失活硫酸催化剂两步法选择性清洁提钒研究

贾美丽; 杜浩; 张懿; 王少娜; 李兰杰; 祁健; 周冰晶; 赵备备

doi:10.7513/j.issn.1004-7638.2024.05.002

失活硫酸催化剂两步法选择性清洁提钒研究

doi: 10.7513/j.issn.1004-7638.2024.05.002

贾美丽^{1, 2,},
杜浩²,
张懿²,
王少娜^2, ,,
李兰杰³,
祁健⁴,
周冰晶⁴,
赵备备⁴

1.
东北大学冶金学院, 辽宁沈阳110004
2.
中国科学院过程工程研究所, 战略金属资源绿色循环利用国家工程研究中心，北京100190
3.
河北河钢材料技术研究院有限公司, 河北承德 067102
4.
承德钒钛新材料有限公司, 河北承德 067102

基金项目: 河北省科技重大专项项目（23293801Z）。

详细信息

作者简介:
贾美丽，1991年出生，女，山西吕梁人，博士，研究方向为含钒废催化剂中钒的提取，E-mail: 18216405130@163.com

通讯作者:
王少娜，1979年出生，女，山西长治人，博士，副研究员，研究方向为含钒资源高效清洁利用，E-mail: shnwang@ipe.ac.cn

中图分类号: TF841.3
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- 被引次数: 0
出版历程
- 收稿日期: 2024-06-21
- 网络出版日期: 2024-10-30
- 刊出日期: 2024-10-30

Research on the vanadium extraction from deactivated sulfuric acid catalyst featured with two-step and selectively

Jia Meili^{1, 2
,},
Du Hao²,
Zhang Yi²,
Wang Shaona^{2
, ,},
Li Lanjie³,
Qi Jian⁴,
Zhou Bingjing⁴,
Zhao Beibei⁴

1.
School of Metallurgy, Northeastern University, Shenyang 110004, Liaoning, China
2.
Institute of Process Engineering, Chinese Academy of Sciences, National Engineering Research Center of Green Recycling for Strategic Metal Resources, Beijing 100190, China
3.
Hebei He Steel Material Technology Research Institute Co., Ltd., Chengde 067102, Hebei, China
4.
Chengde Vanadium Titanium New Material Co., Ltd., Chengde 067102, Hebei, China

摘要

摘要: 针对失活硫酸催化剂直接酸浸、碱浸工艺选择性差，后续分离代价高、介质难回用的问题，使用两步法选择性提钒新工艺，利用钾、硫的强水溶性特点，研究了水洗温度、pH值对钾、硫浸出的影响，发现在温度40～60 ℃、pH值3～5水洗条件下，钾、硫的浸出率分别达到80%、96%以上，而钒的损失率控制在10%以内，实现了钒与钾、硫的选择性分离；第二步利用钒、硅在碱介质中的溶出特性，研究了碱浸温度、时间、液固比及碱液浓度对提钒效果的影响，发现采用5% NaOH溶液在80 ℃、L/S=5条件下反应30 min可实现失活硫酸催化剂中钒95%以上的浸出，而硅基本不浸出，实现了钒、硅的选择性分离。含钒浸出液可经钙化-铵化工艺制备得到偏钒酸铵产品，NaOH介质返回提钒阶段循环使用，介质封闭。
- 失活硫酸催化剂 /
- 提钒 /
- 碱浸 /
- 偏钒酸铵
Abstract: Based on the limited selectivity exhibited by current direct acid leaching and alkaline leaching processes for deactivated sulfuric acid catalysts, resulting in costly subsequent separation and challenging medium reuse, a new two-step process for selective extraction of vanadium was adopted. Using the strong water solubility of potassium and sulfur, the influence of washing temperature and pH value on leaching of potassium and sulfur was studied. It was found that potassium and sulfur can be removed more than 80% and 96% respectively by water washing under the condition of temperature 40~60℃ and pH 3~5, while the loss rate of vanadium was controlled within 10%. Thus, the selective separation of vanadium from potassium and sulfur was realized. In the second step, based on the leaching characteristics of vanadium and silicon in an alkali medium, the effects of leaching temperature, time, liquid-solid ratio and alkali concentration on vanadium extraction were studied. It was found that after reaction with 5% NaOH solution at 80 ℃ and L/S = 5 for 30 min, more than 95% vanadium was deactivated from the sulfuric acid catalyst, while the silicon leaching rate kept almost zero. The vanadium-containing leaching solution can be handled by calcification and ammonium process to obtain ammonium metavanadate products. The NaOH solution can be recycled to vanadium extraction step and wastewater zero emission was achieved.
- deactivated sulfuric acid catalyst /
- extraction of vanadium /
- alkaline leaching /
- ammonium metavanadate

