Preparation of MoO3/γ-Al2O3 sulfur-resistant methanation catalyst with segmented plasma fluidized bed

doi:10.1016/j.cjche.2025.02.014

Abstract

Abstract: In order to solve the shortcomings of MoO₃/γ-Al₂O₃ catalyst for sulfur-resistant methanation, a segmented plasma fluidized bed reactor was designed, where plasma discharge zone and the fluidization zone were separated under higher discharge power. At the bed height of 30 mm, the gas velocity of 0.10 m·s^-1 can provide a better fluidization state. The suitable discharge results can be achieved when the input power is 27 W and the discharge interval is 2.0 mm. With the extension of catalyst plasma treatment time, the conversion of CO decreases, but the selectivity of CH₄ increases. Combined with N₂ physical adsorption-desorption, XRD, TEM, Raman, TGA and TPR characterization, it was found that the active components of the catalyst are uniformly dispersed on the γ-Al₂O₃ support. After plasma treatment, tetrahedral Mo species was used as the active center, and the interaction between Mo and the carrier was strengthened. It provides a novel approach for preparing catalyst with dielectric barrier discharge (DBD) fluidized bed reactor.

Key words: Plasma, Sulfur-resistant methanation, Methane, Catalyst, Fluidized-bed

摘要： In order to solve the shortcomings of MoO₃/γ-Al₂O₃ catalyst for sulfur-resistant methanation, a segmented plasma fluidized bed reactor was designed, where plasma discharge zone and the fluidization zone were separated under higher discharge power. At the bed height of 30 mm, the gas velocity of 0.10 m·s^-1 can provide a better fluidization state. The suitable discharge results can be achieved when the input power is 27 W and the discharge interval is 2.0 mm. With the extension of catalyst plasma treatment time, the conversion of CO decreases, but the selectivity of CH₄ increases. Combined with N₂ physical adsorption-desorption, XRD, TEM, Raman, TGA and TPR characterization, it was found that the active components of the catalyst are uniformly dispersed on the γ-Al₂O₃ support. After plasma treatment, tetrahedral Mo species was used as the active center, and the interaction between Mo and the carrier was strengthened. It provides a novel approach for preparing catalyst with dielectric barrier discharge (DBD) fluidized bed reactor.

关键词: Plasma, Sulfur-resistant methanation, Methane, Catalyst, Fluidized-bed

Baowei Wang, Jiangzhou Kong, Xiaoyan Li. Preparation of MoO₃/γ-Al₂O₃ sulfur-resistant methanation catalyst with segmented plasma fluidized bed[J]. Chinese Journal of Chemical Engineering, 2025, 81(5): 142-150.

Baowei Wang, Jiangzhou Kong, Xiaoyan Li. Preparation of MoO₃/γ-Al₂O₃ sulfur-resistant methanation catalyst with segmented plasma fluidized bed[J]. 中国化学工程学报, 2025, 81(5): 142-150.

