钒铬还原渣酸浸液中钒铬初步分离工艺

doi:10.16085/j.issn.1000-6613.2020-1711

化工进展 ›› 2021, Vol. 40 ›› Issue (7): 4100-4107.DOI: 10.16085/j.issn.1000-6613.2020-1711

钒铬还原渣酸浸液中钒铬初步分离工艺

邓孝伯¹(), 韦林森¹, 申长帅²(), 李千文¹, 汪超¹, 范兵强³, 张贺东², 张洋³()

^1.攀钢集团钒钛资源股份有限公司，四川攀枝花 617023
^2.郑州中科新兴产业技术研究院，河南郑州 450000
^3.中国科学院过程工程研究所，北京 100190

收稿日期:2020-08-26 修回日期:2020-09-20 出版日期:2021-07-06 发布日期:2021-07-19
通讯作者: 申长帅,张洋
作者简介:邓孝伯（1965—），男，高级工程师，长期从事钒钛资源综合利用工作。E-mail：dengxb@pzhsteel.com.cn。
基金资助:
国家重点研发计划(2018YFC1900505)

Preliminary separation process of vanadium and chromium in acid leaching solution of vanadium chromium reduction slag

DENG Xiaobo¹(), WEI Linsen¹, SHEN Changshuai²(), LI Qianwen¹, WANG Chao¹, FAN Bingqiang³, ZHANG Hedong², ZHANG Yang³()

^1.Pangang Group Vanadium and Titanium Resources Company Limited, Panzhihua 617023, Sichuan, China
^2.Zhengzhou Institute of Emerging Industrial Technology, Zhengzhou 450000, Henan, China
^3.Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China

Received:2020-08-26 Revised:2020-09-20 Online:2021-07-06 Published:2021-07-19
Contact: SHEN Changshuai,ZHANG Yang

摘要/Abstract

摘要：

钒铬还原渣是钠化提钒过程的典型危险固体废弃物，其资源化利用需求迫切。中国科学院过程工程研究所提出钒铬还原渣硫酸酸解-钒铬初步分离-铬/钒/铁络合深度分离技术路线，并在攀钢集团建成万吨级示范工程。本文重点考察钒铬还原渣酸解液中钒铬初步分离原理及工艺，研究了H₂O₂和Na₂S₂O₈两种氧化剂对沉钒效果的影响，并通过实验确定了最佳工艺条件。结果表明：以H₂O₂为氧化剂时，H₂O₂与钒摩尔比为0.75、氧化温度为60℃、初始溶液pH为2.0、氧化时间为60min、水解温度为95℃、水解时间为2.5h的条件下可得到84.2%的沉钒率；以Na₂S₂O₈为氧化剂时，Na₂S₂O₈与钒摩尔比为0.65、氧化温度为90℃、氧化时间为45min、沉钒初始溶液pH为2.5、沉钒温度为90℃、沉钒时间为2.5h的条件下可获得93.1%的沉钒率。过硫酸钠氧化过程温和，沉钒率高，铬损失小，更适合工业推广应用。采用SEM获得了沉淀产物的微观形貌，煅烧后得到V₂O₅产品，采用XRF获得了产品组成，通过X射线衍射确定得到的V₂O₅产品为正交晶型。

关键词: 钒铬还原渣, 钒铬分离, 氧化沉钒, 沉钒率, 铬损率

Abstract:

Vanadium chromium reduction slag is a typical hazardous solid waste, which produced from vanadium extraction by sodium roasting, and its resource-oriented utilization is in urgent need. A technical route of separation of vanadium and chromium from vanadium and chromium reduction slag have been proposed by Institute of Process Engineering, Chinese Academy of Sciences via sulfuric acid hydrolysis-preliminary separation of vanadium and chromium-depth separation of chromium/vanadium/iron by complexation, and a 10000-tons demonstration project was built in Pangang Group. The primary principle and process of vanadium/chromium separation in the acidolysis solution of vanadium chromium reduction slag was mainly investigated in this paper. The effect of H₂O₂ and Na₂S₂O₈ on vanadium precipitation was studied, the optimal conditions were determined by experiments. The results showed that when H₂O₂ was used as oxidant, the n(H₂O₂)/n(V) was 0.75, the oxidation temperature was 60℃, the initial pH of the solution was 2.0, the oxidation time was 60min, the hydrolysis temperature was 95℃, and the hydrolysis time was 2.5h, the precipitation rate of vanadium reached 84.2%. Meanwhile, when Na₂S₂O₈was used as oxidant, the n(Na₂S₂O₈)/n(V) was 0.65, the oxidation temperature was 90℃, the oxidation time was 45min, the initial pH of vanadium precipitation was 2.5, the vanadium precipitation temperature was 90℃, and the vanadium precipitation time was 2.5h, the precipitation rate of vanadium reached 93.1%. The results showed that sodium persulfate was more suitable for industrial application due to its mild oxidation process, high vanadium precipitation rate and small chromium loss. The microstructure of precipitated product was obtained by SEM. The V₂O₅ product that obtained after calcination was determined to be orthorhombic by X-ray diffraction.

