废钒-钛系脱硝催化剂回收利用策略与技术进展

doi:10.11896/cldb.20070110

材料导报

2021, Vol. 35

Issue (15): 15001-15010 https://doi.org/10.11896/cldb.20070110

材料与可持续发展(四) ———材料再制造与废弃物料资源化利用*

废钒-钛系脱硝催化剂回收利用策略与技术进展

王宝冬¹, 刘子林¹, 林德海¹, 曹子雄¹, 何发泉¹, 路光杰², 肖雨亭³

1 北京低碳清洁能源研究院,北京 102211
2 北京国电龙源环保工程有限公司,北京 100039
3 江苏龙源催化剂有限公司,宜兴 214201

A Review on Recovery and Utilization of Spent V₂O₅-WO₃/TiO₂ Catalyst

WANG Baodong¹, LIU Zilin¹, LIN Dehai¹, CAO Zixiong¹, HE Faquan¹, LU Guangjie², XIAO Yuting³

1 National Institute of Clean and Low Carbon Energy, Beijing 102211, China
2 Beijing Guodian Longyuan Environmental Protection Engineering Co., Ltd., Beijing 100039, China
3 Jiangsu Longyuan Catalyst Co., Ltd., Yixing 214201, China

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摘要我国以煤为主的能源结构以及日趋严格的氮氧化物排放标准催生了选择性催化还原法(SCR)脱硝技术的广泛应用,由于化学失活或物理结构破损等导致大量的废弃脱硝催化剂产生,造成严重的环境污染。然而,SCR催化剂的主要成分钒、钨、钛等有价金属具有重要的经济和战略价值。随着SCR催化剂的广泛使用,脱硝领域将面临严峻的环境污染和资源浪费问题。
针对从废SCR催化剂回收TiO₂、WO₃、V₂O₅等金属元素,目前主要有酸法、碱法或氯化法等主要回收技术路线。在此过程中,通过化学反应,催化剂中钒、钨、钛等金属转变为其他形式化合物或进入到液相,再经过氧化、水解、结晶及煅烧等反应过程,实现产物分离以及产品性能提升的目的。回收的TiO₂既可以作为催化剂的载体,也可以用作涂料、光催化剂等其他材料;WO₃、V₂O₅、MoO₃等可以直接作为原料用于脱硝催化剂再生或制备中,也可用于生产其他化工产品。
从我国特有的煤电局面,以及钒、钨、钛冶金工业为基础,以资源循环利用的未来绿色化工为理念,从废脱硝催化剂的成分及原料性质出发,建议因地制宜、因时制宜及因材制宜地选择技术路线和生产。通过冶金和化工过程回收其有价金属,从强化工艺、高效回收利用、清洁生产三个方面考虑,探索低温反应降低能耗,减少酸碱用量、水耗,缩短工艺流程,提高产量和品质,从而优化整合出一套适合于废SCR脱硝催化剂回收的工艺,实现脱硝催化剂“生产-再生-回收”绿色循环。
本文归纳了废钒-钛系脱硝催化剂回收的研究进展,分别对酸法、碱法和氯化法回收钛白,以及钒-钨分离提纯工艺等进行介绍,分析了废脱硝催化剂回收面临的问题并展望其前景,以期为开发出一套高效清洁的废脱硝催化剂回收技术提供参考。

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	肖雨亭

关键词: 脱硝催化剂回收选择性催化还原钛白钒钨

Abstract: China’s coal based energy structure and more strict NO_X emission standard have led to the extensive application of selective catalytic reduction (SCR) denitration catalyst. Due to chemical deactivation or physical structure damage, a large number of spent SCR catalyst have been produced, which cause serious environmental pollution. On the other hand, the main components of SCR catalysts, such as vanadium, tungsten and titanium, have important economic and strategic value. The wide application of SCR catalyst will led to serious environmental pollution and resource waste.
For the recovery of TiO₂, WO₃, V₂O₅ and other metal elements from waste SCR catalyst, there are mainly acid, alkali and chlorination met-hods. In these processes, vanadium, tungsten, titanium and other metals in the catalyst are transformed into other forms of compounds or dissolved into liquid phase and then separated through oxidation, hydrolysis, crystallization and calcination. The recovered TiO₂ can be used not only as catalyst carrier, but also as coating, photocatalyst and other materials; WO₃, V₂O₅ and MoO₃ can be directly used as raw materials catalyst production or regeneration.
Based on China’s unique situation of coal power situation and vanadium, tungsten, titanium industry, and the concept of future green chemical industry, it is suggested that the recovery process should be considered according to location, time and materials itself. The process optimization is suggested to further develop to improve the product quality and recovery rate, to reduce energy consumption and waste emission.
This review offers a retrospection of the research efforts with respect to recovery of spent vanadium-titanium based SCR catalyst, including acid leaching, alkali leaching, and chlorination process, followed by separation and purification process of vanadium and tungsten. We then pay attention to the problems confronting the current state-of-the-art spent SCR catalyst recovery processes. We have confidence that a life-cycle process of SCR catalyst has a bright future in terms of “Production-Regeneration-Recycling”.

Key words: DeNO_x catalyst recycling SCR titanium oxide vanadium tungsten

出版日期: 2021-08-10 发布日期: 2021-08-31

ZTFLH:

X789

基金资助: 国家重点研发计划(2019YFC1907500)

作者简介: 王宝冬博士,教授级高工,国家能源集团北京低碳清洁能源研究院,环保领域技术总监,从事大气污染治理领域的研发工作。曾主持国家科技部和工业研发项目十多项,获国家专利银奖1项、省部级科技一等奖4项、以第一或通讯作者身份发表论文98篇、专利110项。主要成果在燃煤电厂及非电行业实现了氮氧化物减排的工业化应用。

引用本文:

王宝冬, 刘子林, 林德海, 曹子雄, 何发泉, 路光杰, 肖雨亭. 废钒-钛系脱硝催化剂回收利用策略与技术进展[J]. 材料导报, 2021, 35(15): 15001-15010.
WANG Baodong, LIU Zilin, LIN Dehai, CAO Zixiong, HE Faquan, LU Guangjie, XIAO Yuting. A Review on Recovery and Utilization of Spent V₂O₅-WO₃/TiO₂ Catalyst. Materials Reports, 2021, 35(15): 15001-15010.

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http://www.mater-rep.com/CN/10.11896/cldb.20070110 或 http://www.mater-rep.com/CN/Y2021/V35/I15/15001

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