References

[1] I. Hussain, G. Tanimu, S. Ahmed, C.U. Aniz, H. Alasiri, K. Alhooshani, A review of the indispensable role of oxygen vacancies for enhanced CO₂ methanation activity over CeO₂-based catalysts: Uncovering, influencing, and tuning strategies, Int. J. Hydrog. Energy 48 (64) (2023) 24663-24696.
[2] J. Ren, H. Lou, N. Xu, F. Zeng, G. Pei, Z.D. Wang, Methanation of CO/CO₂ for power to methane process: Fundamentals, status, and perspectives, J. Energy Chem. 80 (2023) 182-206.
[3] A. Saxena, 10 - Synthetic natural gas from coal, Advances in Natural Gas: Formation, Processing, and Applications Volume: 1: Natural Gas Formation and Extraction, Elsevier,(2024) 245-259.
[4] Q. Guo, D. Shaozhong Li, D. Jin Li, D. Yongke Hu, D. Yanxing Li, Effect of SiO₂ on the CO selective methanation over SiO₂/Ni-ZrO₂ catalysts, ChemCatChem 14 (1) (2022) e202101281.
[5] Y.H. Han, J.X. Zhao, Y.H. Quan, S.N. Yin, S.P. Wu, J. Ren, Highly efficient LaxCe_1-xO_2-x/2 nanorod-supported nickel catalysts for CO methanation: effect of La addition, Energy Fuels 35 (4) (2021) 3307-3314.
[6] M.H. Zhu, P.F. Tian, X.Y. Cao, J.C. Chen, T.C. Pu, B.F. Shi, J. Xu, J. Moon, Z.L. Wu, Y.F. Han, Vacancy engineering of the nickel-based catalysts for enhanced CO₂ methanation, Appl. Catal. B Environ. 282 (2021) 119561.
[7] Z.H. Li, K. Zhang, W.H. Wang, J.L. Qu, Y. Tian, B.W. Wang, X.B. Ma, Kinetics of sulfur-resistant methanation over supported molybdenum-based catalyst, J. Taiwan Inst. Chem. Eng. 68 (2016) 239-245.
[8] K. Zhang, Q. Wang, B.W. Wang, Y. Xu, X.B. Ma, Z.H. Li, A DFT study on CO methanation over the activated basal plane from a strained two-dimensional nano-MoS₂, Appl. Surf. Sci. 479 (2019) 360-367.
[9] D. Pashchenko, I. Makarov, Carbon deposition in steam methane reforming over a Ni-based catalyst: Experimental and thermodynamic analysis, Energy 222 (2021) 119993.
[10] L. Silvester, A. Antzara, G. Boskovic, E. Heracleous, A.A. Lemonidou, D.B. Bukur, NiO supported on Al₂O₃ and ZrO₂ oxygen carriers for chemical looping steam methane reforming, Int. J. Hydrog. Energy 40 (24) (2015) 7490-7501.
[11] F.H. Meng, X. Li, M.H. Li, X.X. Cui, Z. Li, Catalytic performance of CO methanation over La-promoted Ni/Al₂O₃ catalyst in a slurry-bed reactor, Chem. Eng. J. 313 (2017) 1548-1555.
[12] Y. Zeng, H.F. Ma, H.T. Zhang, W.Y. Ying, D.Y. Fang, Highly efficient NiAl₂O₄-free Ni/γ-Al₂O₃ catalysts prepared by solution combustion method for CO methanation, Fuel 137 (2014) 155-163.
[13] J. Li, L. Zhou, P.C. Li, Q.S. Zhu, J.J. Gao, F.N. Gu, F.B. Su, Enhanced fluidized bed methanation over a Ni/Al₂O₃ catalyst for production of synthetic natural gas, Chem. Eng. J. 219 (2013) 183-189.
[14] J. Liu, E.D. Wang, J. Lv, Z.H. Li, B.W. Wang, X.B. Ma, S.D. Qin, Q. Sun, Investigation of sulfur-resistant, highly active unsupported MoS₂ catalysts for synthetic natural gas production from CO methanation, Fuel Process. Technol. 110 (2013) 249-257.
[15] Z.P. Liu, Y. Xu, Z.H. Li, B.W. Wang, W.H. Wang, X.B. Ma, R.J. Liu, Sulfur-resistant methanation over MoO₃/CeO₂-ZrO₂ catalyst: influence of Ce-addition methods, J. Energy Chem. 28 (2019) 31-38.
[16] S.D. Qin, J.B. Li, J.Y. Long, X. Yang, P. Miao, Promotion effect of cerium on Mo/Al₂O₃ catalyst for methanation, Appl. Catal. A Gen. 598 (2020) 117559.
[17] K. Stangeland, D. Kalai, H.L. Li, Z.X. Yu, CO₂ methanation: the effect of catalysts and reaction conditions, Energy Procedia 105 (2017) 2022-2027.
[18] Z.L. Li, Y.Z. Qu, J.J. Wang, H.L. Liu, M.R. Li, S. Miao, C. Li, Highly selective conversion of carbon dioxide to aromatics over tandem catalysts, Joule 3 (2) (2019) 570-583.
