Superior resistance to alkali metal potassium of vanadium-based NH3-SCR catalyst promoted by the solid superacid SO42--TiO2

doi:10.1016/j.cjche.2022.05.031

中国化学工程学报 ›› 2023, Vol. 55 ›› Issue (3): 246-256.DOI: 10.1016/j.cjche.2022.05.031

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Superior resistance to alkali metal potassium of vanadium-based NH₃-SCR catalyst promoted by the solid superacid SO₄^2--TiO₂

Yaoyao Peng¹, Lei Song¹, Siru Lu¹, Ziyu Su¹, Kui Ma¹, Siyang Tang¹, Shan Zhong¹, Hairong Yue^1,2, Bin Liang^1,2

1. Low-Carbon Technology and Chemical Reaction Engineering Laboratory, School of Chemical Engineering, Sichuan University, Chengdu 610065, China;
2. Institute of New Energy and Low-Carbon Technology, Sichuan University, Chengdu 610207, China

收稿日期:2022-02-28 修回日期:2022-05-06 出版日期:2023-03-28 发布日期:2023-06-03
通讯作者: Lei Song,E-mail:songlei@scu.edu.cn
基金资助:
This work was supported by the National Natural Science Foundation of China (22108184), China Postdoctoral Science Foundation (2021TQ0221), the Sichuan Science and Technology Program (2021JDRC0117) and Chengdu Science and Technology Program (2021-YF05-00378-SN). We thank Wen Tian for the experimental support with FTIR (Thermo Fisher iS 50).

Superior resistance to alkali metal potassium of vanadium-based NH₃-SCR catalyst promoted by the solid superacid SO₄^2--TiO₂

Yaoyao Peng¹, Lei Song¹, Siru Lu¹, Ziyu Su¹, Kui Ma¹, Siyang Tang¹, Shan Zhong¹, Hairong Yue^1,2, Bin Liang^1,2

1. Low-Carbon Technology and Chemical Reaction Engineering Laboratory, School of Chemical Engineering, Sichuan University, Chengdu 610065, China;
2. Institute of New Energy and Low-Carbon Technology, Sichuan University, Chengdu 610207, China

Received:2022-02-28 Revised:2022-05-06 Online:2023-03-28 Published:2023-06-03
Contact: Lei Song,E-mail:songlei@scu.edu.cn
Supported by:
This work was supported by the National Natural Science Foundation of China (22108184), China Postdoctoral Science Foundation (2021TQ0221), the Sichuan Science and Technology Program (2021JDRC0117) and Chengdu Science and Technology Program (2021-YF05-00378-SN). We thank Wen Tian for the experimental support with FTIR (Thermo Fisher iS 50).

摘要/Abstract

摘要： The significant decrease of acid sites caused by alkali metal poisoning is the major factor in the deactivation of commercial V₂O₅-WO₃/TiO₂ NH₃-SCR catalysts. In this work, the solid superacid SO₄^2--TiO₂ modified by sulfate radicals, was selected as the catalyst support, which showed superior potassium resistance. The physicochemical properties and K-poisoning resistance of the V₂O₅-WO₃/SO₄^2--TiO₂ (VWSTi) catalyst were carried out by XRD, BET, H₂-TPR, NH₃-TPD, XPS, in situ DRIFTS and TG. The results pointed out that the introduction of SO₄^2- significantly increased the NH₃-SCR catalytic activity at high temperatures, with an exceptionally high NO_x conversion over 90% between 275 ℃ and 500 ℃. When 0.5% (mass) K₂O was doped on the catalysts, the catalytic performance of the traditional V₂O₅-WO₃/TiO₂ (VWTi) catalyst decreased significantly, while the VWSTi catalyst could still maintain a NO_x conversion over 90% in the range of 300–500 ℃. The characterizations suggested that the support of SO₄^2--TiO₂ greatly increased the number of acidic sites, thereby enhancing the adsorption capacity of the reactant NH₃. The results above demonstrated a potential approach to achieve superior potassium resistance for NH₃-SCR catalysts using solid superacid.

