Study on sulfur resistance of MnO2/Beta zeolite in toluene catalytic combustion: The effect of increased acidity on catalytic performance

doi:10.1016/j.cjche.2024.10.023

Chinese Journal of Chemical Engineering ›› 2025, Vol. 78 ›› Issue (2): 187-195.DOI: 10.1016/j.cjche.2024.10.023

Previous Articles Next Articles

Study on sulfur resistance of MnO₂/Beta zeolite in toluene catalytic combustion: The effect of increased acidity on catalytic performance

Zhuo Wang^1,2, Zetao Jin¹, Hanqi Ning¹, Baishun Jiang¹, Kaiyuan Xie¹, Shufeng Zuo¹, Qiuyan Wang³

1. Zhejiang Key Laboratory of Alternative Technologies for Fine Chemicals Process, College of Chemistry and Chemical Engineering, Shaoxing University, Shaoxing 312000, China;
2. College of Materials Science and Engineering, Beijing University of Technology, Beijing 100124, China;
3. State Key Laboratory of Elemento-Organic Chemistry, Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), College of Chemistry, Nankai University, Tianjin 300071, China

Received:2024-08-04 Revised:2024-10-04 Accepted:2024-10-08 Online:2024-12-10 Published:2025-02-08
Supported by:
This work was supported by the National Natural Science Foundation of China (21577094); the Zhejiang Public Welfare Technology Research Project (LGG19B070003).

Study on sulfur resistance of MnO₂/Beta zeolite in toluene catalytic combustion: The effect of increased acidity on catalytic performance

Zhuo Wang^1,2, Zetao Jin¹, Hanqi Ning¹, Baishun Jiang¹, Kaiyuan Xie¹, Shufeng Zuo¹, Qiuyan Wang³

1. Zhejiang Key Laboratory of Alternative Technologies for Fine Chemicals Process, College of Chemistry and Chemical Engineering, Shaoxing University, Shaoxing 312000, China;
2. College of Materials Science and Engineering, Beijing University of Technology, Beijing 100124, China;
3. State Key Laboratory of Elemento-Organic Chemistry, Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), College of Chemistry, Nankai University, Tianjin 300071, China

通讯作者: Shufeng Zuo,E-mail:sfzuo@usx.edu.cn;Qiuyan Wang,E-mail:qywang@nankai.edu.cn
基金资助:
This work was supported by the National Natural Science Foundation of China (21577094); the Zhejiang Public Welfare Technology Research Project (LGG19B070003).

Abstract

Abstract: Sulfur dioxide (SO₂) frequently coexist with volatile organic compounds (VOCs) in exhaust gas. The competitive adsorption of SO₂ and VOCs can adversely affect the efficiency of catalytic combustion, leading to catalyst poisoning and irreversible loss of activity. To investigate the impact of sulfur poisoning on the catalysts, we prepared the MnO₂/Beta zeolite, and a corresponding series of sulfur-poisoned catalysts through in-situ thermal decomposition of (NH₄)₂SO₄. The decrease in toluene catalytic activity of poisoned MnO₂/Beta zeolite primarily results from the conversion of the active species MnO₂ to MnSO₄. However, the crystal structure and the porous structure of MnO₂/Beta zeolite were stable, and original structure was still maintained when 1.6% (mass) sulfur species were introduced. Furthermore, the extra-framework Al of Beta zeolite could capture sulfur species to generate Al₂(SO₄)₃, thereby reducing sulfur species from reacting with Mn⁴⁺ active sites. The combination of sulfur and Beta zeolite was found to directly produce new strong-acid sites, thus effectively compensating for the effect of reduced Mn⁴⁺ active species on the catalytic activity.

