Development of Silicalite-1-encapsulated Ni nanoparticle catalyst from amorphous silica-coated Ni for dry reforming of methane: Achieving coke formation suppression and high thermal stability

Abstract

Dry reforming of methane (DRM) is an important reaction for converting CO2 into synthesis gas (H2 + CO). Though Ni is one of the most promising catalysts, the agglomeration of Ni particles and the formation of coke on the catalyst proceed during DRM, resulting in rapid catalyst deactivation. Therefore, the development of Ni-based catalysts that exhibit high thermal stability and suppress coke formation is indispensable. The encapsulation structure of Ni nanoparticles in porous supports is reported to be effective for high DRM activities and the suppression of coke formation.Herein, we synthesized a Silicalite-1-encapsulated Ni catalyst (Ni@Silicalite-1) for DRM using amorphous silica-encapsulated Ni-oxide nanoparticles (NiOx@SiO2) as the Ni precursor, and the effect of physicochemical properties on DRM activities was investigated using Ni@Silicalite-1, Ni@SiO2 (NiOx@SiO2 after H2 reduction), and Ni/Silicalite-1 (impregnation). For Ni@Silicalite-1, Ni phyllosilicate was formed inside Silicalite-1 during the hydrothermal synthesis, and the encapsulation structure of 4.5-nm-sized Ni particles was realized by reducing Ni phyllosilicate to Ni particles inside the zeolite. Because the small Ni particles were stabilized in the porous supports, Ni@Silicalite-1 and Ni@SiO2 exhibited high and stable activity for DRM at 600 °C with negligible coke formation (6.6 and 8.2 mg-C/g-catalyst for Ni@Silicalite-1 and Ni@SiO2 respectively), whereas a large amount of coke was formed on Ni/Silicalite-1 (532 mg-C/g-catalyst). Ni@Silicalite-1 exhibited high and stable DRM activity throughout 24 h at 600 °C and GHSV = 108000 mL/(g-cat·h). Moreover, because Silicalite1 possessed high thermal stability, the high activity of Ni@Silicalite-1 was maintained throughout the 5 h of DRM at 850 °C, whereas the activity of Ni@SiO2 decreased because of the collapse of the pore structure of SiO2. Ni@Silicalite1 exhibited a higher conversion rate of methane (13.3 mol-CH4/(g-Ni·min) at 850 °C and GHSV = 1080000 mL/(g-cat·h)) than previously reported Ni-based catalysts.