Recycling and reuse of TiO2 carrier from waste SCR catalysts used in coal-fired power plants

doi:10.11949/j.issn.0438-1157.20170504

Abstract

Abstract:

The recycling and reuse of TiO₂ carrier from waste SCR catalysts used in coal-fired power plants was studied. The influence of reaction time, temperature, liquid-to-solid ratio and NaOH concentration on the leaching efficiency of Al, Si, V, W and Ti during leaching process, specific surface area and pore volume of leaching residue was investigated. The optimal leaching conditions were obtained with reaction time of 180 min, temperature of 160℃, liquid-to-solid ratio of 15 ml·g^-1 and NaOH concentration of 2.5 mol·L^-1. The main composition of the leaching residue obtained under optimal conditions was anatase TiO₂, which was then used to synthesize V₂O₅-WO₃/TiO₂ catalysts with various V₂O₅ loadings after acid washing. The activity evaluation revealed that the resynthesized 0.7% V₂O₅-WO₃/TiO₂ catalyst was almost recovered to the level of fresh catalyst with NO conversion being recovered to 97.8% at 300℃, and it also showed a good resistance to SO₂ and H₂O.

Key words: coal-fired power plant, flue gas denitration, selective catalytic reduction, waste catalyst, TiO₂ carrier, reuse

摘要：

以燃煤电厂废弃SCR脱硝催化剂为研究对象，考察了浸出时间、温度、液固比和NaOH浓度对碱浸过程Al、Si、V、W、Ti等元素浸出率以及浸出渣比表面积、孔容的影响。结果表明，碱浸的最优工艺条件为反应时间180 min、温度160℃、液固比15 ml·g^-1、NaOH浓度2.5 mol·L^-1。在最优工艺条件下得到的浸出渣主要成分为锐钛矿型TiO₂，经稀硫酸洗涤后作为载体，通过负载与新鲜催化剂相同含量的WO₃和V₂O₅，制备了V₂O₅-WO₃/TiO₂催化剂。对催化剂进行脱硝活性评价，结果表明，再生载体制备的催化剂脱硝活性恢复至新鲜催化剂水平，300℃时NO转化率达到97.8%，且具有良好的抗硫抗水性。

关键词: 燃煤电厂, 烟气脱硝, 选择性催化还原, 废弃催化剂, TiO₂载体, 再利用

CLC Number:

QI Chunping, WU Wenfen, WANG Chenye, LI Huiquan. Recycling and reuse of TiO₂ carrier from waste SCR catalysts used in coal-fired power plants[J]. CIESC Journal, 2017, 68(11): 4239-4248.

戚春萍, 武文粉, 王晨晔, 李会泉. 燃煤电厂废旧SCR脱硝催化剂中TiO₂载体的回收与再利用[J]. 化工学报, 2017, 68(11): 4239-4248.