Key words: Sulfur-resistant mechanism, VOCs catalytic oxidation, Beta zeolite, In-situ thermal decomposition, (NH₄)₂SO₄

摘要： Sulfur dioxide (SO₂) frequently coexist with volatile organic compounds (VOCs) in exhaust gas. The competitive adsorption of SO₂ and VOCs can adversely affect the efficiency of catalytic combustion, leading to catalyst poisoning and irreversible loss of activity. To investigate the impact of sulfur poisoning on the catalysts, we prepared the MnO₂/Beta zeolite, and a corresponding series of sulfur-poisoned catalysts through in-situ thermal decomposition of (NH₄)₂SO₄. The decrease in toluene catalytic activity of poisoned MnO₂/Beta zeolite primarily results from the conversion of the active species MnO₂ to MnSO₄. However, the crystal structure and the porous structure of MnO₂/Beta zeolite were stable, and original structure was still maintained when 1.6% (mass) sulfur species were introduced. Furthermore, the extra-framework Al of Beta zeolite could capture sulfur species to generate Al₂(SO₄)₃, thereby reducing sulfur species from reacting with Mn⁴⁺ active sites. The combination of sulfur and Beta zeolite was found to directly produce new strong-acid sites, thus effectively compensating for the effect of reduced Mn⁴⁺ active species on the catalytic activity.

关键词: Sulfur-resistant mechanism, VOCs catalytic oxidation, Beta zeolite, In-situ thermal decomposition, (NH₄)₂SO₄

Zhuo Wang, Zetao Jin, Hanqi Ning, Baishun Jiang, Kaiyuan Xie, Shufeng Zuo, Qiuyan Wang. Study on sulfur resistance of MnO₂/Beta zeolite in toluene catalytic combustion: The effect of increased acidity on catalytic performance[J]. Chinese Journal of Chemical Engineering, 2025, 78(2): 187-195.

