铜系低温选择性催化还原脱硝催化剂的研究进展

doi:10.16085/j.issn.1000-6613.2017-2281

化工进展 ›› 2018, Vol. 37 ›› Issue (10): 3858-3866.DOI: 10.16085/j.issn.1000-6613.2017-2281

铜系低温选择性催化还原脱硝催化剂的研究进展

张巍^1,2,3, 卢程^1,2,3, 董鹏飞^1,2,3, 尹艳山^1,2,3, 方毅伟^1,2,3, 邹济遥^1,2,3, 胡章茂^1,2,3, 阮敏^1,2,3, 徐慧芳^1,2,3

1 长沙理工大学能源与动力工程学院, 湖南长沙 410114;
2 可再生能源电力技术湖南省重点实验室, 湖南长沙 410114;
3 清洁能源与智能电网湖南省 2011 协同创新中心, 湖南长沙 410114

收稿日期:2017-11-06 修回日期:2018-03-21 出版日期:2018-10-05 发布日期:2018-10-05
通讯作者: 张巍(1974-),男,讲师,硕士生导师,研究方向为燃烧过程与污染物控制。
作者简介:张巍(1974-),男,讲师,硕士生导师,研究方向为燃烧过程与污染物控制。E-mail:weizhang@csust.edu.cn。
基金资助:
湖南省自然科学基金（13JJ6045）、湖南省教育厅科学研究项目（13C1014）及污染控制与资源化研究国家重点实验室开放基金项目（PCRRF14018）。

Research progress of copper based low temperature SCR denitration catalysts

ZHANG Wei^1,2,3, LU Cheng^1,2,3, DONG Pengfei^1,2,3, YIN Yanshan^1,2,3, FANG Yiwei^1,2,3, ZOU Jiyao^1,2,3, HU Zhangmao^1,2,3, RUAN Min^1,2,3, XU Huifang^1,2,3

1 School of Energy and Power Engineering, Changsha University of Science and Technology, Changsha 410114, Hunan, China;
2 Key Laboratory of Renewable Energy and Electric Power Technology of Hunan Province, Changsha 410114, Hunan, China;
3 Hunan Province 2011 Collarative Innovation Center of Clean Energy and Smart Grid, Changsha 410114, Hunan, China

Received:2017-11-06 Revised:2018-03-21 Online:2018-10-05 Published:2018-10-05

摘要/Abstract

摘要： 选择性催化还原（SCR）技术已广泛应用在燃煤电站烟气脱硝技术中，开发低温高活性、高抗中毒性能的催化剂体系已经成为国内外学者的研究重点。Cu系催化剂由于具有良好的脱硝性能及水热稳定性，得到了广泛的研究和关注。本文综述了近年来活性组分Cu负载在TiO₂、Al₂O₃、碳基材料和分子筛等材料上的研究进展；重点分析了Cu系催化剂低温SCR反应机理，主要包括Eley-Rideal （E-R）机理和Langmuir-Hinshelwood （L-H）机理，同时分析了SCR反应的两个必然过程：吸附（NH₃吸附和NO_x吸附）和反应；简要地介绍了Cu系催化剂的抗水抗硫中毒性能研究现状以及反应机理，同时介绍了碱金属中毒、飞灰和催化剂烧结对催化剂失活的影响，结合生命周期分析SCR脱硝系统还原剂氨和尿素对NO排放的影响。在此基础上展望了未来铜系催化剂的研究方向：采用新型方式对催化剂进行改性、进一步采用表征和模拟技术研究催化体系的反应机理、优化锅炉和催化剂设计减轻催化剂失活以及研究适用于其他还原剂条件的高选择性催化剂。

