Active and Coking Resistant Ni/SBA-15 Catalysts for Low Temperature Dry Reforming of Methane (In Memory of Professor John Gleaves – Inventor of TAP Reactor)

In recent years CO2 reforming of methane has attracted great interest as it produces high CO/H2 ratio syngas suitable for the synthesis of higher hydrocarbons and oxygenated derivatives, since it is a way for disposing and recycling two greenhouse gases with high environmental impact, CH4 and CO2, and because it is regarded as a potential route to store and transmit energy due to its strong endothermic effect. Along with noble metals, all the group VIII metals, except for osmium, have been studied for catalytic CO2 reforming of methane. It was found that the catalytic activity of Ni, though lower than those of Ru and Rh, was higher than the catalytic activity of Pt and Pd. Although noble metals have been proved to be insensitive to coke, the high cost and restricted availability limit their use in this process. It is therefore valuable to develop stable Ni-based catalysts. In this contribution, we show how their activity and coking resistivity is greatly related to the size and dispersion of Ni particles. Well-dispersed Ni nanoparticles were achieved by multistep impregnation on a mesoporous silica support, namely SBA-15, obtained through a sol-gel method, using acetate as nickel precursor and keeping the Ni loading between 5 wt% and 11 wt%. Significant catalytic activity was obtained at temperatures as low as 450 °C, temperature well below their deactivation temperature, i.e., 700 °C. For the pre-reduced samples complete CO2 conversion was obtained around 680 ºC. As such, their deactivation by sintering and coke formation was prevented. To the best of our knowledge, no Ni-based catalysts with complete CO2 conversion at temperatures lower than 800 ºC were reported so far.