References

[1] Y.N. Guan, H.Y. Shen, X. Guo, B.Y. Mao, Z.Y. Yang, Y.T. Zhou, H. Liang, X.L. Fan, Y.L. Jiao, J.S. Zhang, Structured hierarchical Mn-Co mixed oxides supported on silicalite-1 foam catalyst for catalytic combustion, Chin. J. Chem. Eng. 28 (9) (2020) 2319-2327.
[2] X. Chen, X. Chen, S.C. Cai, E.Q. Yu, J. Chen, H.P. Jia, MnOx/Cr₂O₃ composites prepared by pyrolysis of Cr-MOF precursors containing in situ assembly of MnOx as high stable catalyst for toluene oxidation, Appl. Surf. Sci. 475 (2019) 312-324.
[3] P. Djinovic, A. Ristic, T. Zumbar, V.D.B.C. Dasireddy, M. Rangus, G. Drazic, M. Popova, B. Likozar, N. Zabukovec Logar, N. Novak Tusar, Synergistic effect of CuO nanocrystals and Cu-oxo-Fe clusters on silica support in promotion of total catalytic oxidation of toluene as a model volatile organic air pollutant, Appl. Catal. B Environ. 268 (2020) 118749.
[4] W.B. Pei, Y.X. Liu, J.G. Deng, K.F. Zhang, Z.Q. Hou, X.T. Zhao, H.X. Dai, Partially embedding Pt nanoparticles in the skeleton of 3DOM Mn₂O₃: an effective strategy for enhancing catalytic stability in toluene combustion, Appl. Catal. B Environ. 256 (2019) 117814.
[5] R.S. Peng, X.B. Sun, S.J. Li, L.M. Chen, M.L. Fu, J.L. Wu, D.Q. Ye, Shape effect of Pt/CeO₂ catalysts on the catalytic oxidation of toluene, Chem. Eng. J. 306 (2016) 1234-1246.
[6] J. Lei, P. Wang, S. Wang, J.P. Li, Y.P. Xu, S.Y. Li, Enhancement effect of Mn doping on Co₃O₄ derived from Co-MOF for toluene catalytic oxidation, Chin. J. Chem. Eng. 52 (2022) 1-9.
[7] J. Zeng, H.M. Xie, Z. Liu, X.C. Liu, G.L. Zhou, Y. Jiang, Oxygen vacancy induced MnO₂ catalysts for efficient toluene catalytic oxidation, Catal. Sci. Technol. 11 (20) (2021) 6708-6723.
[8] Y. Liu, H. Zhou, R.R. Cao, X.Y. Liu, P.Y. Zhang, J.J. Zhan, L.F. Liu, Facile and green synthetic strategy of birnessite-type MnO₂ with high efficiency for airborne benzene removal at low temperatures, Appl. Catal. B Environ. 245 (2019) 569-582.
[9] B.D. Napruszewska, A. Michalik-Zym, R. Dula, E. Bielanska, W. Rojek, T. Machej, R.P. Socha, L. Litynska-Dobrzynska, K. Bahranowski, E.M. Serwicka, Composites derived from exfoliated laponite and Mn-Al hydrotalcite prepared in inverse microemulsion: a new strategy for design of robust VOCs combustion catalysts, Appl. Catal. B Environ. 211 (2017) 46-56.
[10] M.T. Nguyen Dinh, C.C. Nguyen, T.L. Truong Vu, V.T. Ho, Q.D. Truong, Tailoring porous structure, reducibility and Mn⁴⁺ fraction of ε-MnO₂ microcubes for the complete oxidation of toluene, Appl. Catal. A Gen. 595 (2020) 117473.
[11] Q. Liu, G. Cheng, M. Sun, W.X. Yu, Xiaohong, Zeng, S.C. Tang, Y.F. li, L. Yu, A facile preparation of hausmannite as a high-performance catalyst for toluene combustion, Chin. J. Chem. Eng. 44 (2022) 392-401.
[12] Y.S. Wu, Y. Lu, C.J. Song, Z.C. Ma, S.T. Xing, Y.Z. Gao, A novel redox-precipitation method for the preparation of α-MnO₂ with a high surface Mn⁴⁺ concentration and its activity toward complete catalytic oxidation of o-xylene, Catal. Today 201 (2013) 32-39.
[13] G.L. Wei, P. Liu, D. Chen, T.H. Chen, X.L. Liang, H.L. Chen, Activity of manganese oxides supported on halloysite towards the thermal catalytic oxidation of formaldehyde: constraint from the manganese precursor, Appl. Clay Sci. 182 (2019) 105280.
[14] P.G. S, Effect of support on the catalytic activity of manganese oxide catalyts for toluene combustion, J. Hazard. Mater. 221-222 (2012) 124-130.
[15] S.C. Jung, Y.K. Park, H.Y. Jung, U.I. Kang, J.W. Nah, S.C. Kim, Effects of calcination and support on supported manganese catalysts for the catalytic oxidation of toluene as a model of VOCs, Res. Chem. Intermed. 42 (1) (2016) 185-199.
[16] W.B. Li, M. Zhuang, T.C. Xiao, M.L.H. Green, MCM-41 supported Cu-Mn catalysts for catalytic oxidation of toluene at low temperatures, J. Phys. Chem. B 110 (43) (2006) 21568-21571.
[17] Z.W. Wang, H.G. Yang, R. Liu, S.H. Xie, Y.X. Liu, H.X. Dai, H.B. Huang, J.G. Deng, Probing toluene catalytic removal mechanism over supported Pt nano- and single-atom-catalyst, J. Hazard. Mater. 392 (2020) 122258.