References 33

[1]	HU Y H, GRIFFITHS K, NORTON P R. Surface science studies of selective catalytic reduction of NO:progress in the last ten years[J]. Surface Science, 2009, 603(10/11/12):1740-1750.
[2]	LISI L, LASORELLA G, MALLOGGI S, et al. Single and combined deactivating effect of alkali metals and HCl on commercial SCR catalysts[J].Applied Catalysis B:Environmental, 2004, 50(4):251-258.
[3]	高岩, 栾涛, 彭吉伟, 等. 燃煤电厂真实烟气条件下SCR催化剂脱硝性能[J]. 化工学报, 2013, 64(7):2611-2618. GAO Y, LUAN T, PENG J W, et al. DeNOx performance of SCR catalyst for exhaust gas from coal-fired power plant[J]. CIESC Journal, 2013, 64(7):2611-2618.
[4]	ZHENG Y, JENSEN A D, JOHNSSON J E. Laboratory investigation of selective catalytic reduction catalysts:deactivation by potassium compounds and catalyst generation[J]. Industrial & Engineering Chemistry Research, 2004, 43(4):941-947.
[5]	姜烨, 高翔, 吴卫红, 等. 选择性催化还原脱硝催化剂失活研究综述[J]. 中国电机工程学报, 2013, 33(14):18-31. JIANG Y, GAO X, WU W H, et al. Review of the deactivation of selective catalytic reduction DeNOx catalysts[J]. Proceedings of CSEE, 2013, 33(14):18-31.
[6]	张烨, 徐晓亮, 缪明烽. SCR脱硝催化剂失活机理研究进展[J]. 能源环境保护, 2011, 25(4):14-18. ZHANG Y, XU X L, MIAO M F. Advance in deactivation mechanism for SCR denitration catalyst[J]. Energy Environmental Protection, 2011, 25(4):14-18.
[7]	PENG Y, LI J, CHEN L, et al. Alkali metal poisoning of a CeO2-WO3 catalyst used in the selective catalytic reduction of NOx with NH3:an experimental and theoretical study[J]. Environmental Science & Technology, 2012, 46:2864-2869.
[8]	马建蓉, 黄张根, 刘振宇, 等. 再生方法对V2O5/AC催化剂同时脱硫脱硝活性的影响[J]. 催化学报, 2005, 26(6):463-469. MA J R, HUANG Z G, LIU Z Y, et al. Effect of regeneration method on activity for simultaneous removal of SO2 and NO over V2O5/AC catalyst-sorbent[J]. Chinese Journal of Catalysis, 2005, 26(6):463-469.
[9]	XIE G, LIU Z, ZHU Z, et al. Reductive regeneration of sulfated CuO/Al2O3 catalyst-sorbent in ammonia[J]. Applied Catalysis B:Environmental, 2003, 45(3):213-221.
[10]	LEE J B, KIM S K, KIM D W, et al. Effect of H2SO4 concentration in washing solution on regeneration of commercial selective catalytic reduction catalyst[J]. Korean Journal of Chemical Engineering, 2012, 29:270-276.
[11]	YU Y K, HE C, CHEN J S, et al. Regeneration of deactivated commercial SCR catalyst by alkali washing[J]. Catalysis Communications, 2013, 39:78-81.
[12]	YU Y K, MENG X R, CHEN J S, et al. Deactivation mechanism and feasible regeneration approaches for the used commercial NH3-SCR catalysts[J]. Environmental Science & Technology, 2016, 37:828-836.
[13]	KHODAYARI R, ODENBRAND C I. Regeneration of commercial SCR catalysts by washing and sulphation:effect of sulphate groups on the activity[J]. Applied Catalysis B:Environmental, 2001, 33:277-291.
[14]	李俊峰, 张兵兵, 李翼然, 等. 基于钒钛基SCR法废脱硝催化剂的回收利用[J]. 广州化工, 2014, 42(24):130-132. LI J F, ZHANG B B, LI Y R, et al. Study on reclamation of deactivated De-NOx catalyst based on V2O5-TiO2[J]. Guangzhou Chemical Industry, 2014, 42(24):130-132.
[15]	汪德志, 吴刚, 肖雨亭, 等. 从选择性催化还原脱硝催化剂中回收钨组分的方法:103088217A[P]. 2013-05-08. WANG D Z, WU G, XIAO Y T, et al. Method for recovering tungsten component from selective catalytic reduction denitrification catalyst:103088217A[P]. 2013-05-08.
[16]	陈晨, 陆强, 蔺卓玮, 等. 燃煤电厂废弃SCR脱硝催化剂元素回收研究进展[J]. 化工进展, 2016, 35(10):3306-3312. CHEN C, LU Q, LIN Z W, et al. Research progress of element recovery of waste De-NOx SCR catalyst from coal-fired power plants[J]. Chemical Industry and Engineering Progress, 2016, 35(10):3306-3312.
