Study on deactivation of commercial SCR catalyst used in 1000MW coal-fired power plant
FANG Tuo-tuo1, GAO Er-hao1, WANG Liang1,2, XU Nan1, WANG Xiao-xiang1, HE Yi1, PAN Hua3, SHI Yao1
1. Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, China;
2. Zhejiang Zheneng Jiahua Power Plant Co. LTD., Jiaxing 314200, China;
3. College of Biological and Environment Engineering, Zhejiang Shuren University, Hangzhou 310015, China
Fresh and used commercial SCR catalysts (40000hours) obtained from a 1000MW coal-fired plant in Zhejiang Province (China) were examined by catalyst characterization and De-NOx activity test to investigate the deactivation mechanism. The results showed that the deactivation of the catalyst wasattributed to different aspects. (1)Commercial SCR catalyst was poisoned by Fe,S,K and As. The content of Fe, S, K and As on deactivated catalyst increased by 318.0%, 233.3%, 199.3% and 99.8% compared with fresh catalyst, respectively. (2)Deposition of sulphate species and fly ash blocked the pores of SCR catalyst were blocked by Deposition of sulphate species and fly ash, resulting in the decrease of about 20.3%for surface area. (3)Valence of active component (vanadium) and Lewis acid site were changed during the process of deactivation. Compared with fresh catalyst, the V4+/V5+ ratio of deactivated catalyst fell from 6.46 to 1.35, as well as the reduction of 34.2% for Lewis acid site.
方拓拓, 高尔豪, 王亮, 许楠, 王晓祥, 何奕, 潘华, 施耀. 1000MW燃煤电厂商业SCR脱硝催化剂的失活[J]. 中国环境科学, 2019, 39(2): 583-590.
FANG Tuo-tuo, GAO Er-hao, WANG Liang, XU Nan, WANG Xiao-xiang, HE Yi, PAN Hua, SHI Yao. Study on deactivation of commercial SCR catalyst used in 1000MW coal-fired power plant. CHINA ENVIRONMENTAL SCIENCECE, 2019, 39(2): 583-590.
田贺忠,郝吉明,陆永琪,等.中国氮氧化物排放清单及分布特征[J]. 中国环境科学, 2001,21(6):493-497. Tian H Z, HAO J M, LU Y Q, et al. Inventories and distribution characteristics of NOx emissions in China[J]. China Environmental Science, 2001,21(6):493-497.
[2]
李新艳,李恒鹏.中国大气NH3和NOx排放的时空分布特征[J]. 中国环境科学, 2012,32(1):37-42. Li X Y, LI H P. Emission and distribution of NH3and NOx in China[J]. China Environmental Science, 2012,32(1):37-42.
[3]
李帅英,武宝会,姚皓,等.SCR催化剂活性评估对NOx超低排放影响[J]. 中国电力, 2017,50(8):163-167. Li S W, Wu B H, Yao H, et al. Effect of SCR catalyst activity assessment on ultra-low NOx emission[J]. Electric Power, 2017,50(8):163-167.
[4]
王志轩.论我国火电厂氮氧化物控制[J]. 中国电力企业管理, 2009,(22):16-19. Wang Z X. Discussion on nitrogen oxide control of thermal power plant in China[J]. China Power Enterprise Management, 2009,(22):16-19.
[5]
王春兰,宋浩,韩东琴.SCR脱硝催化剂再生技术的发展及应用[J]. 中国环保产业, 2014,(4):22-25. Wang C L, SONG H, Han D Q. Development and Application of Recycling Technology of SCR Denitration Catalytic Agent[J]. Technology & Engineering Application, 2014,(4):22-25.
[6]
李德波,廖永进,徐齐胜,等.燃煤电站SCR脱硝催化剂更换策略研究[J]. 中国电力, 2014,47(3):155-159. Li D B, Liao Y J, Xu Q S, et al. Study on replacement strategy of SCR denitrification catalyst in coal-fired power station[J]. Electric Power, 2014,47(3):155-159.
[7]
雷嗣远,孔凡海,王乐乐,等.燃煤电厂SCR脱硝催化剂磨损诊断及对策研究[J]. 中国电力, 2018,51(1):158-163. Lei S Y, Kong F H, Wang L L, et al. Diagnosis and countermeasures of SCR denitrification catalyst wear in coal-fired power plants[J]. Electric Power, 2018,51(1):158-163.
