-182.17	-35.63	2.15	1.62	1.14
40	V₂O₄+4H⁺ $? ? ???????? ?$ 2VO²⁺+2H₂O	-247.78	-300.58	-46.77	2.20	1.64	1.13

表4 Mn-V-H2O体系主要电化学反应以及不同温度下的热力学数据

序号	方程式	ΔS	比热容/J·K^-1		电势/V
序号	方程式	ΔS	333K	373K	298K	333K	373K
19	MnO+2H⁺ $? ? ???????? ?$ Mn²⁺+H₂O	-105.55	36.00	98.33	7.65	6.56	5.62
20	Mn²⁺+2e^- $? ? ???????? ?$ Mn	17.13	-19.97	-20.51	-1.18	-1.18	-1.17
21	MnO+2H⁺+2e^- $? ? ???????? ?$ Mn+H₂O	-88.42	13.85	15.10	-0.73	-0.74	-0.76
22	Mn₃O₄+2H⁺+2e^- $? ? ???????? ?$ 3MnO+H₂O	-37.19	17.72	19.63	0.46	0.46	0.45
23	Mn₃O₄+8H⁺+2e^- $? ? ???????? ?$ 3Mn²⁺+4H₂O	-353.31	119.18	126.25	1.82	1.76	1.68
24	Mn₂O₃+6H⁺+2e^- $? ? ???????? ?$ 2Mn²⁺+3H₂O	-262.91	89.56	93.59	1.44	1.40	1.34
25	3Mn₂O₃+2H⁺+2e^- $? ? ???????? ?$ 2Mn₃O₄+H₂O	-81.02	30.32	28.28	0.69	0.67	0.66
26	MnO₂+4H++2e^- $? ? ???????? ?$ Mn²⁺+2H₂O	-159.61	54.81	56.95	1.23	1.20	1.17
27	2MnO₂+2H++2e^- $? ? ???????? ?$ Mn₂O₃+H2O	-56.32	20.07	20.30	1.02	1.00	0.99
28	2MnO₂+2H⁺+2e^- $? ? ???????? ?$ Mn₂O₃+H₂O	-432.00	230.80	131.90	1.69	1.64	1.58
29	MnO^4-+4H+3e^- $? ? ???????? ?$ MnO₂+2H₂O	76.68	-53.11	-57.13	-0.44	-0.43	-0.41
30	Fe²⁺+2e^- $? ? ???????? ?$ Fe	269.23	-14.23	-11.61	0.77	0.82	0.88
31	Fe³⁺+e^- $? ? ???????? ?$ Fe²⁺	-128.41	75.29	80.46	6.57	5.54	4.62
32	Fe（OH）₂+2H⁺ $? ? ???????? ?$ Fe²⁺+2H₂O	-277.31	121.81	124.94	1.53	0.87	0.32
33	Fe（OH）₃+3H⁺ $? ? ???????? ?$ Fe³⁺+3H₂O	435.68	-116.71	-158.32	1.06	1.01	0.95
34	Fe（OH）₃+3H⁺ $? ? ???????? ?$ Fe³⁺+3H₂O	-51.72	22.18	23.33	-0.05	-0.06	-0.07
35	Fe（OH）₂+2H⁺+2e^- $? ? ???????? ?$ Fe+2H₂O	-28.56	78.82	77.35	0.27	0.27	0.26
36	Fe（OH）₃+H⁺+e^- $? ? ???????? ?$ Fe（OH）₂+H₂O	-200.91	9.42	-2.33	0.34	0.32	0.30
37	V³⁺+H₂O $? ? ???????? ?$ VO²⁺+2H⁺+e^-	367.08	1.58	8.21	1.04	1.01	0.99
38	VO²⁺+H₂O $? ? ???????? ?$ VO $2 +$ +2H⁺+e^-	-281.24	55.14	15.04	0.96	0.93	0.90
39	V₂O₅+6H⁺+2e^- $? ? ???????? ?$ 2VO²⁺+3H₂O	-65.27	-182.17	-35.63	2.15	1.62	1.14
40	V₂O₄+4H⁺ $? ? ???????? ?$ 2VO²⁺+2H₂O	-247.78	-300.58	-46.77	2.20	1.64	1.13

