CO₂ methanation and co-methanation of CO and CO₂ over Mn-promoted Ni/Al₂O₃ catalysts

Abstract

A series of Mn-promoted 15 wt-% Ni/Al₂O₃ catalysts were prepared by an incipient wetness impregnation method. The effect of the Mn content on the activity of the Ni/Al₂O₃ catalysts for CO₂ methanation and the co-methanation of CO and CO₂ in a fixed-bed reactor was investigated. The catalysts were characterized by N₂ physisorption, hydrogen temperature-programmed reduction and desorption, carbon dioxide temperature-programmed desorption, X-ray diffraction and high-resolution transmission electron microscopy. The presence of Mn increased the number of CO₂ adsorption sites and inhibited Ni particle agglomeration due to improved Ni dispersion and weakened interactions between the nickel species and the support. The Mn-promoted 15 wt-% Ni/Al₂O₃ catalysts had improved CO₂ methanation activity especially at low temperatures (250 to 400 °C). The Mn content was varied from 0.86% to 2.54% and the best CO₂ conversion was achieved with the 1.71Mn-Ni/Al₂O₃ catalyst. The co-methanation tests on the 1.71Mn-Ni/Al₂O₃ catalyst indicated that adding Mn markedly enhanced the CO₂ methanation activity especially at low temperatures but it had little influence on the CO methanation performance. CO₂ methanation was more sensitive to the reaction temperature and the space velocity than the CO methanation in the co-methanation process.

Graphical abstract

Keywords

Mn promotion / nickel catalysts / CO₂ methanation / co-methanation of CO and CO₂

References

[1] Lu X, Gu F, Liu Q, Gao J, Liu Y, Li H, Jia L, Xu G, Zhong Z, Su F. VO_x promoted Ni catalysts supported on the modified bentonite for CO and CO₂ methanation. Fuel Processing Technology, 20 15, 135: 34– 46

[2] Liu H, Zou X, Wang X, Lu X, Ding W. Effect of CeO₂ addition on Ni/Al₂O₃ catalysts for methanation of carbon dioxide with hydrogen. Journal of Natural Gas Chemistry, 2012, 21(6): 703–707

[3] Ocampo F, Louis B, Kiwi-Minsker L, Roger A. Effect of Ce/Zr composition and noble metal promotion on nickel based Ce_xZr₁-_xO₂ catalysts for carbon dioxide methanation. Applied Catalysis A, General, 2011, 392(1-2): 36–44

[4] Cai M, Wen J, Chu W, Cheng X, Li Z. Methanation of carbon dioxide on Ni/ZrO₂-Al₂O₃ catalysts: Effects of ZrO₂ promoter and preparation method of novel ZrO₂-Al₂O₃ carrier. Journal of Natural Gas Chemistry, 2011, 20(3): 318–324

[5] B°Chel R, Baiker A, Pratsinis S. Effect of Ba and K addition and controlled spatial deposition of Rh in Rh/Al₂O₃ catalysts for CO₂ hydrogenation. Applied Catalysis A, General, 2014, 477: 93–101

[6] Li L, Wei S, Xu G. Influence of second metal on Ni-based catalysts preparated by CO-preciptation method for methanation on of carbon dioxide. Natural Gas Chemical Industry, 2004, 29: 27–31 (in Chinese)

[7] Guo C, Wu Y, Qin H, Zhang J. CO methanation over ZrO₂/Al₂O₃ supported Ni catalysts: A comprehensive study. Fuel Processing Technology, 2014, 124: 61–69

[8] Lin X, Yang K, Si R, Chen X, Dai W, Fu X. Photo-assisted catalytic methanation of CO in H₂-rich stream over Ru/TiO₂. Applied Catalysis B: Environmental, 2014, 147: 585–591

[9] Urasaki K, Tanpo Y, Nagashima Y, Kikuchi R, Satokawa S. Effects of preparation conditions of Ni/TiO₂ catalysts for selective CO methanation in the reformate gas. Applied Catalysis A, General, 2013, 452: 174–178

[10] Hwang S, Lee J, Hong U, Baik J, Koh D, Lim H, Song I. Methanation of carbon dioxide over mesoporous Ni-Fe-Ru-Al₂O₃ xerogel catalysts: Effect of ruthenium content. Journal of Industrial and Engineering Chemistry, 2013, 19(2): 698–703

[11] Lu H, Yang X, Gao G, Wang K, Shi Q, Wang J, Han C, Liu J, Tong M, Liang X, Li C. Mesoporous zirconia-modified clays supported nickel catalysts for CO and CO₂ methanation. International Journal of Hydrogen Energy, 2014, 39(33): 18894–18907

[12] Gao J, Jia C, Li J, Zhang M, Gu F, Xu G, Zhong Z, Su F. Ni/Al₂O₃ catalysts for CO methanation: Effect of Al₂O₃ supports calcined at different temperatures. Journal of Energy Chemistry, 2013, 22(6): 919–927

[13] Garbarino G, Valsamakis I, Riani P, Busca G. On the consistency of results arising from different techniques concerning the nature of supported metal oxide (nano)particles. The case of NiO/Al₂O₃. Catalysis Communications, 2014, 51: 37–41