[8]
Yan K Y, Chi H E, Chen J S, et al. Deactivation mechanism of De-NOx catalyst (V2O5-WO3/TiO2) used in coal fired power plant[J]. Journal of Fuel Chemistry & Technology, 2012,40(11):1359-1365.
[9]
曹俊,傅敏,周林,等.SCR脱硝催化剂中毒的研究进展[J]. 应用化工, 2018,(2):380-385. Cao J, Fu M, Zhou L, et al. Research progress of SCR denitrification catalyst poisoning[J]. Applied Chemical Industry, 2018,(2):380-385.
[10]
孙晓亮.CuO-CexZr(1-x)O2/TiO2催化剂NH3选择性催化还原柴油机NOx的基础研究[D]. 天津:天津大学, 2014. Sun X L. Study on CuO-CexZr1-xO2/TiO2 catalysts for the selective catalytic reduction of NOx with NH3 from diesel engines[D]. Tianjin University, 2014.
[11]
Kamata H, Takahashi K, Odenbrand C U I. The role of K2O in the selective reduction of NO with NH3 over a V2O5(WO3)/TiO2 commercial selective catalytic reduction catalyst[J]. Journal of Molecular Catalysis A Chemical, 1999,139(2/3):189-198.
[12]
Hilbrig F, Goebel H E, Knoezinger H, et al. X-ray absorption spectroscopy study of the titania-and alumina-supported tungsten oxide system[J]. Cheminform, 1991,22(47):6973-6978.
[13]
Chen J P, Yang R T. Mechanism of poisoning of the V2O5/TiO2 catalyst for the reduction of NO by NH3[J]. Journal of Catalysis, 1990,125(2):411-420.
[14]
Zheng Y, And A D J, Johnsson J E. Laboratory Investigation of Selective Catalytic Reduction Catalysts:Deactivation by Potassium Compounds and Catalyst Regeneration[J]. Industrial & Engineering Chemistry Research, 2004,43(4):941-947.
[15]
张秋林.CaO对SCR催化剂选择的影响[J]. 能源研究与利用, 2006, (6):34-35. Zhang Q L. The influence of CaO on SCR catalyst selection[J]. Energy Research & Utilization, 2006,(6):34-35.
[16]
何德良,任慧莺,朱天时,等.V2O5-WO3/TiO2SCR催化剂的钙中毒机理研究[J]. 应用基础与工程科学学报, 2018,(1):1-11. He D L, Ren H Y, Zhu T S, et al. Calcium poisoning mechanism of V2O5-WO3/TiO2 SCR catalyst[J]. Journal of Basic Science and Engineering, 2018,(1):1-11.
[17]
Foerster M. Method for regeneration iron-loaded De-NOx catalysts[M]. US. 2009.
[18]
商雪松,陈进生,赵金平,等.SCR脱硝催化剂失活及其原因研究[J]. 燃料化学学报, 2011,39(6):465-470. Shang X S, Chen J S, Zhao J P, et al. Discussion on the deactivation of SCR denitrification catalyst and its reasons[J]. Journal of Fuel Chemistry and Technology, 2011,39(6):465-470.
[19]
Emeis C A. ChemInform Abstract:Determination of Integrated Molar Extinction Coefficients for IR Absorption Bands of Pyridine Adsorbed on Solid Acid Catalysts[J]. Cheminform, 2010,24(38).
[20]
Forzatti P. Present status and perspectives in De-NOx SCR catalysis[J]. Applied Catalysis A General, 2001,222(1):221-236.
[21]
Handbook of the Elements and Native Oxides. XPS International, Inc.1999[Z].
[22]
段瑞瑞. V4+/V5+比值调变影响因素及其V4+和V5+转化的氧化还原速率与SCR脱硝活性[D]. 哈尔滨:哈尔滨工程大学, 2014. Duan R R. Influences on modulation of the V4+/V5+ ratio and rate of V4+ and V5+ redox and SCR DeNOx activity[D]. Harbin:Harbin Engineering University, 2014.
[23]
陈艳萍.1000MW燃煤电厂钒钛系商业催化剂失活原因分析和再生研究[D]. 杭州:浙江大学, 2015. Chen Y P. The Study of deactivation mechanism and regeneration of commercial V2O5-WO3/TiO2 SCR catalysts used in 1000MW coal fired power plant[D]. Hangzhou:Zhejiang University, 2015.