Research progress in the SO2 resistance of Mn-Ce SCR catalysts

doi:10.16085/j.issn.1000-6613.2015.07.009

Abstract

Abstract: Low temperature selective catalytic reduction (SCR) has the advantage of low energy consumption and operating cost. However, the poor SO₂ resistance of catalysts hampers its industrial application. Mn-Ce catalysts were studied by many researchers due to their relatively better SO₂ resistance. This paper introduces the deactivation mechanisms of Mn-Ce catalysts. In addition, based on support selection, methods of catalyst preparation, modification of metallic element and quantum chemistry application in this field, the development of SO₂ resistance of Mn-Ce catalysts are discussed. Among them, the rapid development of quantum chemistry is helpful to the research of SO₂ resistance and may become a main research area in this field in the future. Moreover, it may provide a reference for future research to improve the performance of catalysts.

Key words: selective catalytic reduction, manganese-cerium, sulfur dioxide resistance

摘要： 低温选择性催化还原(SCR)工艺具有节约能耗和运行成本的优点, 但是其催化剂存在SO₂中毒的问题, 使其难以用于工业化, 因此对低温SCR催化剂抗硫性的研究就尤为重要, 其中Mn-Ce系列催化剂是研究较多、抗硫效果较好的催化剂。本文介绍了SO₂对Mn-Ce系列催化剂的毒化机制及Ce提高催化剂抗硫性的原因, 并且从载体选择、制备方法、金属元素改性和量子化学在抗硫性领域中的应用等方面综述了近年来关于Mn-Ce系列催化剂抗硫性的研究进展, 其中量子化学在SCR领域中的迅速发展对催化剂抗硫性的研究有重要帮助, 可能成为未来脱硝领域的研究发展方向, 为今后进一步提高催化剂的性能提供借鉴。

关键词: 选择性催化还原, Mn-Ce, 抗硫性

CLC Number:

O643.36⁺2

ZHANG Chengxiang, ZHANG Xiaopeng. Research progress in the SO₂ resistance of Mn-Ce SCR catalysts[J]. Chemical Industry and Engineering Progree, 2015, 34(07): 1866-1871,1932.

张呈祥, 张晓鹏. Mn-Ce系列低温SCR催化剂抗硫性研究进展[J]. 化工进展, 2015, 34(07): 1866-1871,1932.