HTML全文

图 1 失活硫酸催化剂样品外观形貌

Figure 1. Sample appearance of deactivated sulfuric acid catalyst

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图 2 失活硫酸催化剂XRD分析结果

Figure 2. XRD result of deactivated sulfuric acid catalyst

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图 3 失活硫酸催化剂XPS分析

Figure 3. XPS spectrum of deactivated sulfuric acid catalyst

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图 4 失活硫酸催化剂两步法清洁提钒工艺设计

Figure 4. Design of vanadium extraction process by two-stage cleaning with deactivated sulfuric acid catalyst

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图 5 pH对失活硫酸催化剂中元素浸出率的影响

Figure 5. Effect of pH on leaching rate of elements from deactivated sulfuric acid catalyst

(a) 15 ℃；(b) 40 ℃；(c) 60 ℃；(d) 95 ℃

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图 6 NaOH浓度对失活硫酸催化剂主要元素浸出率影响

Figure 6. The effect of NaOH concentration on the leaching rate of main elements in deactivated sulfuric acid catalyst

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图 7 NaOH浸出失活硫酸催化剂工艺条件的选择

（a）浸出温度；（b）液固比；（c）浸出时间

Figure 7. Selection of process conditions for NaOH leaching of deactivated sulfuric acid catalyst

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图 8 不同批次碱浸提钒效果

Figure 8. Vanadium extraction results from different batches of alkali leaching

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图 9 NaOH介质中钒产品转化路线

Figure 9. Roadmap for conversion of vanadium products in NaOH medium

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图 10 钙化反应吉布斯自由能变

Figure 10. Gibbs free energy change of calcification reaction

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图 11 V、Si、P发生钙化反应优先级

Figure 11. Priority of V, Si, P in calcification

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图 12 铵化反应吉布斯自由能变

Figure 12. Gibbs free energy change for ammonium reaction

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图 13 NH₄VO₃结晶产物的表征

（a）XRD表征；（b）SEM形貌

Figure 13. XRD (a) and SEM (b) of NH₄VO₃ crystallization products

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表 1 失活硫酸催化剂成分分析结果

Table 1. Result of ICP analysis of deactivated sulfuric acid catalyst %

Na₂O	SiO₂	V₂O₅	K₂O	MgO	CaO	TiO₂	Fe₂O₃	Al₂O₃	P₂O₅	As₂O₅	SO₃
5.31	53.04	5.23	11.73	0.17	0.20	0.10	1.21	1.62	1.45	0.02	19.92

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表 2 最佳水洗条件下失活硫酸催化剂水洗液成分

Table 2. Composition of water lotion of deactivated sulfuric acid catalyst under optimal water washing condition

温度/℃	pH	含量/（g·L⁻¹）
温度/℃	pH	Na₂O	SiO₂	V₂O₅	K₂O	MgO	CaO	TiO₂	Fe₂O₃	Al₂O₃	P₂O₅	S
40	3	11.56	＜检测下限	0.70	22.00	0.50	0.42	＜检测下限	0.31	1.92	0.07	17.03
40	5	13.60	＜检测下限	0.17	23.41	0.49	0.42	＜检测下限	0.02	1.85	0.03	17.11
60	3	8.50	＜检测下限	0.10	19.80	0.38	0.30	＜检测下限	0.32	1.39	＜检测下限	13.85
60	5	8.54	＜检测下限	0.24	19.25	0.36	0.30	＜检测下限	＜检测下限	1.05	0.02	13.55

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表 3 NaOH浸液钙化铵化成分变化

Table 3. Changes of calcified ammonium compositions in NaOH infusion

成分	含量/（g·L⁻¹）			含量/%
成分	NaOH浸出液	钙化后碱液	铵化后液	钒酸钙	碳酸钙
Na₂O	34.95	34.82	0.02
SiO₂	0.39	0.32	0.06	0.17	0.99
Al₂O₃	0.58	0.55
P₂O₅	3.11	0.28	0.18	8.34	6.85
V₂O₅	16.22	0.52	29.45	40.38	1.55

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