Key words: vanadium chromium reduction slag, separation of vanadium and chromium, precipitation of vanadium by oxidation, vanadium precipitation rate, chromium loss rate

中图分类号:

TD982

邓孝伯, 韦林森, 申长帅, 李千文, 汪超, 范兵强, 张贺东, 张洋. 钒铬还原渣酸浸液中钒铬初步分离工艺[J]. 化工进展, 2021, 40(7): 4100-4107.

DENG Xiaobo, WEI Linsen, SHEN Changshuai, LI Qianwen, WANG Chao, FAN Bingqiang, ZHANG Hedong, ZHANG Yang. Preliminary separation process of vanadium and chromium in acid leaching solution of vanadium chromium reduction slag[J]. Chemical Industry and Engineering Progress, 2021, 40(7): 4100-4107.

图/表 13

参考文献 14

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元素	质量浓度/g·L^-1
V	15~30
Cr	70~100
Si	0.1
Fe	0.5~1.0
P	0.05

元素	质量浓度/g·L^-1
V	15~30
Cr	70~100
Si	0.1
Fe	0.5~1.0
P	0.05

序号	氧化剂	元素质量浓度/g·L^-1					沉钒率/%	铬损率/%
序号	氧化剂	V	Cr	Si	Fe	P	沉钒率/%	铬损率/%
0	—	26.57	75.65	0.05	0.75	0.04	—	—
1	H₂O₂	4.62	66.35	0.05	0.62	0.04	82.6	12.3
2	H₂O₂	3.89	68.06	0.03	0.55	0.02	85.4	10.0
3	H₂O₂	4.12	65.45	0.04	0.59	0.04	84.5	13.5
4	Na₂S₂O₈	1.95	70.89	0.02	0.65	0.04	92.7	6.3
5	Na₂S₂O₈	1.01	68.82	0.04	0.52	0.03	96.2	9.0
6	Na₂S₂O₈	2.56	69.91	0.03	0.72	0.03	90.4	7.6

序号	氧化剂	元素质量浓度/g·L^-1					沉钒率/%	铬损率/%
序号	氧化剂	V	Cr	Si	Fe	P	沉钒率/%	铬损率/%
0	—	26.57	75.65	0.05	0.75	0.04	—	—
1	H₂O₂	4.62	66.35	0.05	0.62	0.04	82.6	12.3
2	H₂O₂	3.89	68.06	0.03	0.55	0.02	85.4	10.0
3	H₂O₂	4.12	65.45	0.04	0.59	0.04	84.5	13.5
4	Na₂S₂O₈	1.95	70.89	0.02	0.65	0.04	92.7	6.3
5	Na₂S₂O₈	1.01	68.82	0.04	0.52	0.03	96.2	9.0
6	Na₂S₂O₈	2.56	69.91	0.03	0.72	0.03	90.4	7.6

序号	氧化剂	沉淀产物元素质量分数/%
序号	氧化剂	V	Cr	Si	Fe	P	S	Na
1	H₂O₂	27.9	5.2	4.2	0.4	<0.1	3.6	2.5
2	H₂O₂	28.5	5.6	4.6	0.5	<0.1	3.2	2.2
3	H₂O₂	28.2	5.8	3.8	0.5	<0.1	3.2	2.4
4	Na₂S₂O₈	32.0	3.9	3.5	0.4	<0.1	3.1	2.7
5	Na₂S₂O₈	28.6	3.9	4.1	0.4	<0.1	3.3	2.3
6	Na₂S₂O₈	30.6	3.4	3.7	0.5	<0.1	3.5	1.4

钒铬还原渣酸浸液中钒铬初步分离工艺

Preliminary separation process of vanadium and chromium in acid leaching solution of vanadium chromium reduction slag

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序号	氧化剂	质量分数/%
序号	氧化剂	V₂O₅	Cr₂O₃	SiO₂	Fe₂O₃	Na₂O	SO₃
1	H₂O₂	96.0	0.8	0.5	0.2	1.2	0.8
2	Na₂S₂O₈	97.5	0.5	0.4	0.2	0.8	0.5