选择性催化还原脱硝废弃催化剂回收技术研究进展

doi:10.16085/j.issn.1000-6613.2017-0672

摘要/Abstract

摘要： 对目前比较常见的选择性还原脱硝催化剂回收方法（固化处理回收法、化学处理回收法）进行了分类及总结。主要介绍了回收废弃脱硝催化剂的化学回收方法，包括酸浸出法、碱浸出法、焙烧法。对3种方法中的不同工艺进行分析和总结，通过对比分析，碱法回收工艺能回收钛、钒、钨、硅、铝等多种元素，综合性优于其他工艺。目前，针对研究工艺回收物质种类少，回收率低等问题，改进的碱法回收工艺路线有利于问题的解决，通过进一步优化碱法回收技术具有工业化前景。

关键词: 催化剂, 脱硝催化剂, 回收, 废物处理, 选择性催化还原

Abstract: The common methods of recovery technology of spent selective catalytic reduction denitration catalyst (solidification and chemical recovery methods) were classified and summarized. The chemical recovery methods for recovery of SCR catalyst are introduced,including acid leaching,alkali leaching and roasting. The different processes of the three methods were analyzed and concluded. Compared with the recovery process,the alkali recovery process was superior to other processes in the comprehensive recovery of titanium,vanadium,tungsten,silicon,aluminum and other elements. The solve to the problems of fewer types of material and the low recovery rate,the corresponding solutions was the improved alkali recovery process,by further optimization of industrial prospects.

Key words: catalyst, denitrification catalyst, recovery, waste treatment, selective calalytic reduction(SCR)

中图分类号:

X773

董子龙, 杨巧文, 贾卓泰, 李靖涛, 刘向辉, 周玉. 选择性催化还原脱硝废弃催化剂回收技术研究进展[J]. 化工进展, 2017, 36(S1): 449-456.

DONG Zilong, YANG Qiaowen, JIA Zhuotai, LI Jingtao, LIU Xianghui, ZHOU Yu. Research progress on recovery technology of spent selectivecatalytic reduction denitration catalyst[J]. Chemical Industry and Engineering Progress, 2017, 36(S1): 449-456.