[18] B. Solsona, T. Garcia, R. Sanchis, M.D. Soriano, M. Moreno, E. Rodriguez-Castellon, S. Agouram, A. Dejoz, J.M. Lopez Nieto, Total oxidation of VOCs on mesoporous iron oxide catalysts: soft chemistry route versus hard template method, Chem. Eng. J. 290 (2016) 273-281.
[19] M. Assebban, A.E. Kasmi, S. Harti, T. Chafik, Intrinsic catalytic properties of extruded clay honeycomb monolith toward complete oxidation of air pollutants, J. Hazard. Mater. 300 (2015) 590-597.
[20] C. He, J. Cheng, X. Zhang, M. Douthwaite, S. Pattisson, Z.P. Hao, Recent advances in the catalytic oxidation of volatile organic compounds: a review based on pollutant sorts and sources, Chem. Rev. 119 (7) (2019) 4471-4568.
[21] P. Wu, S.Q. Zhao, J.W. Yu, X.J. Jin, D.Q. Ye, S.H. Yang, Y.C. Qiu, Effect of absorbed sulfate poisoning on the performance of catalytic oxidation of VOCs over MnO₂, ACS Appl. Mater. Interfaces 12 (45) (2020) 50566-50572.
[22] Z. Wang, K.Y. Xie, B.S. Jiang, S.F. Zuo, Q.Y. Wang, Effects of sulfur poisoning on physicochemical properties and performance of MnO₂/AlNi-PILC for toluene catalytic combustion, J. Hazard. Mater. 435 (2022) 128950.
[23] P. Gelin, L. Urfels, M. Primet, E. Tena, Complete oxidation of methane at low temperature over Pt and Pd catalysts for the abatement of lean-burn natural gas fuelled vehicles emissions: influence of water and sulphur containing compounds, Catal. Today 83 (1-4) (2003) 45-57.
[24] Y.X. Peng, L. Zhang, L. Chen, D.Z. Yuan, G.X. Wang, X.J. Meng, F.S. Xiao, Catalytic performance for toluene abatement over Al-rich Beta zeolite supported manganese oxides, Catal. Today 297 (2017) 182-187.
[25] Q.H. Xia, S.C. Shen, J. Song, S. Kawi, K. Hidajat, Structure, morphology, and catalytic activity of β zeolite synthesized in a fluoride medium for asymmetric hydrogenation, J. Catal. 219 (1) (2003) 74-84.
[26] Z. Chen, J.R. Li, Z. Cheng, S.F. Zuo, Well-defined and highly stable AlNi composite pillared clay supported PdOx nanocrystal catalysts for catalytic combustion of benzene, Appl. Clay Sci. 163 (2018) 227-234.
[27] Z.W. Yu, A.M. Zheng, Q. Wang, L. Chen, J. Xu, J.P. Amoureux, F. Deng, Insights into the dealumination of zeolite HY revealed by sensitivity-enhanced 27Al DQ-MAS NMR spectroscopy at high field, Angew. Chem. Int. Ed 49 (46) (2010) 8657-8661.
[28] S.C. Kim, W.G. Shim, Catalytic combustion of VOCs over a series of manganese oxide catalysts, Appl. Catal. B Environ. 98 (3-4) (2010) 180-185.
[29] Z. Wang, K.Y. Xie, J. Zheng, S.F. Zuo, Studies of sulfur poisoning process via ammonium sulfate on MnO₂/γ-Al₂O₃ catalyst for catalytic combustion of toluene, Appl. Catal. B Environ. 298 (2021) 120595.
[30] Y.X. Yu, W. Tan, D.Q. An, X.W. Wang, A.N. Liu, W.X. Zou, C.J. Tang, C.Y. Ge, Q. Tong, J.F. Sun, L. Dong, Insight into the SO₂ resistance mechanism on γ-Fe₂O₃ catalyst in NH₃-SCR reaction: a collaborated experimental and DFT study, Appl. Catal. B Environ. 281 (2021) 119544.
[31] R.Z. Li, L. Zhang, S.M. Zhu, S.Y. Fu, X.P. Dong, S. Ida, L.X. Zhang, L.M. Guo, Layered δ-MnO₂ as an active catalyst for toluene catalytic combustion, Appl. Catal. A Gen. 602 (2020) 117715.
[32] P.F. Sun, Y. Long, Y.P. Long, S. Cao, X.L. Weng, Z.B. Wu, Deactivation effects of Pb(II) and sulfur dioxide on a γ-MnO₂ catalyst for combustion of chlorobenzene, J. Colloid Interface Sci. 559 (2020) 96-104.
[33] C.T. Hou, X.Y. Zhou, Y.F. Hu, P.Q. Mao, Q.J. Fan, Z.T. Wang, L.P. Wang, M.Y. Zhang, Promote the efficient co-combustion of toluene & CO in Pt/CeO₂ catalyst: orientally adjusting the oxidized SMSI to optimize acid site and oxygen vacancy, Sep. Purif. Technol. 347 (2024) 127557.

Study on sulfur resistance of MnO₂/Beta zeolite in toluene catalytic combustion: The effect of increased acidity on catalytic performance

Study on sulfur resistance of MnO₂/Beta zeolite in toluene catalytic combustion: The effect of increased acidity on catalytic performance

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

References

Related Articles 1

Recommended Articles 0

Metrics

Comments