References

[1] 韦正乐, 黄碧纯, 叶代启, 等. 烟气NO低温选择性催化还原催化剂研究进展[J]. 化工进展, 2007, 26(3):320-325.
[2] 谭青, 冯雅晨. 我国烟气脱硝行业现状与前景及SCR脱硝催化剂的研究进展[J]. 化工进展, 2011, 30(s1):709-713.
[3] 沈伯雄, 施建伟, 杨婷婷, 等. 选择性催化还原脱氮催化剂的再生及其应用评述[J]. 化工进展, 2008, 27(1):64-67.
[4] 杨超, 程华, 黄碧纯. 抗SO₂和H₂O中毒的低温NH₃-SCR脱硝催化剂研究进展[J]. 化工进展, 2014, 33(4):907-913.
[5] 于国锋, 顾月平, 金瑞奔.Mn/TiO₂和Mn-Ce/TiO₂低温脱硝催化剂的抗硫性研究[J].环境科学学报, 2013, 33(8):2149-2157.
[6] Yang Shijian, Guo Yongfu, Chang Huazhen, et al. Novel effect of SO₂ on the SCR reaction over CeO₂:Mechanism and significance[J]. Applied Catalysis B:Environmental, 2013, 136-137:19-28.
[7] Gu Tingting, Jin Ruiben, Liu Yue, et al. Promoting effect of calcium doping on the performances of MnO_x/TiO₂ catalysts for NO reduction with NH₃ at low temperature[J]. Applied Catalysis B:Environmental, 2013, 129:30-38.
[8] Jiang Haoxi, Zhao Jing, Jiang Dongyu, et al. Hollow MnO_x-CeO₂ nanospheres prepared by a green route:A novel low-temperature NH₃-SCR catalyst[J]. Catalysis Letters, 2014, 144 :325-332.
[9] Jin R B, Liu Y, Wu Z B, et al. The role of cerium in the improved SO₂ tolerance for NO reduction with NH₃ over Mn-Ce/TiO₂ catalyst at low temperature[J]. Applied Catalysis B:Environmental, 2014, 148-149:582-588.
[10] Ji Y, Toops T, Crocker M. Effect of ceria on the sulfation and desulfation characteristics of a model lean NO_x trap catalyst[J]. Catalysis Letters, 2008, 127(1-2):55-62.
[11] Qi G S, Ralph T Yang. Performance and kinetics study for low-temperature SCR of NO with NH₃ over MnO_x-CeO₂ catalyst[J]. Journal of Catalysis, 2003, 217:434-441.
[12] Liu Zhiming, Zhu Junzhi, Li Junhua, et al. Novel Mn-Ce-Ti mixed-oxide catalyst for the selective catalytic reduction of NO_x with NH₃[J]. ACS Appl. Mater. Interfaces, 2014, 6(16):14500-14508.
[13] Wu Z B, Jin R B, Wang H Q, et al. Effect of ceria doping on SO₂ resistance of Mn/TiO₂ for selective catalytic reduction of NO with NH₃ at low temperature[J]. Catalysis Communications, 2009, 10(6):935-939.
[14] Jiang B Q, Wu Z B, Liu Y, et al. DRIFT study of the SO₂ effect on low-temperature SCR reaction over Fe-Mn/TiO₂[J]. The Journal of Physical Chemistry C, 2010, 116:4961-4965.
[15] Liu Fudong, He Hong, Zhang Changbin, et al. Selective catalytic reduction of NO with NH₃ over iron titanate catalyst:Catalytic performance and characterization[J]. Applied Catalysis B:Environmental, 2010, 96:408-420.
[16] Kijlstra W S, Biervliet M, Poels E K, et al. Deactivation by SO₂ of MnO_x/Al₂O₃ catalysts used for the selective catalytic reduction[J]. Applied Catalysis B:Environmental, 1998, 16:327-337.
[17] Chang H Z, Ma L, Yang S J, et al. Comparison of preparation methods for ceria catalyst and the effect of surface and bulk sulfates on its activity toward NH₃-SCR[J]. Journal of Hazardous Materials, 2013, 262:782-8.
[18] Park Tae Sung, Jeong Soon Kwan, Hong Sung Ho, et al. Selective catalytic reduction of nitrogen oxides with NH₃ over natural manganese ore at low temperature[J]. Ind. Eng. Chem. Res., 2001, 40:4491-4495.
[19] Xie G Y, Liu Z Y, Zhu Z P, 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.
[20] Ji Y Y, Todd J Toops, Josh A Pihl, et al. NO_x storage and reduction in model lean NO_x trap catalysts studied by in situ DRIFTS[J]. Applied Catalysis B:Environmental, 2009, 91(1-2):329-338.
[21] Peralta M A, Milt V G, Cornaglia L M, et al. Stability of Ba, K/CeO₂ catalyst during diesel soot combustion:Effect of temperature, water, and sulfur dioxide[J]. Journal of Catalysis, 2006, 242:118-130.
[22] Martra G. Lewis acid and base sites at the surface of microcrystalline TiO₂ anatase:Relationships between surface morphology and chemical behaviour[J]. Applied Catalysis A:General, 2000(200):275-285.
[23] Jin R B, Liu Y, Wu Z B, et al. Relationship between SO₂ poisoning effects and reaction temperature for selective catalytic reduction of NO over Mn-Ce/TiO₂ catalyst[J]. Catalysis Today, 2010, 153(3-4):84-89.
[24] Sheng Z Y, Hu Y F, Xue J M, et al. SO₂ poisoning and regeneration of Mn-Ce/TiO₂ catalyst for low temperature NO_x reduction with NH₃[J]. Journal of Rare Earths, 2012, 30(7):676-682.
[25] Panagiotis G Smirniotis, Pavani M Sreekanth, Donovan A Peña, et al. Manganese oxide catalysts supported on TiO₂, Al₂O₃, and SiO₂:A comparison for low-temperature SCR of NO with NH₃[J]. Ind. Eng. Chem. Res., 2006, 45(19):6436-6443.
