Novel Ni/Ce(Ti)ZrO2 Catalysts for Methane Dry Reforming Prepared in Supercritical Alcohol Media

Yuliya Bespalko,Tamara Krieger,Valeria Fedorova,Ekaterina Smal,Vladimir Rogov,Svetlana Cherepanova,Vladislav Sadykov,Mikhail Simonov,Konstantin Valeev,Arcady Ishchenko

doi:10.3390/en13133365

Yuliya Bespalko, Tamara Krieger + Show 8 more

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https://doi.org/10.3390/en13133365

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Abstract

To achieve a high activity and coking stability of nickel catalysts in dry reforming of methane, materials comprised of ceria–zirconia doped by Ti were investigated as supports. Ceria–zirconia supports doped with titanium were prepared either via the Pechini method or by synthesis in supercritical alcohol media. Ni-containing catalysts were prepared by two techniques: standard incipient wetness impregnation and one-pot synthesis. The catalytic reaction of DRM to synthesis gas was carried out in the 600–750 °C range over 5% wt. Ni/Ce(Ti)ZrO2. Dried and calcined supports and catalysts were characterized by physicochemical methods including N2 adsorption, XRD, Raman, H2-TPR, and HRTEM. Both preparation methods led to formation of solid solution with cubic fluorite-like structure, as well as after addition of Ti. Introduction of Ti should provide improved oxygen storage capacity and mobility of support oxygen. The highest activity was observed with the catalyst of 5% wt. Ni/Ce0.75Ti0.2Zr0.05O2−δ composition due to optimized oxide support structure and support oxygen mobility.

Highlights

IntroductionOver the last several years, a large number of studies have been focused on the Ni-based Dry reforming of methane (DRM) catalysts, which proved to be very promising for the practical application due to their high activity and low cost [1,4,5,6,7,8,9,10]
Dry reforming of methane (DRM) is reaction (CH4 + CO2 = 2H2 + 2CO) for biogas utilization into two useful resource gases—Hydrogen and carbon monoxide
Ce0.75 Zr0.25 O2−δ and Ce0.75 Tix Zr0.25-x O2−δ (x = 0.1, 0.2) oxides were prepared by the solvothermal continuous synthesis using isopropanol along with acetylacetone as a complexing agent, which was added into the Zr solution at a 2:1 molar ratio to Zr amount

Summary

Introduction

Over the last several years, a large number of studies have been focused on the Ni-based DRM catalysts, which proved to be very promising for the practical application due to their high activity and low cost [1,4,5,6,7,8,9,10]. Many research studies aimed to increase catalytic activity and stability by controlling the morphology of the active component and using it in the form of highly dispersed nano-particles, which should minimize carbon formation [11,12]. Since the process of coking is sensitive to the support structure and dispersion of active metal deposited on the catalyst surface is very important, activity and stability of catalysts can be provided by developing supports with required characteristics. Ceria has been extensively studied in the literature, and the oxygen storage capacity of ceria can be increased

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