[19] J. Wang, W. Liu, G. Luo, Z.J. Li, C. Zhao, H.R. Zhang, M.Z. Zhu, Q. Xu, X.Q. Wang, C.M. Zhao, Y.T. Qu, Z.K. Yang, T. Yao, Y.F. Li, Y. Lin, Y.E. Wu, Y.D. Li, Synergistic effect of well-defined dual sites boosting the oxygen reduction reaction, Energy Environ. Sci. 11 (12) (2018) 3375-3379.
[20] G.P. Vissokov, Plasma-chemical preparation of nanostructured catalysts for low-temperature steam conversion of carbon monoxide: catalytic activity, Catal. Today 89 (1-2) (2004) 223-231.
[21] M. Georgieva, G. Vissokov, I. Grancharov, Physical-chemical characterization of nanodispersed powders produced by a plasma-chemical technique, Plasma Sci. Technol. 9 (3) (2007) 273-279.
[22] S. Chen, H.Q. Wang, F. Dong, Activation and characterization of environmental catalysts in plasma-catalysis: Status and challenges, J. Hazard. Mater. 427 (2022) 128150.
[23] J. Kruszelnicki, K.W. Engeling, J.E. Foster, M.J. Kushner, Interactions between atmospheric pressure plasmas and metallic catalyst particles in packed bed reactors, J. Phys. D: Appl. Phys. 54 (10) (2021) 104001.
[24] A. Nemati Tamar, T. Hamzehlouyan, M.R. Khani, M. Alihoseini, B. Shokri, Synergistic effects of plasma and catalyst in formaldehyde conversion over a Ni/α-Al₂O₃ catalyst in a dielectric barrier discharge reactor, Results Eng. 17 (2023) 100997.
[25] Z.P. Ye, L. Zhao, A. Nikiforov, J.M. Giraudon, Y. Chen, J.D. Wang, X. Tu, A review of the advances in catalyst modification using nonthermal plasma: Process, Mechanism and Applications, Adv. Colloid Interface Sci. 308 (2022) 102755.
[26] M.H. Jiang, B.W. Wang, J. Lv, H.Y. Wang, Z.H. Li, X.B. Ma, S.D. Qin, Q. Sun, Effect of sulfidation temperature on the catalytic activity of MoO₃/CeO₂-Al₂O₃ toward sulfur-resistant methanation, Appl. Catal. A Gen. 466 (2013) 224-232.
[27] H.R. Wu, S.L. Xiong, C.J. Liu, Preparation of In₂O₃/ZrO₂ catalyst via DBD plasma decomposition of Zr(OH)4 for CO₂ hydrogenation to methanol, Catal. Today 423 (2023) 114024.
[28] N. Ullah, M. Su, Y.W. Yang, Z.H. Li, Enhanced CO₂ hydrogenation to light hydrocarbons on Ni-based catalyst by DBD plasma, Int. J. Hydrog. Energy 48 (57) (2023) 21735-21751.
[29] C.J. Liu, M.Y. Li, J.Q. Wang, X.T. Zhou, Q.T. Guo, J.M. Yan, Y.Z. Li, Plasma methods for preparing green catalysts: Current status and perspective, Chin. J. Catal. 37 (3) (2016) 340-348.
[30] J. Werther, E.U. Hartge, S. Heinrich, Fluidized-bed reactors-status and some development perspectives, Chem. Ing. Tech. 86 (12) (2014) 2022-2038.
[31] X.Z. Chen, H.H. Kim, T. Nozaki, Plasma catalytic technology for CH₄ and CO₂ conversion: a review highlighting fluidized-bed plasma reactor, Plasma Process. Polym. 21 (1) (2024) 2200207.
[32] T. Kroker, T. Kolb, A. Schenk, K. Krawczyk, M. Mlotek, K.H. Gericke, Catalytic conversion of simulated biogas mixtures to synthesis gas in a fluidized bed reactor supported by a DBD, Plasma Chem. Plasma Process. 32 (3) (2012) 565-582.
[33] T. Nozaki, X.Z. Chen, D.Y. Kim, C.Y. Zhan, Combination of DBD and catalysts for CH₄ and CO₂ conversion: basics and applications, Plasma Chem. Plasma Process. 43 (6) (2023) 1385-1410.
[34] E. Defoort, R. Bellanger, C. Batiot-Dupeyrat, E. Moreau, Ionic wind produced by a DC needle-to-plate corona discharge with a gap of 15 mm, J. Phys. D: Appl. Phys. 53 (17) (2020) 175202.
[35] S.S. Xu, S. Chansai, Y. Shao, S.J. Xu, Y.C. Wang, S. Haigh, Y.B. Mu, Y.L. Jiao, C.E. Stere, H.H. Chen, X.L. Fan, C. Hardacre, Mechanistic study of non-thermal plasma assisted CO₂ hydrogenation over Ru supported on MgAl layered double hydroxide, Appl. Catal. B Environ. 268 (2020) 118752.
[36] X.Z. Chen, Z.R. Sheng, S. Murata, S. Zen, H.H. Kim, T. Nozaki, CH₄ dry reforming in fluidized-bed plasma reactor enabling enhanced plasma-catalyst coupling, J. CO₂ Util. 54 (2021) 101771.