关键词: Selective catalytic reduction (NH₃-SCR), V₂O₅-WO₃/TiO₂, Solid superacid, Anti-poisoning, Acidity

Abstract: The significant decrease of acid sites caused by alkali metal poisoning is the major factor in the deactivation of commercial V₂O₅-WO₃/TiO₂ NH₃-SCR catalysts. In this work, the solid superacid SO₄^2--TiO₂ modified by sulfate radicals, was selected as the catalyst support, which showed superior potassium resistance. The physicochemical properties and K-poisoning resistance of the V₂O₅-WO₃/SO₄^2--TiO₂ (VWSTi) catalyst were carried out by XRD, BET, H₂-TPR, NH₃-TPD, XPS, in situ DRIFTS and TG. The results pointed out that the introduction of SO₄^2- significantly increased the NH₃-SCR catalytic activity at high temperatures, with an exceptionally high NO_x conversion over 90% between 275 ℃ and 500 ℃. When 0.5% (mass) K₂O was doped on the catalysts, the catalytic performance of the traditional V₂O₅-WO₃/TiO₂ (VWTi) catalyst decreased significantly, while the VWSTi catalyst could still maintain a NO_x conversion over 90% in the range of 300–500 ℃. The characterizations suggested that the support of SO₄^2--TiO₂ greatly increased the number of acidic sites, thereby enhancing the adsorption capacity of the reactant NH₃. The results above demonstrated a potential approach to achieve superior potassium resistance for NH₃-SCR catalysts using solid superacid.

Key words: Selective catalytic reduction (NH₃-SCR), V₂O₅-WO₃/TiO₂, Solid superacid, Anti-poisoning, Acidity

Yaoyao Peng, Lei Song, Siru Lu, Ziyu Su, Kui Ma, Siyang Tang, Shan Zhong, Hairong Yue, Bin Liang. Superior resistance to alkali metal potassium of vanadium-based NH₃-SCR catalyst promoted by the solid superacid SO₄^2--TiO₂[J]. 中国化学工程学报, 2023, 55(3): 246-256.