[17]	李冬芳, 朱彤, 林德海, 等. V-W-Ti基脱硝催化剂资源化回收[J]. 环境工程, 2015, 33(增):335-338. LI D F, ZHU T, LIU D H, et al. Resource recycling of V-W-Ti SCR catalyst[J]. Environmental Engineering, 2015, 33(suppl.):335-338.
[18]	MAZUREK K, BIALOWICZ K, TRYPUC M. Recovery of vanadium, potassium and iron from a spent catalyst using urea solution[J]. Hydrometallurgy, 2010, 103:19-24.
[19]	MAZUREK K. Recovery of vanadium, potassium and iron from a spent vanadium catalyst by oxalic acid solution leaching, precipitation and ion exchange processes[J]. Hydrometallurgy, 2013, 134/135:26-31.
[20]	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 and Engineering Chemistry, 2015, 28:73-77.
[21]	HUO Y T, CHANG Z D, LI W J, et al. Reuse and valorization of vanadium and tungsten from waste V2O5-WO3/TiO2 catalyst[J]. Waste Biomass Valoration, 2015, 6:159-165.
[22]	ZHAO Z P, GUO M, ZHANG M. Extraction of molybdenum and vanadium from the spent diesel exhaust catalyst by ammonia leaching method[J]. Journal of Hazardous Materials, 2015, 286:402-409.
[23]	吴晓东, 许腾飞, 刘雪松, 等. 一种从废钒钨钛催化剂中回收锐钛矿型钛钨粉的方法:104789780B[P]. 2016-09-21. WU X D, XU T F, LIU X S, et al. A process for recovering anatase titanium tungsten powder from scrap tungsten titanium vanadium catalyst:104789780B[P]. 2016-09-21.
[24]	LI W, ZHANG Q G, GU M Y, et al. Effect of temperature on rheological behavior of silicon carbide aqueous suspension[J]. Ceramics International, 2006, 32:761-765.
[25]	冯雅丽, 刘鹏伟, 李浩然, 等. 大洋多金属结核高压低质量分数碱浸过程中SiO2溶出行为[J]. 中南大学学报(自然科学版), 2016, 47(7):2196-2204. FENG Y L, LIU P W, LI H R, et al. Dissolving behavior of silica of ocean polymetallic nodules in low mass fraction of alkali leaching under high pressure[J]. Journal of Central South University(Science and Technology), 2016, 47(7):2196-2204.
[26]	LI J H, PENG Y, CHANG H Z, et al. Chemical poison and regeneration of SCR catalysts for NOx removal from stationary sources[J]. Frontiers of Environmental Science & Engineering, 2016, 10:413-427.
[27]	TANG F S, ZHUANG K, YANG F, et al. Effect of dispersion state and surface properties of supported vanadia on the activity of V2O5/TiO2 catalysts for the selective catalytic reduction of NO by NH3[J]. Chinese Journal of Catalysis, 2012, 33(6):933-940.
[28]	MARBERGER A, ELSENER M, FERRI D, et al. VOx surface coverage optimization of V2O5/WO3-TiO2 SCR catalysts by variation of the V loading and by aging[J]. Catalysts, 2015, 5:1704-1720.
[29]	李丽, 盘思伟, 赵宁, 等. 燃煤电厂SCR脱硝催化剂评价与再生[M]. 北京:中国电力出版社, 2015:3-15. LI L, PAN S W, ZHAO N, et al. Evaluation and Regeneration of SCR Denitration Catalyst Used in Coal-Fired Power Plants[M]. Beijing:China Electric Power Press, 2015:3-15.
[30]	HUANG Z G, ZHU Z P, LIU Z Y. Combined effect of H2O and SO2 on V2O5/AC catalysts for NO reduction with ammonia at lower temperatures[J]. Applied Catalysis B:Environmental, 2002, 39:361-368.
[31]	CHEN L, LI J, GE M. The poisoning effect of alkali metals doping over nano V2O5-WO3/TiO2 catalysts on selective catalytic reduction of NOx by NH3[J]. Chemical Engineering Journal, 2011, 170(2/3):531-537.
[32]	ARFAOUI J, BOUDALI L K, GHORBEL A, et al. Effect of vanadium on the behaviour of unsulfated and sulfated Ti-pillared clay catalysts in the SCR of NO by NH3[J]. Catalysis Today, 2009, 142(3/4):234-238.
[33]	CHMIELARZ L, KU?TROWSKI P, ZBROJA M, et al. Selective reduction of NO with NH3 over pillared clays modified with transition metals[J]. Catalysis Today, 2004, 90(1/2):43-49.

Recycling and reuse of TiO₂ carrier from waste SCR catalysts used in coal-fired power plants

燃煤电厂废旧SCR脱硝催化剂中TiO₂载体的回收与再利用

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