Hydrogen Production by Steam Reforming of Ethanol and Dry Reforming of Methane with CO2 on Ni/Vermiculite: Stability Improvement via Acid or Base Treatment of the Support

Abstract

In this study, vermiculite was explored as a support material for nickel catalysts in two key processes in syngas production: dry reforming of methane with CO₂ and steam reforming of ethanol. The vermiculite underwent acid or base treatment, followed by the preparation of Ni catalysts through incipient wetness impregnation. Characterization was conducted using various techniques, including X-ray diffraction (XRD), SEM-EDS, FTIR, and temperature-programmed reduction (H₂-TPR). TG-TD analyses were performed to assess the formation of carbon deposits on spent catalysts. The Ni-based catalysts were used in reaction tests without a reduction pre-treatment. Initially, raw vermiculite-supported nickel showed limited catalytic activity in the dry reforming of methane. After acid (Ni/VTA) or base (Ni/VTB) treatment, vermiculite proved to be an effective support for nickel catalysts that displayed outstanding performance, achieving high methane conversion and hydrogen yield. The acidic treatment improved the reduction of nickel species and reduced carbon deposition, outperforming the Ni over alkali treated support. The prepared catalysts were also evaluated in ethanol steam reforming under various conditions including temperature, water/ethanol ratio, and space velocity, with acid-treated catalysts confirming the best performance.