参考文献

[1] 赵永椿,马斯鸣,杨建平,等.燃煤电厂污染物超净排放的发展及现状[J].煤炭学报,2015,40(11):2629-2640.ZHAO Y C,MA S M,YANG J P,et al. Status of ultra-low emission technology in coal-fired power plant[J].Journal of China Coal Society,2015,40(11):2629-2640.
[2] 井鹏,岳涛,李晓岩,等.火电厂氮氧化物控制标准、政策分析及研究[J].中国环保产业,2009(4):19-23.JING P, YUE T,LI X Y,et al. Control standards, policy analysis and research on nitrogen oxides in thermal power plants[J].China Environmental Protection Industry,2009(4):19-23.
[3] MA X,REN B,KE G,et al. Oxalic acid influence on selective catalytic reduction of NO_x over tungsten-based zeolite[J].Sciencepaper Online, 2010.
[4] 李想,李俊华,何煦,等.烟气脱硝催化剂中毒机制与再生技术[J].化工进展, 2015,34(12):4129-4138.LI X,LI J H,HE X,et al. Poisoning mechanism and regeneration process of the denitration catalyst[J].Chemical Industry and Engineering Progress, 2015,34(12):4129-4138.
[5] NICOSIA D,CZEKAJ I,KRÖCHER O. Chemical deactivation of V₂O₅/WO₃-TiO₂ SCR catalysts by additives and impurities from fuels, lubrication oils and urea solution:Part Ⅱ. Characterization study of the effect of alkali and alkaline earth metals[J].Applied Catalysis B:Environmental,2008(77):228-236.
[6] 赵炜,于爱华,王虎,等.湿法工艺回收板式SCR废弃催化剂中的钛、钒、钼[J].化工进展,2015,34(7):2039-2042,2048.ZHAO W,YU A H,WANG H,et al. Recovery of waste SCR catalyst from titanium, vanadium and molybdenum by wet method[J]. Chemical Industry and Engineering Progress,2015,34(7):2039-2042,2048.
[7] ZHANG F M,CHEN F,XIAO Q,et al. Ammoxidation of 3-picoline over V₂O₅/TiO₂ catalysts:effects of TiO₂ supports on the catalytic performance[J].Advanced Materials Research,2011, 396-398:791-797.
[8] RAZIYEH K. Regeneration of commercial SCR catalysts by washing and sulphation:effect of sulphate groups on the activity[J].Applied CatalysisB:Environmental,2001,33:277-291.
[9] BENSON S A, LAUMB J D, CROCKER C R, et al. SCR catalyst performance in flue gases derived from subbituminous and lignite coals[J].Fuel Processing Technology,2005, 86(5):577-613.
[10] DUAN J F,SHI W W,XIA Q B,et al. Characterization and regeneration of deactivated commercial SCR catalyst[J].Journal of Functional Materials,2012,43(16):2191-2195.
[11] ZENG R. Consideration on reclaiming industry of SCR waste catalyzer in China[J].China Environmental Protection Industry,2013(4):55-61.
[12] 陈颖通.一种报废SCR脱硝催化剂填埋前的处理及固化方法:104926235A[P]. 2015-09-23.CHEN Y T. Waste SCR denitration catalyst landfill treatment and curing method:104926235A[P]. 2015-09-23.
[13] 周昊,国旭涛,周明熙.一种废弃SCR烟气脱硝催化剂冶金烧结处理方法:105907950A[P]. 2016-08-31.ZHOU H,GUO X T,ZHOU M X. Metallurgical sintering treatment method for waste SCR flue gas denitration catalyst:105907950A[P]. 2016-08-31.
[14] 郑志海,郑逸枫.废烟气脱硝催化剂无害化处理工艺:104609753A[P]. 2015-05-13.ZHENG Z H,ZHENG Y F. Harmless treatment process of waste gas denitration catalyst:104609753A[P]. 2015-05-13.
[15] 徐芙蓉,周立荣.燃煤电厂SCR脱硝装置失效催化剂处理方案探讨[J].中国环保产业,2010(11):25-27.XU F R, ZHOU L R. Discussion about processing scheme for disabled SCR catalyst in coal-fired power plant[J].China Environmental Protection Industry,2010(11):25-27.
[16] 李力成,王磊,赵学娟,等.几种酸在废弃脱硝催化剂中提钒效果的比较[J].中国有色金属学报,2016(10):2230-2237.LI L C,WANG L,ZHAO X J,et al. Comparison of effect of different acid treatments on vanadium extraction of waste deNO_x catalyst[J].Transactions of Nonferrous Metals Society of China,2016(10):2230-2237.
[17] 张兵兵,于丹丹,王芳,等.废脱硝催化剂中五氧化二钒回收工艺研究[J].河南科学,2016,34(6):866-870.ZHANG B B,YU D D, WANG F,et al. Technology of vanadiun recovery from deactivated denitration catalyst[J].Henan Science,2016,34(6):866-870.
[18] 陈颖敏,谢宗,王超凡.燃煤电厂废弃催化剂回收钒的研究[J].钢铁钒钛,2016(4):69-75.CHEN Y M,XIE Z,WANG C F. Study on the recovery of vanadium from waste catalyst in coal-fired power plants[J].Iron Steel Vanadium Titanium, 2016(4):69-75.
[19] 唐丁玲,宋浩,刘丁丁,等.废弃脱硝催化剂碱浸提取钒和钨的浸出动力学研究[J].环境工程学报,2017,11(2):1093-1100.TANG D L,SONG H,LIU D D,et al. Study on leaching kinetics of extracting vanadium and tungsten by sodium hy-droxide from spent SCR catalyst[J].Chinese Journal of Environmental Engineering,2017,11(2):1093-1100.
[20] WU W C,TSAI T Y,SHEN Y H,et al. Tungsten recovery from spent SCR catalyst using alkaline leaching and ion exchange[J]. Minerals,2016,6(4):107.
[21] LEE J Y,KIM J S. Method for leaching precious metals contained in waste denitrification catal using pressure leaching process:EP20150757987[P]. 2017-01-11.
[22] KIM J W,LEE W G,HWANG I S,et al. Recovery of tungsten from spent selective catalytic reduction catalysts by pressure leaching[J].Journal of Industrial & Engineering Chemistry,2015, 28:73-77.
[23] HUO Y,CHANG Z,LI W,et al. Reuse and valorization of vanadium and tungsten from waste V₂O₅-WO₃/TiO₂,SCR catalyst[J].Waste and Biomass Valorization,2015,6(2):159-165.
[24] LEE J Y,KIM J S,KUMAR R,et al. Method for leaching valuable metals contained in waste denitrification catalyst by using roasting and water leaching:EP2894233[P].2015-07-15.
[25] KIM H R,LEE J Y,KIM J S,et al. Leaching of vanadium and tungsten from spent SCR catalysts for De-NO_x by soda roasting and water leaching method[J].Journal of the Korean Institute of Resources Recycling,2012,21(6):65-73.
[26] 张琛,刘建华,杨晓博,等.超声强化废SCR催化剂浸出V和W的研究[J].功能材料,2015,46(20):20063-20067.ZHANG C,LIU J H,YANG X B,et al. Ultrasound assisted enhancement in vanadium and tungsten leaching from waste SCR catalyst[J].Functional Materials,2015,46(20):20063-20067.
[27] 张琛.废SCR催化剂中钒、钨的浸出与萃取分离研究[D].广州:华南理工大学,2016.ZHANG C. The study on leaching and solvent extraction separation of vanadium and tungsten from waste SCR catalysts[D]. Guangzhou:South China University of Technology,2016.
[28] 贾勇,丁万丽,丁希楼,等.废SCR脱硝催化剂中钨和钒的浸出实验研究[J].环境科学学报,2016,36(10):3759-3764.JIA Y,DING W L,DING X L,et al. The leaching of tungsten and vanadium from spent selective catalytic reduction catalyst[J].Acta Scientiae Circumstantiae,2016,36(10):3759-3764.
[29] SANG H Y. Recycling of the waste TiO₂-WO₃-V₂O₅ system honeycomb type SCR catalyst for De-NO_x[D]. Gyeong Sang:Gyeong Sang National University,2011.
[30] 李启超.钒钛基SCR催化剂的中毒、再生与回收[D].北京:北京化工大学, 2015.LI Q C. Study of deactivation,regeneration and recovery of vanadium-titanium based SCR catalysts[D]. Beijing:Beijing University of Chemical Technology,2015.
[31] 刘子林,王宝冬,马瑞新,等.废SCR催化剂钠化焙烧回收钨和钒的机理探究[J].无机盐工业,2016(7):63-67.LIU Z L,WANG B D,MA R X,et al. Study on mechanism of recovery of tungsten and vanadium from waste SCR catalysts by soda roasting[J]. Inorganic Chemicals Industry,2016(7):63-67.
[32] 陈颖敏,谢宗,王超凡.燃煤电厂废弃SCR催化剂回收二氧化钛的研究[J].中国电力,2016,49(6):151-156.CHEN Y M,XIE Z, WANG C F. Study on the TiO₂ recovery from SCR catalyst waste in coal-fired power plants[J].Electric Power,2016,49(6):151-156.