Highly active and stable Ni-based bimodal pore catalyst for dry reforming of methane

Abstract Bimodal pore NiCeMgAl catalysts were synthesized via the refluxed co-precipitation method. Methane reforming using carbon dioxide over this bimodal pore NiCeMgAl catalyst for syngas production was systematically studied by optimizing the active component NiO-loading, calcination temperature, reduction temperature and gas hourly space velocity (GHSV). The Ni 15 CeMgAl sample with 15 wt% NiO loading, was found to be active enough at 750 °C with a high CH 4 conversion of 96.5%. The proper reduction temperature for the NiCeMgAl catalyst is either 550–650 °C or 850 °C. Higher calcination temperature favors the formation of NiAl 2 O 4 and MgAl 2 O 4 spinel structures. The Ni active sites derived from the NiAl 2 O 4 spinel structure had longer stability than those from the free NiO. Compared with non-bimodal pore NiCeMgAl catalyst, bimodal pore NiCeMgAl catalyst has a longer stability in the feed gas without dilution. The large pores in the bimodal pore Ni 15 CeMgAl catalyst were supposed to contribute to the quick molecule transfer during the dry reforming of methane (DRM) reaction when the GHSV was less than 96,000 h −1 . The evolution of the Ni 15 CeMgAl catalyst before and after the DRM reaction was investigated by BET, XRD, TEM, and TGA techniques. A schema of the DRM reaction on the bimodal pore Ni 15 CeMgAl catalyst was proposed, and the correlation between the structure evolution and catalytic performance change was also discussed.

[1]  Subhash Bhatia,et al.  Catalytic Technology for Carbon Dioxide Reforming of Methane to Synthesis Gas , 2009 .

[2]  Leilei Xu,et al.  Ordered mesoporous alumina supported nickel based catalysts for carbon dioxide reforming of methane , 2012 .

[3]  A. Mohamed,et al.  Direct use of as-synthesized multi-walled carbon nanotubes for carbon dioxide reforming of methane for producing synthesis gas , 2014 .

[4]  Alexander V. Neimark,et al.  A New Templated Ordered Structure with Combined Micro- and Mesopores and Internal Silica Nanocapsules , 2002 .

[5]  Yi Zhang,et al.  Chemical and spatial promotional effects of bimodal pore catalysts for methane dry reforming , 2011 .

[6]  J. A. Calles,et al.  Hydrogen production by steam reforming of ethanol using Ni catalysts based on ternary mixed oxides prepared by coprecipitation , 2012 .

[7]  C. Cabrera,et al.  Syngas production from CO2 reforming of methane using Ce-doped Ni-catalysts obtained from hydrotalcites by reconstruction method , 2010 .

[8]  Liyi Shi,et al.  Morphology Dependence of Catalytic Properties of Ni/CeO2 Nanostructures for Carbon Dioxide Reforming of Methane , 2012 .

[9]  C. Daza,et al.  Ce-incorporation in mixed oxides obtained by the self-combustion method for the preparation of high performance catalysts for the CO2 reforming of methane , 2010 .

[10]  Xiaoming Zheng,et al.  The deposition of coke from methane on a Ni/MgAl2O4 catalyst , 2007 .

[11]  M. A. Lansarin,et al.  Effect of composition and thermal pretreatment on properties of Ni–Mg–Al catalysts for CO2 reforming of methane , 2006 .

[12]  S. Kawi,et al.  Yolk–Satellite–Shell Structured Ni–Yolk@Ni@SiO2 Nanocomposite: Superb Catalyst toward Methane CO2 Reforming Reaction , 2014 .

[13]  N. Rahemi,et al.  Syngas production from reforming of greenhouse gases CH4/CO2 over Ni–Cu/Al2O3 nanocatalyst: Impregnated vs. plasma-treated catalyst , 2014 .

[14]  C. Petit,et al.  Reactivity of perovskite-type precursor in MWCNTs synthesis , 2008 .

[15]  Qingjun Chen,et al.  Effect of reflux digestion treatment on the catalytic performance of Ni–CaO–ZrO2 nanocomposite catalysts for CO2 reforming of CH4 , 2013 .

[16]  Z. Pászti,et al.  Methane dry reforming with CO2: A study on surface carbon species , 2010 .

[17]  Fereshteh Meshkani,et al.  Effects of support modifiers on the catalytic performance of Ni/Al2O3 catalyst in CO2 reforming of methane , 2014 .

[18]  A. Al-Fatesh,et al.  Effects of calcination and activation temperature on dry reforming catalysts , 2012 .

[19]  X. Verykios,et al.  Carbon dioxide reforming of methane to synthesis gas over supported Ni catalysts , 1994 .

[20]  Javier Pérez-Ramírez,et al.  Pore size determination in modified micro- and mesoporous materials. Pitfalls and limitations in gas adsorption data analysis , 2003 .

[21]  A. Steinfeld,et al.  Dry Reforming of Methane Using a Solar-Thermal Aerosol Flow Reactor , 2004 .

[22]  W. Ding,et al.  Effect of Fe/Cu ratio on the activity of Fe–Al–Cu catalysts for water gas shift reaction under hydrogen-rich atmosphere , 2012 .

[23]  James Spivey,et al.  A review of dry (CO2) reforming of methane over noble metal catalysts. , 2014, Chemical Society reviews.

[24]  Yuhan Sun,et al.  Higher alcohol synthesis over Cu-Fe composite oxides with high selectivity to C2+OH , 2013 .

[25]  J. Lunsford.  CATALYTIC CONVERSION OF METHANE TO MORE USEFUL CHEMICALS AND FUELS: A CHALLENGE FOR THE 21ST CENTURY , 2000 .

[26]  Yi Zhang,et al.  A new and direct preparation method of iron-based bimodal catalyst and its application in Fischer–Tropsch synthesis , 2009 .

[27]  Christian Sattler,et al.  Solar thermal reforming of methane feedstocks for hydrogen and syngas production—A review , 2014 .

[28]  A. Serrano-Lotina,et al.  Long-term stability test of Ni-based catalyst in carbon dioxide reforming of methane , 2014 .

[29]  L. Guczi,et al.  Sol-derived AuNi/MgAl2O4catalysts: Formation, structure and activityin dry reforming of methane , 2013 .

[30]  P. Jacobs,et al.  Influence of composition of MgAl2O4 supported NiCeO2ZrO2 catalysts on coke formation and catalyst stability for dry reforming of methane , 2008 .

[31]  F. Mondragón,et al.  High stability of Ce-promoted Ni/Mg―Al catalysts derived from hydrotalcites in dry reforming of methane , 2010 .

[32]  C. Daza,et al.  Co-precipitated Ni–Mg–Al catalysts containing Ce for CO2 reforming of methane , 2011 .

[33]  Hui Lou,et al.  Dry reforming of methane over nickel catalysts supported on magnesium aluminate spinels , 2004 .

[34]  Xinmei Liu,et al.  Facile route to prepare bimodal mesoporous γ-Al2O3 as support for highly active CoMo-based hydrodesulfurization catalyst , 2012 .

[35]  F. Yu,et al.  Catalytic conversion of syngas to mixed alcohols over Zn-Mn promoted Cu-Fe based catalyst , 2012 .