关键词: 选择性催化还原, 催化剂载体, 吸附, 反应, 失活

Abstract: Selective catalytic reduction (SCR) technology has been widely used for flue gas denitrification in coal-fired power plants and the development of catalyst system with high activity at low temperature and high resistance to poisoning has become the key. Cu based catalysts have gained a wide range of research and attention because of its good denitrification performance and hydrothermal stability. In this paper, the recent progress in the studies on Cu loading on supports such as TiO₂, Al₂O₃, carbon-based materials and molecular sieves is reviewed. The mechanism of low temperature SCR reaction with Cu based catalyst is analyzed emphatically. There are two processes in the SCR denitrification reaction:adsorption and reaction. The adsorption process includes the NH₃ adsorption and the NO_x (NO and NO₂ adsorption. The mechanisms of Eley-Rideal (E-R) and Langmuir-Hinshelwood (L-H) are used for the denitration catalyst. The research status and reaction mechanism of Cu-based catalysts for water and sulfur resistance are briefly introduced. The effects of alkali metal poisoning, fly ash and catalyst sintering on catalyst deactivation are also introduced. Using the life cycle analysis(LCA) of SCR denitrification system, we also investigate the effect of ammonia and urea on NO emissions. Finally, the research direction for the copper based catalysts is prospected. The catalyst should be modified by new methods, and the reaction mechanism of the catalytic system, the optimization of the boiler and the catalyst design should be studied by using the characterization and simulation techniques to reduce the deactivation of the catalyst and to study highly selective catalysts for other reducing conditions.

Key words: selective catalytic reduction, catalyst support, adsorption, reaction, deactivation

中图分类号:

X511
TQ-9

张巍, 卢程, 董鹏飞, 尹艳山, 方毅伟, 邹济遥, 胡章茂, 阮敏, 徐慧芳. 铜系低温选择性催化还原脱硝催化剂的研究进展[J]. 化工进展, 2018, 37(10): 3858-3866.

ZHANG Wei, LU Cheng, DONG Pengfei, YIN Yanshan, FANG Yiwei, ZOU Jiyao, HU Zhangmao, RUAN Min, XU Huifang. Research progress of copper based low temperature SCR denitration catalysts[J]. Chemical Industry and Engineering Progress, 2018, 37(10): 3858-3866.