参考文献

[1] M. Kampa, E. Castanas, Human health effects of air pollution, Environ. Pollut. 151 (2008) 362-367.
[2] T. Ohara, H. Akimoto, J. Kurokawa, N. Horii, K. Yamaji, X. Yan, T. Hayasaka, An Asian emission inventory of anthropogenic emission sources for the period 1980-2020, Atmos. Chem. Phys 7 (2007) 4419-4444.
[3] D.G. Streets, S.T. Waldhoff, Present and future emissions of air polluants in China SO₂, NO_x and CO, Atmos. Environ. 34 (2000) 363-374.
[4] K. Skalska, J. S. Miller, S. Ledakowicz, Trends in NO_x abatement: A review, Sci. Total Environ. 408 (2010) 3976-3989.
[5] S. Roy, M.S. Hegde, G. Madras, Catalysis for NO_x abatement, Appl. Energy 86 (2009) 2283-2297.
[6] Y. Peng, J. Li, W. Shi, J. Xu, J. Hao, Design strategies for development of SCR catalyst improvement of alkali poisoning resistance and novel regeneration method, Environ. Sci. Technol. 46 (2012) 12623-12629.
[7] L. Lisi, S. Cimino, Poisoning of SCR catalysts by alkali and alkaline earth metals, Catalysts. 10 (2020) 1475.
[8] B.K. Olsen, F. Kügler, F. Castellino, A.D. Jensen, Poisoning of vanadia based SCR catalysts by potassium: influence of catalyst composition and potassium mobility, Catal. Sci. Technol. 6 (7) (2016) 2249-2260.
[9] D. Nicosia, M. Elsener, O. Kröcher, P. Jansohn, Basic investigation of the chemical deactivation of V₂O₅/WO₃-TiO₂ SCR catalysts by potassium, calcium, and phosphate, Top. Catal. 42-43 (1-4) (2007) 333-336.
[10] X. Li, X. Li, R.T. Yang, J. Mo, J. Li, J. Hao, The poisoning effects of calcium on V₂O₅-WO₃/TiO₂ catalyst for the SCR reaction: Comparison of different forms of calcium, Mol. Catal. 434 (2017) 16-24.
[11] S.M. Jung, P. Grange, Characterization and reactivity of V₂O₅-WO₃ supported on TiO₂-SO₄^2- catalyst for the SCR reaction, Appl. Catal., B. 32 (1) (2001) 123-131.
[12] P. Hu, Z. Huang, X. Gu, F. Xu, J. Gao, Y. Wang, Y. Chen, X. Tang, Alkali-resistant mechanism of a hollandite DeNO_x catalyst, Environ. Sci. Technol. 49 (11) (2015) 7042-7047.
[13] J. Zhang, Z. Huang, Y. Du, X. Wu, H. Shen, G. Jing, Alkali-poisoning-resistant Fe₂O₃/MoO₃/TiO₂ catalyst for the selective reduction of NO by NH₃: The role of the MoO₃ safety buffer in protecting surface active sites, Environ. Sci. Technol. 54 (1) (2020) 595-603.
[14] X. Wang, Q. Cong, L. Chen, Y. Shi, Y. Shi, S. Li, W. Li, The alkali resistance of CuNbTi catalyst for selective reduction of NO by NH₃: A comparative investigation with VWTi catalyst, Appl. Catal., B 246 (2019) 166-179.
[15] S.M. Jung, P. Grange, Characterization and reactivity of pure TiO₂-SO₄^2- SCR catalyst: influence of SO₄^2- content, Catal. Today 59 (3) (2000) 305-312.
[16] X. Guo, C. Bartholomew, W. Hecker, L.L. Baxter, Effects of sulfate species on V₂O₅/TiO₂ SCR catalysts in coal and biomass-fired systems, Appl. Catal., B 92 (1) (2009) 30-40.
[17] R.Q. Long, M.T. Chang, R.T. Yang, Enhancement of activities by sulfation on Fe-exchanged TiO₂-pillared clay for selective catalytic reduction of NO by ammonia, Appl. Catal., B 33 (2) (2001) 97-107.
[18] T. Gu, Y. Liu, X. Weng, H. Wang, Z. Wu, The enhanced performance of ceria with surface sulfation for selective catalytic reduction of NO by NH₃, Catal. Commun. 12 (2020) 310-313.
[19] S.M. Jung, P. Grange, Investigation of the promotional effect of V₂O₅ on the SCR reaction and its mechanism on hybrid catalyst with V₂O₅ and TiO₂-SO₄^2- catalysts, Appl. Catal., B 36 (2002) 207-215.
[20] S. Yang, Y. Guo, H. Chang, L. Ma, Y. Peng, Z. Qu, N. Yan, C. Wang, J. Li, Novel effect of SO₂ on the SCR reaction over CeO₂: Mechanism and significance, Appl. Catal., B 136-137 (2013) 19-28.
[21] F. Zeng, D. Luo, Z. Zhang, B. Liang, X. Yuan, L. Fu, Study on the behavior of sulfur in hydrolysis process of titanyl sulfate solution, J. Alloys Compd. 670 (2016) 249-257.
[22] P. Li, Y. Gu, Z. Yu, P. Gao, Y. An, J. Li, TiO₂-SnO₂/SO₄^2- mesoporous solid superacid decorated nickel-based material as efficient electrocatalysts for methanol oxidation reaction, Electrochim. Acta 297 (2019) 864-871.
