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过程工程学报 ›› 2023, Vol. 23 ›› Issue (4): 562-570.DOI: 10.12034/j.issn.1009-606X.222146

• 研究论文 • 上一篇    下一篇

空气焙烧-碱浸法回收废加氢催化剂中的钼和钒

李雨恩1， 于博1， 凌江华1， 张成2， 胡久刚3， 刘美1*
  

  1. 1. 辽宁石油化工大学石油化工学院，辽宁 抚顺 113001 2. 中国石油化工股份有限公司大连石油化工研究院，辽宁 大连 116041 3. 中南大学化学化工学院，湖南 长沙 410083
  • 收稿日期:2022-04-26 修回日期:2022-05-26 出版日期:2023-04-28 发布日期:2023-05-04
  • 通讯作者: 刘美 liumeifushun@163.com
  • 作者简介:李雨恩，硕士研究生，化学工程专业，E-mail: 532484116@qq.com；通讯联系人，刘美，副教授，主要从事重质油加工方面的研究，E-mail: liumeifushun@163.com
  • 基金资助:
    辽宁省高等学校创新人才支持计划;中国石油化工股份有限公司资助项目;国家自然科学基金资助项目;重质油国家重点实验室开放课题

Recovering molybdenum and vanadium from spent hydroprocessing catalyst by air roasting-alkaline leaching process

Yuen LI1,  Bo YU1,  Jianghua LING1,  Cheng ZHANG2,  Jiugang HU3,  Mei LIU1*   

  1. 1. College of Petrochemical Engineering, Liaoning Petrochemical University, Fushun, Liaoning 113001, China 2. Dalian Petrochemical Research Institute, China Petrochemical Corporation, Dalian, Liaoning 116041, China 3. College of Chemistry and Chemical Engineering, Central South University, Changsha, Hunan 410083, China
  • Received:2022-04-26 Revised:2022-05-26 Online:2023-04-28 Published:2023-05-04

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摘要： 废加氢催化剂中含有大量的有机污染物和金属元素，如钼、钒、镍和铝，若处理不当，会造成严重的生态污染和资源浪费。本研究采用空气焙烧-碳酸钠浸出法处理废弃加氢催化剂以回收其中的钼和钒。通过热力学计算可知低温碳酸钠浸出可以实现废催化剂中钼、钒与铝、镍的分离。单因素实验考察了空气焙烧温度、碳酸钠浓度、反应时间、浸出温度、液固比等工艺条件对钼和钒浸出率的影响。实验结果表明，在焙烧温度500℃，碳酸钠浓度4 mol/L，浸出温度80℃，反应时间90 min，液固比为20:1的条件下，钼和钒的浸出率可分别达到98.02%和94.36%。为了最大限度地回收钼和钒，采用二段逆流浸出流程处理废加氢催化剂，可将钼和钒的浸出率维持在98%和97%。浸出渣中主要含有Al2O3, NiO和NiAl26O40，而绝大部分钼和钒被转移至浸出液中。

关键词: 废加氢催化剂, 钼, 钒, 空气焙烧-碱浸, 二段逆流浸出

Abstract: With the rapid development of oil refining industry, the annual generation of global spent hydroprocessing catalysts is gradually increasing. Spent hydroprocessing catalysts are rich in organic pollutants and metals including molybdenum, vanadium, nickel, and aluminum, which will lead to not only serious deterioration of ecological environment but also waste a great amount of resource. In this study, a process featured by air roasting-alkaline leaching was proposed to treat the spent hydroprocessing catalyst in the purpose of recovering molybdenum and vanadium. Thermogravimetric (TG), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy/energy dispersive spectroscopy (SEM/EDS) techniques were employed to characterize the raw spent catalysts, the roasted product and the leaching residues. Air-roasting can make the metal sulfides convert to oxides which were able to be dissolved into leaching solution by sodium carbonate. Thermodynamic analysis showed that the low-temperature leaching can separate molybdenum and vanadium from aluminum and nickel in the spent catalysts. The effects of air roasting temperature, sodium carbonate concentration, reaction time, leaching temperature and liquid to solid ratio on the leaching rate of molybdenum and vanadium were investigated by the single factor experiments. The experimental results showed that the leaching rates of molybdenum and vanadium reached 98.02% and 94.36%, respectively, under the optimum conditions with roasting temperature of 500℃, sodium carbonate concentration of 4 mol/L, leaching temperature of 80℃, reaction time of 90 min and liquid-solid ratio of 20:1. In order to maximize the recovery of molybdenum and vanadium, the two-stage counter current leaching process was adopted subsequently, and the leaching rate of molybdenum and vanadium were able to maintain at 98% and 97%, respectively. The leaching residue mainly contained Al2O3, NiO and NiAl26O40, and most of molybdenum and vanadium transferred into leaching solution. The advantage of this process is that molybdenum and vanadium can be fully recovered and satisfactorily separated from nickel and aluminum with the mild leaching conditions, which is benefit for the following treatment of leaching residues.

Key words: spent hydroprocessing catalyst, molybdenum, vanadium, air roasting-alkaline leaching, two-stage counter-current leaching