参考文献

[1] YU T, HAO T, FAN D, et al. Recent NH₃-SCR mechanism research over Cu/SAPO-34 catalyst[J]. Journal of Physical Chemistry C, 2014, 118(13):6565-6575.
[2] SIERRA-PEREIRA C A. Reduction of NO with CO on CuO or Fe₂O₃, catalysts supported on TiO₂, in the presence of O₂, SO₂, and water steam[J]. Fuel, 2014, 118(1):137-147.
[3] MRAD R, AISSAT A, COUSIN R, et al. Catalysts for NO_x selective catalytic reduction by hydrocarbons (HC-SCR)[J]. Applied Catalysis A:General, 2015, 504:542-548.
[4] 高珊. 铈钒锆固体超强酸催化剂的脱硝活性及其抗中毒能力[D]. 杭州:浙江大学, 2016. GAO S. Cerium and vanadium supported on sulfated zirconia as a solid superacid catalyst with enhanced deNO_x activity and poison resistance[D]. Hangzhou:Zhejiang University, 2016.
[5] 杜云贵, 杨佳, 沈世玉,等. 工业钛钨粉制备选择性催化还原催化剂的对比研究[J]. 化工进展, 2014, 33(4):935-940. DU Y G, YANG J, SHEN S Y, et al. Comparative study on SCR catalysts prepared from industrial titanium tungsten powder[J]. Chemical Industry and Engineering Progress, 2014, 33(4):935-940.
[6] LIU F, SHAN W, SHI X, et al. Research progress in vanadium-free catalysts for the selective catalytic reduction of NO with NH₃[J]. Chinese Journal of Catalysis, 2011, 32(7):1113-1128.
[7] PEÑA D A, UPHADE B S, SMIRNIOTIS P G. TiO₂-supported metal oxide catalysts for low-temperature selective catalytic reduction of NO with NH₃:Ⅰ. Evaluation and characterization of first row transition metals[J]. Journal of Catalysis, 2004, 221(2):421-431.
[8] RAMIS G, YI L, BUSCA G, et al. Adsorption, activation, and oxidation of ammonia over SCR catalysts[J]. Journal of Catalysis, 1995, 157(2):523-535.
[9] 李云涛, 钟秦. 低温NH₃-SCR反应机理及动力学研究进展[J]. 化学进展, 2009, 21(6):1094-1100. Li Y T, ZHONG Q. Recent Advances in mechanisms and kinetics of low-temperature selective catalytic reduction of NO_x with NH₃[J]. Progress in Chemistry, 2009, 21(6):1094-1100.
[10] YU Y, CHEN J, WANG J, et al. Performances of CuSO₄/TiO₂, catalysts in selective catalytic reduction of NO_x, by NH₃[J]. Chinese Journal of Catalysis, 2016, 37(2):281-287.
[11] 黄海凤, 金丽丽, 张宏华,等. 高抗硫性的铜钒钛低温SCR脱硝催化剂的制备表征及催化活性[J]. 高校化学工程学报, 2013, 27(4):721-728. HUANG H F, JIN L L, ZHANG H H, et al. Preparation and characterization of Cu-V/TiO₂ catalysts with strong resistance to SO₂ for low-temperature SCR of NO_x[J]. Journal of Chemical Engineering of Chinese Universities, 2013, 27(4):721-728.
[12] XIE G, LIU Z, ZHU Z, et al. Simultaneous removal of SO₂, and NO_x, from flue gas using a CuO/Al₂O₃, catalyst sorbent:Ⅰ. Deactivation of SCR activity by SO₂, at low temperatures[J]. Journal of Catalysis, 2004, 224(1):36-41.
[13] BOUKHA Z, TORRE U D L, PEREDA-AYO B, et al. Catalytic properties of CuO/Al₂O₃-based microreactors in SCR of NO_x, with NH₃[J]. Topics in Catalysis, 2016, 59(10/12):1002-1007.
[14] BOYANO A, GÁLVEZ M E, MOLINER R, et al. Carbon-based catalytic briquettes for the reduction of NO:effect of H₂SO₄, and HNO₃ carbon support treatment[J]. Fuel, 2008, 87(10/11):2058-2068.
[15] ZHU Z, LIU Z, LIU S, et al. NO reduction with NH₃ over an activated carbon-supported copper oxide catalysts at low temperatures[J]. Applied Catalysis B:Environmental, 2000, 26(1):25-35.
[16] MA Z, YANG H, QIAN L, et al. Catalytic reduction of NO by NH₃ over Fe-Cu-O_x/CNTs-TiO₂ composites at low temperature[J]. Applied Catalysis A:General, 2012, 427/428(10):43-48.
[17] 任雯, 赵博, 禚玉群, 等. NaY分子筛担载FeSO₄催化剂用于氨气还原NO_x的性能[J]. 化工学报, 2011, 62(2):362-368. REN W, ZHAO B, ZHUO Y Q, et al. Capability of molecular sieve-supported FeSO₄ catalyst for selective catalytic reduction of NO_x[J]. CIESC Journal, 2011, 62(2):362-368.