[37] S. Zen, N. Takeuchi, Y. Teramoto, Ammonia synthesis using atmospheric pressure fluidized bed plasma, J. Phys. D: Appl. Phys. 57 (11) (2024) 115203.
[38] S.J. Li, X.Q. Dang, X. Yu, R. Yu, G. Abbasd, Q. Zhang, High energy efficient degradation of toluene using a novel double dielectric barrier discharge reactor, J. Hazard. Mater. 400 (2020) 123259.
[39] B.W. Wang, J.Z. Kong, X.Y. Li, Characteristics of integral plasma-fluidized bed and preparation of Mo-based catalysts for sulfur-resistant methanation, React. Kinet. Mech. Catal. 138 (1) (2025) 285-302.
[40] J. Jang, H. Nishiyama, Discharge study of argon DC arc jet assisted by DBD plasma for metal surface treatment, IEEE Trans. Plasma Sci. 43 (10) (2015) 3688-3694.
[41] D. Danhua Mei, D. Xin Tu, Atmospheric pressure non-thermal plasma activation of CO₂ in a packed-bed dielectric barrier discharge reactor, ChemPhysChem 18 (22) (2017) 3253-3259.
[42] V.P. Pakharukova, D.A. Yatsenko, E.Y. Gerasimov, E. Vlasova, G.A. Bukhtiyarova, S.V. Tsybulya, Total scattering Debye function analysis: effective approach for structural studies of supported MoS₂-based hydrotreating catalysts, Ind. Eng. Chem. Res. 59 (23) (2020) 10914-10922.
[43] H.Y. Wang, Z.H. Li, B.W. Wang, X.B. Ma, S.D. Qin, S.L. Sun, Q. Sun, Precursor effect on catalytic properties of Mo-based catalyst for sulfur-resistant methanation, Korean J. Chem. Eng. 31 (12) (2014) 2157-2161.
[44] B.W. Wang, D.J. Meng, W.H. Wang, Z.H. Li, X.B. Ma, Effect of citric acid addition on MoO₃/CeO₂-Al₂O₃ catalyst for sulfur-resistant methanation, J. Fuel Chem. Technol. 44 (12) (2016) 1479-1484.
[45] S. Imamura, H. Sasaki, M. Shono, H. Kanai, Structure of molybdenum supported on α-, γ-, and Y-aluminas in relation to its epoxidation activity, J. Catal. 177 (1) (1998) 72-81.
[46] X.H. Yang, Y.F. Zuo, P.F. Feng, N. Wang, J. Li, Y.Q. Wang, G.H. Zhang, K.C. Chou, Mechanism and kinetics of decomposition reaction of ultrafine ammonium molybdate for preparing ultrafine MoO₃ powder, Mater. Chem. Phys. 302 (2023) 127760.
[47] Z.L. Yin, X.H. Li, Q.Y. Chen, Study on the kinetics of the thermal decompositions of ammonium molybdates, Thermochim. Acta 352 (2000) 107-110.
[48] T.N. Zhou, H.L. Yin, Y.Q. Liu, S.N. Han, Y.M. Chai, C.G. Liu, Effect of phosphorus content on the active phase structure of NiMoP/Al₂O₃ catalyst, J. Fuel Chem. Technol. 38 (1) (2010) 69-74.
[49] P. Afanasiev, The influence of reducing and sulfiding conditions on the properties of unsupported MoS₂-based catalysts, J. Catal. 269 (2) (2010) 269-280.
[50] Z.H. Li, K. Zhang, W.H. Wang, B.W. Wang, X.B. Ma, DFT study into the reaction mechanism of CO methanation over pure MoS₂, Int. J. Quantum Chem. 118 (16) (2018) e25643.
[51] Z.H. Li, Z.J. Yin, W.H. Wang, Y. Tian, B.W. Wang, X.B. Ma, The effect of citric acid on the catalytic activity of nano-sized MoS₂ toward sulfur-resistant CO methanation, Appl. Organomet. Chem. 32 (5) (2018) e4339.
[52] S. Cristol, J.F. Paul, E. Payen, D. Bougeard, F. Hutschka, S. Clemendot, DBT derivatives adsorption over molybdenum sulfide catalysts: a theoretical study, J. Catal. 224 (1) (2004) 138-147.
[53] C. Liu, W.H. Wang, Y. Xu, Z.H. Li, B.W. Wang, X.B. Ma, Effect of zirconia morphology on sulfur-resistant methanation performance of MoO₃/ZrO₂ catalyst, Appl. Surf. Sci. 441 (2018) 482-490.
[54] B.W. Wang, T.T. Wang, J. Zhao, Z.H. Li, Y. Xu, X.B. Ma, Effect of phosphorus precursor on the catalytic performance of metal phosphides in the methanation of syngas, J. Fuel Chem. Technol. 49 (7) (2021) 952-958.

Preparation of MoO₃/γ-Al₂O₃ sulfur-resistant methanation catalyst with segmented plasma fluidized bed

Preparation of MoO₃/γ-Al₂O₃ sulfur-resistant methanation catalyst with segmented plasma fluidized bed

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