[23] Y. Gu, H. Yang, B. Li, J. Mao, Y. An, A ternary nanooxide NiO-TiO₂-ZrO₂/SO₄^2- as efficient solid superacid catalysts for electro-oxidation of glucose, Electrochim. Acta 194 (2016) 367-376.
[24] P. Yang, S. Fan, Z. Chen, G. Bao, S. Zuo, C. Qi, Synthesis of Nb₂O₅ based solid superacid materials for catalytic combustion of chlorinated VOCs, Appl. Catal., B 239 (2018) 114-124.
[25] N. Prasongthum, P. Natewong, P. Reubroycharoen, R. Idem, Solvent Regeneration of a CO₂-Loaded BEA–AMP Bi-Blend Amine Solvent with the Aid of a Solid Brønsted Ce(SO₄)₂/ZrO₂ Superacid Catalyst, Energy Fuels 33 (2) (2019) 1334-1343.
[26] J.R. Sohn, S.H. Lee, J.S. Lim, New solid superacid catalyst prepared by doping ZrO₂ with Ce and modifying with sulfate and its catalytic activity for acid catalysis, Catal. Today 116 (2) (2006) 143-150.
[27] C. Zhang, J. Zhang, Y. Zhao, J. Sun, G. Wu, Study on the preparation and catalytic activities of SO₄^2- promoted metal oxide solid superacid catalysts for model oil desulfurization, Catal. Lett. 146 (7) (2016) 1256-1263.
[28] Y. Yu, J. Miao, C. He, J. Chen, C. Li, M. Douthwaite, The remarkable promotional effect of SO₂ on Pb-poisoned V₂O₅-WO₃/TiO₂ catalysts: An in-depth experimental and theoretical study, Chem. Eng. J. 338 (2018) 191-201.
[29] W. Yu, X. Wu, Z. Si, D. Weng, Influences of impregnation procedure on the SCR activity and alkali resistance of V₂O₅–WO₃/TiO₂ catalyst, Appl. Surf. Sci. 283 (2013) 209-214.
[30] P. Wang, S. Gao, H. Wang, S. Chen, X. Chen, Z. Wu, Enhanced dual resistance to alkali metal and phosphate poisoning: Mo modifying vanadium-titanate nanotubes SCR catalyst, Appl. Catal., A 561 (2018) 68-77.
[31] T. Tong, J. Chen, S. Xiong, W. Yang, Q. Yang, L. Yang, Y. Peng, Z. Liu, J. Li, Vanadium-density-dependent thermal decomposition of NH₄HSO₄ on V₂O₅/TiO₂ SCR catalysts, Catal. Sci. Technol 9 (14) (2019) 3779-3787.
[32] X. Wang, Y. Shi, S. Li, W. Li, Promotional synergistic effect of Cu and Nb doping on a novel Cu/Ti-Nb ternary oxide catalyst for the selective catalytic reduction of NO_x with NH₃, Appl. Catal., B 220 (2018) 234-250.
[33] H. Chang, C. Shi, M. Li, T. Zhang, C. Wang, L. Jiang, X. Wang, The effect of cations (NH⁴⁺, Na⁺, K⁺, and Ca²⁺) on chemical deactivation of commercial SCR catalyst by bromides, Chin. J. Catal 39 (4) (2018) 710-717.
[34] L. Zheng, M. Zhou, Z. Huang, Y. Chen, J. Gao, Z. Ma, J. Chen, X. Tang, Self-protection mechanism of hexagonal WO₃-based DeNO_x catalysts against alkali poisoning, Environ. Sci. Technol. 50 (21) (2016) 11951-11956.
[35] L. Xu, C. Wang, H. Chang, Q. Wu, T. Zhang, J. Li, New insight into SO₂ poisoning and regeneration of CeO₂–WO₃/TiO₂ and V₂O₅–WO₃/TiO₂ catalysts for low-temperature NH₃–SCR, Chem. Eng. J. 170 (2011) 531-537.
[36] W. Hu, X. Gao, Y. Deng, R. Qu, C. Zheng, X. Zhu, K. Cen, Deactivation mechanism of arsenic and resistance effect of SO₄^2- on commercial catalysts for selective catalytic reduction of NO with NH₃, Chem. Eng. J. 293 (2016) 118-128.
[37] R. Guo, C. Lu, W. Pan, W. Zhen, Q. Wang, Q. Chen, H. Ding, N. Yang, A comparative study of the poisoning effect of Zn and Pb on Ce/TiO₂ catalyst for low temperature selective catalytic reduction of NO with NH₃, Catal. Commun. 59 (2015) 136-139.
[38] L. Chen, J. Li, M. Ge, The poisoning effect of alkali metals doping over nano V₂O₅–WO₃/TiO₂ catalysts on selective catalytic reduction of NO_x by NH₃, Chem. Eng. J. 170 (2011) 531-537.
[39] Y. Yu, C. Chen, M. Ma, M. Douthwaite, C. He, J. Miao, J. Chen, C. Li, SO₂ promoted in situ recovery of thermally deactivated Fe₂(SO₄)₃-TiO₂ NH₃-SCR catalysts: From experimental work to theoretical study, Chem. Eng. J. 361 (2019) 820-829.
[40] J. Miao, H. Li, Q. Su, Y. Yu, Y. Chen, J. Chen, J, The combined promotive effect of SO₂ and HCl on Pb-poisoned commercial NH₃-SCR V₂O₅-WO₃/TiO₂ catalysts, Catal. Commun. 125 (2019) 118-122.