[18] IWAMOTO M, FURUKAWA H, MINE Y, et al. Copper(Ⅱ) ionexchanged ZSM-5 zeolites as highly active catalysts for direct and continuous decomposition of nitrogen monoxide[J]. Journal of the Chemical Society Chemical Communications, 1986, 16(16):1272-1273.
[19] PANAHI P N, SALARI D, NIAEI A, et al. NO reduction over nanostructure M-Cu/ZSM-5(M:Cr, Mn, Co and Fe) bimetallic catalysts and optimization of catalyst preparation by RSM[J]. Journal of Industrial & Engineering Chemistry, 2013, 19(6):1793-1799.
[20] FENG B, SONG C, LÜ G, et al. Selective catalytic reduction of nitric oxide with ammonia over zirconium-doped copper/ZSM-5 catalysts[J]. Applied Catalysis B:Environmental, 2014, 150/151(11):532-543.
[21] TAO Z, JIAN L, WANG D, et al. Selective catalytic reduction of NO with NH₃, over HZSM-5-supported Fe-Cu nanocomposite catalysts:the Fe-Cu bimetallic effect[J]. Applied Catalysis B:Environmental, 2014, 148/149(6):520-531.
[22] 陈影, 高志娟, 常丽萍, 等. Cu-SAPO-34/堇青石原位制备条件中硅铝比的优化及其对NO_x催化还原性能的影响[J]. 化工进展, 2013, 32(s1):174-178. CHEN Y, GAO Z J, CHENG L P, et al. Optimization of different SiO₂/Al₂O₃ of in situ synthesis of Cu-SAPO-34/cordierite and its performance for catalytic reduction of NO_x[J]. Chemical Industry and Engineering Progress,2013, 32(s1):174-178.
[23] DONG X, WANG J, ZHAO H, et al. The promotion effect of CeOx on Cu-SAPO-34 catalyst for selective catalytic reduction of NO_x with ammonia[J]. Catalysis Today, 2015, 258(3):28-34.
[24] XIE L, LIU F, REN L, et al. Excellent performance of one-pot synthesized Cu-SSZ-13 catalyst for the selective catalytic reduction of NO_x with NH₃[J]. Environmental Science & Technology, 2014, 48(1):566-572.
[25] 赵文雅, 李永红, 刘小娇, 等. Fe改性Cu-SSZ-13的方法对催化剂NH₃-SCR脱硝性能的影响[J]. 化工进展, 2016, 35(12):3898-3906. ZHAO W Y, LI Y H, LIU X J, et al. Effect of preparation methods on de-NO_x performance of Fe/Cu-SSZ-13 catalyst for NH₃-SCR[J]. Chemical Industry and Engineering Progress, 2016, 35(12):3898-3906.
[26] XIE L, LIU F, SHI X, et al. Effects of post-treatment method and Na co-cation on the hydrothermal stability of Cu-SSZ-13 catalyst for the selective catalytic reduction of NO_x with NH₃[J]. Applied Catalysis B:Environmental, 2015, 179(1):206-212.
[27] WU Z, JIANG B, LIU Y, et al. DRIFT study of manganese/titania-based catalysts for low-temperature selective catalytic reduction of NO with NH₃[J]. Environmental Science & Technology, 2007, 41(16):5812-5817.
[28] REICHE M A, HUG P, BAIKER A. Effect of grafting sequence on the behavior of titania-supported V₂O₅-WO₃, catalysts in the selective reduction of NO by NH₃[J]. Journal of Catalysis, 2000, 192(2):400-411.
[29] SI Z, DUAN W, WU X, et al. Structure, acidity and activity of CuO_x/WO_x-ZrO₂, catalyst for selective catalytic reduction of NO by NH₃[J]. Journal of Catalysis, 2010, 271(1):43-51.
[30] WANG D, ZHANG L Z, LI J H, et al. NH₃-SCR over Cu/SAPO-34-Zeolite acidity and Cu structure changes as a function of Cu loading[J]. Catalysis Today, 2014, 231:64-74.
[31] MA L, CHENG Y, CAVATAIO G, et al. In situ DRIFTS and temperature-programmed technology study on NH₃-SCR of NO_x, over Cu-SSZ-13 and Cu-SAPO-34 catalysts[J]. Applied Catalysis B:Environmental, 2014, 156/157:428-437.
[32] 江博琼. Mn/TiO₂系列低温SCR脱硝催化剂制备及其反应机理研究[D]. 杭州:浙江大学, 2008. JIANG B Q. The preparation of Mn/TiO₂ series low-temperature SCR DeNO_x catalysts and its reaction mechanism[D]. Hangzhou:Zhejiang University, 2008.