表5 Fe-V-H2O体系主要化学反应以及平衡常数

序号	方程式	lgK^?
41	VO $4 3 -$ +4H⁺ $? ? ???????? ?$ VO $2 +$ +2H₂O	24.70
42	VO $4 3 -$ +H⁺ $? ? ???????? ?$ HVO $4 2 -$	11.54
43	VO $4 3 -$ +2H⁺ $? ? ???????? ?$ H₂VO $4 -$	21.10
44	2VO $4 3 -$ +5H⁺ $? ? ???????? ?$ H₃V₂O $7 -$	46.45
45	VO $4 3 -$ +4H⁺+SO $4 2 -$ $? ? ???????? ?$ VO₂ SO $4 -$ +2H₂O	29.37
46	VO⁺+H⁺ $? ? ???????? ?$ V（OH）²⁺	-1.83
47	V（OH）²⁺+H⁺ $? ? ???????? ?$ H₂O+V³⁺	2.96
48	Fe³⁺+OH^- $? ? ???????? ?$ Fe（OH）²⁺	11.89
49	Fe³⁺+2OH^- $? ? ???????? ?$ Fe（OH） $2 +$	23.62
50	Fe³⁺+3OH^- $? ? ???????? ?$ Fe（OH）₃	35.30
51	Fe³⁺+SO $4 2 -$ $? ? ???????? ?$ FeSO $4 +$	2.03
52	Fe³⁺+2SO $4 2 -$ $? ? ???????? ?$ Fe（SO $4 -$ ） $2 -$	2.98
53	H+HSO $4 -$ $? ? ???????? ?$ H₂SO₄	-11.60
54	H+SO $4 2 -$ $? ? ???????? ?$ HSO $4 -$	1.96
55	H⁺+OH^- $? ? ???????? ?$ H₂O	14.00

表5 Fe-V-H2O体系主要化学反应以及平衡常数

序号	方程式	lgK^?
41	VO $4 3 -$ +4H⁺ $? ? ???????? ?$ VO $2 +$ +2H₂O	24.70
42	VO $4 3 -$ +H⁺ $? ? ???????? ?$ HVO $4 2 -$	11.54
43	VO $4 3 -$ +2H⁺ $? ? ???????? ?$ H₂VO $4 -$	21.10
44	2VO $4 3 -$ +5H⁺ $? ? ???????? ?$ H₃V₂O $7 -$	46.45
45	VO $4 3 -$ +4H⁺+SO $4 2 -$ $? ? ???????? ?$ VO₂ SO $4 -$ +2H₂O	29.37
46	VO⁺+H⁺ $? ? ???????? ?$ V（OH）²⁺	-1.83
47	V（OH）²⁺+H⁺ $? ? ???????? ?$ H₂O+V³⁺	2.96
48	Fe³⁺+OH^- $? ? ???????? ?$ Fe（OH）²⁺	11.89
49	Fe³⁺+2OH^- $? ? ???????? ?$ Fe（OH） $2 +$	23.62
50	Fe³⁺+3OH^- $? ? ???????? ?$ Fe（OH）₃	35.30
51	Fe³⁺+SO $4 2 -$ $? ? ???????? ?$ FeSO $4 +$	2.03
52	Fe³⁺+2SO $4 2 -$ $? ? ???????? ?$ Fe（SO $4 -$ ） $2 -$	2.98
53	H+HSO $4 -$ $? ? ???????? ?$ H₂SO₄	-11.60
54	H+SO $4 2 -$ $? ? ???????? ?$ HSO $4 -$	1.96
55	H⁺+OH^- $? ? ???????? ?$ H₂O	14.00

图2 298K时Mn-V-H2O电位-pH图

表6 活化酸浸综合条件试验结果

浸出工艺	产品名称	质量/g	钒品位/%	浸出率/%
活化酸浸	浸渣	85.50	0.18	92.58
	浸出液	228	8.24
	浸出原料	100	2.04
不活化酸浸	浸渣	86.80	0.54	76.86
	浸出液	230	6.76
	浸出原料	100	2.04

图3 333K、373K时Mn-V-H2O电位-pH图

图4 浸出温度对浸出率的影响

图5 298K、333K、373K时Fe-V-H2O电位-pH图

表7 浸出液化学成分分析（质量分数）

产品	化学成分/%
产品	V₂O₅	Fe	SiO₂	MgO	CaO	Na	K	P
活化酸浸液	8.24	6.56	<0.01	2.03	0.01	0.04	3.31	0.97
不活化酸浸液	6.76	6.48	<0.01	1.14	0.08	0.04	1.92	0.95

图6 浸出前后矿粒SEM图（放大10000倍）

图7 298K时S-Fe-V-H2O溶液组分图

图8 333K时S-Fe-V-H2O溶液组分图

图9 硫酸用量对浸出率的影响

图10 不同总硫含量下pH与含钒、铁阴阳离子含量的关系

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