[26] Costello C K, Yang J H, Law H Y, et al. On the potential role of hydroxyl groups in CO oxidation over Au/A1₂O₃[J]. Applied Catalysis A:General, 2003, 243:15-24.
[27] Cao F, Xiang J, Su S, et al. The activity and characterization of MnO_x-CeO₂-ZrO₂/γ-Al₂O₃ catalysts for low temperature selective catalytic reduction of NO with NH₃[J]. Chemical Engineering Journal, 2014, 243:347-354.
[28] Yin C Y, Wei Y J, Wang F W, et al. Introduction of mesopority in zeolite ZSM-5 using resin as templates[J]. Materials Letters, 2013, 98:194-196.
[29] Zhang D S, Zhang L, Fang C, et al. MnO_x-CeO_x/CNTs pyridine-thermally prepared via a novel in situ deposition strategy for selective catalytic reduction of NO with NH₃[J]. RSC Adv., 2013, 3:8811-8819.
[30] Carja G, Kameshima Y, Okada K, et al. Mn-Ce/ZSM5 as a new superior catalyst for NO reduction with NH₃[J]. Applied Catalysis B:Environmental, 2007, 73:60-64.
[31] 金瑞奔. 负载型Mn-Ce系列低温SCR脱硝催化剂制备、反应机理及抗硫性能研究[D].杭州:浙江大学, 2010.
[32] Shen B X, Wang Y Y, Wang F M, et al. The effect of Ce-Zr on NH₃-SCR activity over MnO_x(0.6)/Ce_0.5Zr_0.5O₂ at low temperature[J]. Chemical Engineering Journal, 2014, 236:171-180.
[33] Zhang X P, Shen B X, Wang K, et al. A contrastive study of the introduction of cobalt as a modifier for active components and supports of catalysts for NH₃-SCR[J]. Journal of Industrial and Engineering Chemistry, 2013, 19(4):1272-1279.
[34] Kang M, Tae Hun Yeon, Jae Eui Yie, et al. Novel MnO_x catalysts for NO reduction at low temperature with ammonia[J]. Catalysis Letters, 2006, 106(1-2):77-80.
[35] Sheng Zhongyi, Hu Yufeng, Xue Jianming, et al. A novel co-precipitation method for preparation of Mn-Ce/TiO₂ composites for NO_x reduction with NH₃ at low temperature[J]. Environmental Technology, 2012, 33(21):2421-2428.
[36] Yu J, Guo F, Gao S Q, et al. Sulfur poisoning resistant mesoporous Mn-base catalyst for low-temperature SCR of NO with NH₃[J]. Applied Catalysis B:Environmental, 2010, 95(1-2):160-168.
[37] Lu Xining, Song Cunyi, Chang Chein-Chig, et al. Manganese oxides supported on TiO₂-graphene nanocomposite catalysts for selective catalytic reduction of NO_x with NH₃ at low temperature[J]. Ind. Eng. Chem. Res., 2014, 53:11601-11610.
[38] Qu L, Li C T, Zeng G M, et al. Support modification for improving the performance of MnO_x-CeO_y/γ-Al₂O₃ in selective catalytic reduction of NO by NH₃[J]. Chemical Engineering Journal, 2014, 42:76-85.
[39] Li Le, Diao Yongfa, Liu Xin. Ce-Mn mixed oxides supported on glass-fiber for low-temperature selective catalytic reduction of NO with NH₃[J]. Journal of Rare Earths, 2014, 32(5):409-415.
[40] Tang Xiaolong, Hao Jiming, Yi Honghong, et al. Low-temperature SCR of NO with NH₃ over AC/C supported manganese-based monolithic catalysts[J]. Catal. Today, 2007, 126:406-411.
[41] Shen B X, Liu T, Yang X Y, et al. MnO_x/Ce_0.6Zr_0.4O₂ catalysts for low-temperature selective catalytic reduction of NO_x with NH₃[J]. Environmental Engineering Science, 2011, 28(4):291-298.
[42] Shen B X, Wang F M, Liu T. Homogeneous MnO_x-CeO₂ pellets prepared by a one-step hydrolysis process for low-temperature NH₃-SCR[J]. Powder Technology, 2014, 253:152-157.
[43] Chang H Z, Li J H, Chen X Y, et al. Improvement of activity and SO₂ tolerance of Sn-modified MnO_x-CeO₂ catalysts for NH₃-SCR at low temperatures[J]. Environmental science & technology, 2013, 47(10):5294-301.
[44] Chang H Z, Li J H, Chen X Y, et al. Effect of Sn on MnO_x-CeO₂ catalyst for SCR of NO_x by ammonia:Enhancement of activity and remarkable resistance to SO₂[J]. Catalysis Communications, 2012, 27:54-57.
[45] Shen B X, Liu T, Zhao N, et al. Iron-doped Mn-Ce/TiO₂ catalyst for low temperature selective catalytic reduction of NO with NH₃[J]. Journal of Environmental Sciences, 2010, 22(9):1447-1454.
[46] Peng Y, Li J H, Shi W B, et al. Design strategies for development of SCR catalyst:Improvement of alkali poisoning resistance and novel regeneration method[J]. Environmental science & technology, 2012, 46(22):12623-9.
[47] Liu Y, Cen W L, Wu Z B, et al. SO₂ poisoning structures and the effects on pure and Mn doped CeO₂:A first principles investigation[J]. The Journal of Physical Chemistry C, 2012, 116(43):22930-22937.
[48] Lu Z S, Carsten Müller, Yang Z X, et al. SO_x on ceria from adsorbed SO₂[J]. The Journal of Chemical Physics, 2011, 134(18):184703.