[33] KONDURU M V, CHUANG S S C. Dynamics of NO and N₂O decomposition over Cu-ZSM-5 under transient reducing and oxidizing conditions[J]. Journal of Catalysis, 2000, 196(2):271-286.
[34] MAHESH V, KONDURU, STEVEN S C C. Active and spectator adsorbates during NO decomposition over Cu-ZSM-5:transient IR, site-poisoning, and site-promotion studies[J]. Journal of Catalysis, 1999, 187(2):436-452.
[35] KAPTEIJN F, MARBÁN G, RODRIGUEZ-MIRASOL J, et al. Kinetic analysis of the decomposition of nitrous oxide over ZSM-5 catalysts[J]. Journal of Catalysis, 1997, 167(1):256-265.
[36] KOMATSU T, NUNOKAWA M, MOON I S, et al. Kinetic studies of reduction of nitric oxide with ammonia on Cu²⁺-exchanged zeolites[J]. Cheminform, 1994, 148(2):427-437.
[37] LAI S, MENG D, ZHAN W, et al. The promotional role of Ce in Cu/ZSM-5 and in situ surface reaction for selective catalytic reduction of NO_x with NH₃[J]. RSC Advances, 2015, 5(110):90235-90244.
[38] MAIBÁN G, FUERTES A B. Kinetics of the low-temperature selective catalytic reduction of NO with NH₃, over activated carbon fiber composite-supported iron oxides[J]. Catalysis Letters, 2002, 84(1/2):13-19.
[39] ZHANG W, LU C, DONG P F, et al. Fractal reconstruction of microscopic rough surface for soot layer during ceramic filtration based on Weierstrass-Mandelbrot function[J]. Industrial & Engineering Chemistry Research, 2018,57(11):4033-4044.
[40] 王燕彩. 酸或稀土元素(Ce、La)改性对Cu-SAPO-34上NH₃选择性催化还原NO_x抗水热性能的影响[D]. 昆明:昆明理工大学, 2016. WANG Y C. The influence of acid/rare earth elements(Ce, La)-modification on the hydrothermal stability of Cu-SAPO-34 for NH₃-SCR[D]. Kunming:Kunming University of Science and Technology, 2016.
[41] ZHEN P Z, ZHEN Y L, HONG X N, et al. Mechanism of SO₂ promotion for NO reduction with NH₃ over activaed carbon-supported vanadium oxide catalyst[J]. Journal of Catalysis, 2001, 197(1):6-16.
[42] ZHANG L, WANG D, LIU Y, et al. SO₂ poisoning impact on the NH₃-SCR reaction over a commercial Cu-SAPO-34 SCR catalyst[J]. Applied Catalysis B:Environmental, 2014, 156/157(9):371-377.
[43] JANGJOU Y, WANG D, KUMAR A, et al. SO₂ poisoning of the NH₃-SCR reaction over Cu-SAPO-34:impact of ammonium sulfate versus other S-containing species[J]. ACS Catalysis, 2016, 6(10):6612-6622.
[44] 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.
[45] 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.
[46] 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.
[47] 钱宇, 杨思宇, 贾小平, 等. 能源和化工系统的全生命周期评价和可持续性研究[J]. 化工学报, 2013, 64(1):133-147. QIAN Y, YANG S Y, JIA X P, et al. Life cycle assessment and sustainability of energy and chemical processes[J]. CIESC Journal, 2013, 64(1):133-147.
[48] 周建国, 周春静, 赵毅. 基于生命周期评价的选择性催化还原脱硝技术还原剂的选择研究[J]. 环境污染与防治, 2010, 32(3):102-104. ZHOU J G, ZHOU C J, ZHAO Y. Selection of reducing agents based on life cycle assessment in selective catalytic reduction denitration technology[J]. Environmental Pollution & Control, 2010, 32(3):102-104.
[49] 洪巧巧. 燃煤电厂烟气脱硫脱硝除尘技术生命周期评价[D]. 杭州:浙江大学, 2015. HONG Q Q. LCA of desulfurization, denitration and dedusting technologies in coal-fired power plants[D]. Hangzhou:Zhejiang University, 2015.
[50] 王鲁元, 程星星, 王志强, 等. 低温催化脱硝技术的研究进展[J]. 化工进展, 2016, 35(7):2222-2235. WANG L Y, CHENG X X, WANG Z Q, et al. Recent research progress in catalytic reduction of NO_x at low temperature[J]. Chemical Industry and Engineering Progress,2016, 35(7):2222-2235.

铜系低温选择性催化还原脱硝催化剂的研究进展

Research progress of copper based low temperature SCR denitration catalysts

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