[41] M. Li, B. Liu, X. Wang, X. Yu, S. Zheng, H. Du, D. Dreisinger, Y. Zhang, A promising approach to recover a spent SCR catalyst: Deactivation by arsenic and alkaline metals and catalyst regeneration, Chem. Eng. J. 342 (2018) 1-8.
[42] D. Ye, R. Qu, H. Song, C. Zheng, X. Gao, Z. Luo, M. Ni, K. Cen, Investigation of the promotion effect of WO₃ on the decomposition and reactivity of NH₄HSO₄ with NO on V₂O₅–WO₃-TiO₂ SCR catalysts, RSC Advances 6 (2016) 55584.
[43] L. Chen, J. Li, M. Ge, Promotional Effect of Ce-doped V₂O₅-WO₃/TiO₂ with Low Vanadium Loadings for Selective Catalytic Reduction of NO_x by NH₃, J. Phys. Chem. C 113 (2009) 21177-21184.
[44] W. Shan, Y. Yu, Y. Zhang, G. He, Y. Peng, J. Li, H. He, Theory and practice of metal oxide catalyst design for the selective catalytic reduction of NO_x with NH₃, Catal. Today. 376 (2021) 292-301.
[45] K. Zha, L. Kang, C. Feng, L. Han, H. Li, T. Yan, P. Maitarad, L. Shi, D. Zhang, Improved NO_x reduction in the presence of alkali metals by using hollandite Mn–Ti oxide promoted Cu-SAPO-34 catalysts, Environ. Sci. Nano 5 (6) (2018) 1408-1419.
[46] P. Zhang, P. Wang, A. Chen, L. Han, T. Yan, J. Zhang, D. Zhang, Alkali-resistant catalytic reduction of NO_x by using Ce–O–B alkali-capture sites, Environ Sci Technol. 55 (17) (2021) 11970-11978.
[47] Y. Li, S. Cai, P. Wang, T. Yan, J. Zhang, D. Zhang, Improved NO_x Reduction over phosphate-modified Fe₂O₃/TiO₂ catalysts via tailoring reaction paths by in situ creating alkali-poisoning sites, Environ Sci Technol. 55 (13) (2021) 9276-9284.
[48] C. Feng, P.L. Wang, X.Y. Liu, F.L. Wang, T.T. Yan, J.P. Zhang, G.Y. Zhou, D.S. Zhang, Alkali-resistant catalytic reduction of NO_x via naturally coupling active and poisoning sites, Environ. Sci. Technol. 55 (16) (2021) 11255–11264.
[49] Y.K. Yu, J.X. Wang, J.S. Chen, X.R. Meng, Y.T. Chen, C. He, Promotive effect of SO₂ on the activity of a deactivated commercial selective catalytic reduction catalyst: an in situ DRIFT study, Ind. Eng. Chem. Res. 53 (42) (2014) 16229–16234.
[50] P.L. Wang, L.J. Yan, Y.D. Gu, S. Kuboon, H.R. Li, T.T. Yan, L.Y. Shi, D.S. Zhang, Poisoning-resistant NO_x reduction in the presence of alkaline and heavy metals over H-SAPO-34-supported Ce-promoted Cu-based catalysts, Environ. Sci. Technol. 54 (10) (2020) 6396–6405.
[51] S. Cai, T. Xu, P. Wang, L. Han, S. Impeng, Y. Li, T. Yan, G. Chen, L. Shi, D. Zhang, Self-protected CeO₂–SnO₂@SO₄^2–/TiO₂ catalysts with extraordinary resistance to alkali and heavy metals for NO_x reduction, Environ Sci Technol. 54 (2020) 12752-12760.
[52] M.N. Khan, L.P. Han, P.L. Wang, D.S. Zhang, Tailored alkali resistance of DeNO_x catalysts by improving redox properties and activating adsorbed reactive species, iScience 23 (6) (2020) 101173.
[53] L.J. Yan, Y.Y. Ji, P.L. Wang, C. Feng, L.P. Han, H.R. Li, T.T. Yan, L.Y. Shi, D.S. Zhang, Alkali and phosphorus resistant zeolite-like catalysts for NO_x reduction by NH₃, Environ. Sci. Technol. 54 (14) (2020) 9132–9141.
[54] L.J. Yan, F.L. Wang, P.L. Wang, S. Impeng, X.Y. Liu, L.P. Han, T.T. Yan, D.S. Zhang, Unraveling the unexpected offset effects of Cd and SO₂ deactivation over CeO₂-WO₃/TiO₂ catalysts for NO_x reduction, Environ. Sci. Technol. 54 (12) (2020) 7697–7705.
[55] Z.Z. Jia, Y.J. Shen, T.T. Yan, H.R. Li, J. Deng, J.H. Fang, D.S. Zhang, Efficient NO_x abatement over alkali-resistant catalysts via constructing durable dimeric VOx species, Environ. Sci. Technol. 56 (4) (2022) 2647–2655.

Superior resistance to alkali metal potassium of vanadium-based NH₃-SCR catalyst promoted by the solid superacid SO₄^2--TiO₂

Superior resistance to alkali metal potassium of vanadium-based NH₃-SCR catalyst promoted by the solid superacid SO₄^2--TiO₂

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[9]	耿艳楼, 胡利彦, 赵新强, 安华良, 王延吉. Synthesis of 4,4'-MDC in the Presence of Sulfonic Acid-functionalized Ionic Liquids[J]. , 2009, 17(5): 756-760.