[14] Zhen W, Li B, Lu G, Ma J. Enhancing catalytic activity and stability for CO₂ methanation on Ni-Ru/gamma-Al₂O₃ via modulating impregnation sequence and controlling surface active species. RSC Advances, 2014, 4(32): 16472–16479

[15] Hwang S, Hong U, Lee J, Seo J, Baik J, Koh D, Lim H, Song I. Methanation of carbon dioxide over mesoporous Ni-Fe-Al₂O₃ catalysts prepared by a coprecipitation method: Effect of precipitation agent. Journal of Industrial and Engineering Chemistry, 2013, 19(6): 2016–2021

[16] Zhou L, Wang Q, Ma L, Chen J, Ma J, Zi Z. CeO₂ Promoted mesoporous Ni/gamma-Al₂O₃ catalyst and its reaction conditions for CO₂ methanation. Catalysis Letters, 2015, 145(2): 612–619

[17] Hwang S, Lee J, Hong U, Jung J, Koh D, Lim H, Byun C, Song I. Hydrogenation of carbon monoxide to methane over mesoporous nickel-M-alumina (M=Fe, Ni, Co, Ce, and La) xerogel catalysts. Journal of Industrial and Engineering Chemistry, 2012, 18(1): 243–248

[18] Liu Q, Gao J, Zhang M, Li H, Gu F, Xu G, Zhong Z, Su F. Highly active and stable Ni/g-Al₂O₃ catalysts selectively deposited with CeO₂ for CO methanation dagger. RSC Advances, 2014, 4(31): 16094–16103

[19] Zeng Y, Ma H, Zhang H, Ying W, Fang D. Highly efficient NiAl₂O₄-free Ni/g-Al₂O₃ catalysts prepared by solution combustion method for CO methanation. Fuel, 2014, 137: 155–163

[20] Lohitharn N, Goodwin J Jr. Impact of Cr, Mn and Zr addition on Fe Fischer-Tropsch synthesis catalysis: Investigation at the active site level using SSITKA. Journal of Catalysis, 2008, 257(1): 142–151

[21] Jiang Q. The methanation of carbon dioxide on supported nickel catalyst. Natural Gas Chemical Industry, 2000, 25: 9–14 (in Chinese)

[22] Wang C, Gong J. Study on Ni-Mn-based catalysts for methanation of carbon dioxide. Natural Gas Chemical Industry, 2011, 36: 4–6 (in Chinese)

[23] Gao X, Wang Y, Li H, Zhao Y. Effect of mnaganese promoter on the catalystic performance of Ni/γ-Al₂O₃ catalyst for CO₂ metnanation. Journal of Molecular Catalysis (China), 2011, 25: 49–54

[24] Zhao A, Ying W, Zhang H, Ma H, Fang D. Ni/Al₂O₃ catalysts for syngas methanation: Effect of Mn promoter. Journal of Natural Gas Chemistry, 2012, 21(2): 170–177 (in Chinese)

[25] Liu D, Quek X, Cheo W, Lau R, Borgna A, Yang Y. MCM-41 supported nickel-based bimetallic catalysts with superior stability during carbon dioxide reforming of methane: Effect of strong metal-support interaction. Journal of Catalysis, 2009, 266(2): 380–390

[26] Yang C, Yang W, Ling F, Fan F. Determination of metal dispersion on supported metal catalyst surface. Chemical Industry and Engineering Progress, 2010, 29(8): 1468–1473

[27] Velu S, Gangwal S. Synthesis of alumina supported nickel nanoparticle catalysts and evaluation of nickel metal dispersions by temperature programmed desorption. Solid State Ionics, 2006, 177(7-8): 803–811

[28] Zamani A, Ali R, Bakar W. The investigation of Ru/Mn/Cu-Al₂O₃ oxide catalysts for CO₂/H₂ methanation in natural gas. Journal of the Taiwan Institute of Chemical Engineers, 2014, 45(1): 143–152

[29] Qin H, Guo C, Wu Y, Zhang J. Effect of La₂O₃ promoter on NiO/Al₂O₃ catalyst in CO methanation. Korean Journal of Chemical Engineering, 2014, 31(7): 1168–1173

[30] Bai X, Wang S, Sun T, Wang S. The sintering of Ni/Al₂O₃ methanation catalyst for substitute natural gas production. Reaction Kinetics, Mechanisms and Catalysis, 2014, 112(2): 437–451

[31] Razzaq R, Zhu H, Jiang L, Muhammad U, Li C, Zhang S. Catalytic methanation of CO and CO₂ in coke oven gas over Ni-Co/ZrO₂-CeO₂. Industrial & Engineering Chemistry Research, 2013, 52(6): 2247–2256

[32] Pan Q, Peng J, Sun T, Wang S, Wang S. Insight into the reaction route of CO₂ methanation: Promotion effect of medium basic sites. Catalysis Communications, 2014, 45: 74–78

[33] Habazaki H, Yamasaki M, Zhang B, Kawashima A, Kohno S, Takai T, Hashimoto K. Co-methanation of carbon monoxide and carbon dioxide on supported nickel and cobalt catalysts prepared from amorphous alloys. Applied Catalysis A, General, 1998, 172(1): 131–140

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