Research progress in the SO₂ resistance of Mn-Ce SCR catalysts

Mn-Ce系列低温SCR催化剂抗硫性研究进展

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

References

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	DENG Liping, SHI Haoyu, LIU Xiaolong, CHEN Yaoji, YAN Jingying. Non-noble metal modified vanadium titanium-based catalyst for NH₃-SCR denitrification simultaneous control VOCs [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 542-548.
[2]	WANG Lele, YANG Wanrong, YAO Yan, LIU Tao, HE Chuan, LIU Xiao, SU Sheng, KONG Fanhai, ZHU Canghai, XIANG Jun. Influence of spent SCR catalyst blending on the characteristics and deNO _x performance for new SCR catalyst [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 489-497.
[3]	LI Jia, FAN Xing, CHEN Li, LI Jian. Research progress of simultaneous removal of NO _x and N₂O from the tail gas of nitric acid production [J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3770-3779.
[4]	YIN Chengyang, HOU Ming, YANG Shuang, MAO Di, LIU Junyan. Research progress in transition metals modified Cu-SSZ-13 zeolite denitration catalysts [J]. Chemical Industry and Engineering Progress, 2023, 42(6): 2963-2974.
[5]	ZHANG Wei, QIN Chuan, XIE Kang, ZHOU Yunhe, DONG Mengyao, LI Jie, TANG Yunhao, MA Ying, SONG Jian. Application and performance enhancement challenges of H₂-SCR modified platinum-based catalysts for low-temperature denitrification [J]. Chemical Industry and Engineering Progress, 2023, 42(6): 2954-2962.
[6]	HE Chuan, WU Guoxun, LI Ang, ZHANG Fajie, BIAN Zijun, LU Chengzheng, WANG Lipeng, ZHAO Min. Characteristics of calcium and magnesium deactivation and regeneration of waste incineration SCR catalyst [J]. Chemical Industry and Engineering Progress, 2023, 42(5): 2413-2420.
[7]	NING Shuying, SU Yaxin, YANG Honghai, WEN Nini. Research progress on supported Cu-based zeolite catalysts for the selective catalytic reduction of NO _x with hydrocarbons [J]. Chemical Industry and Engineering Progress, 2023, 42(3): 1308-1320.
[8]	ZHANG Chenguang, FENG Shuo, XING Yuye, SHEN Boxiong, SU Lichao. Research progress of isolated Cu²⁺ in copper based zeolite NH₃-SCR catalyst for diesel vehicles [J]. Chemical Industry and Engineering Progress, 2023, 42(3): 1321-1331.
[9]	ZHOU Hao, ZHANG Heng, WEN Nini, WANG Xurui, XU Lu, LI Wei, SU Yaxin. Preparation and de-NO _x performance of C₃H₆-SCR over Cu-SAPO-44 catalyst [J]. Chemical Industry and Engineering Progress, 2023, 42(3): 1373-1382.
[10]	LIU Liang, WANG Zhaoxi, LI Xinlong, ZHANG Gaoshan, WANG Shouyang, ZHANG Linlin, LU Chang, QING Mengxia. Research progress on the improvement of vanadium and titanium denitrification catalysts against ammonium bisulfate poisoning [J]. Chemical Industry and Engineering Progress, 2023, 42(1): 215-225.
[11]	SONG Yukun, WANG Guogang, ZHANG Xingong, LIU Dakuo, ZHANG Jinqing, LIN Han. SNAR: a new non-amino reduction technology for acid and denitration [J]. Chemical Industry and Engineering Progress, 2022, 41(S1): 606-612.
[12]	YU Zhengwei, ZHANG Xiaoxia, LEI Jie, LI Ao, WANG Guangying, DING Xiang, LONG Hongming. Comprehensive recovery of cerium and manganese from waste CeO _x -MnO _x -based SCR denitrification catalysts by reductive acid leaching [J]. Chemical Industry and Engineering Progress, 2022, 41(9): 5122-5131.
[13]	ZHOU Jiali, MA Ziran, ZHAO Junping, MA Jing, ZHAO Chunlin, LI Ge, WANG Hongyan, WANG Baodong. HPAs-modified V-Mo/Ti-W catalysts for the selective catalytic reduction of NO _x over a wide temperature range [J]. Chemical Industry and Engineering Progress, 2022, 41(7): 3615-3623.
[14]	LI Yanlin, CHENG Xingxing, ZHAO Mingliang, WANG Luyuan, WANG Zhiqiang. Kinetic model of NO_x removal by CO onto forming catalysts [J]. Chemical Industry and Engineering Progress, 2021, 40(S1): 245-252.
[15]	LU Qiang, PEI Xinqi, XU Mingxin, WANG Hanxiao, WU Yachang, OUYANG Haodong. Progress in the development and regeneration of SCR catalysts for anti-arsenic poisoning [J]. Chemical Industry and Engineering Progress, 2021, 40(5): 2365-2374.