Catalytic and adsorption studies for the hydrogenation of CO2 to methane

Abstract

CO2 methanation has been evaluated as a means of storing intermittent renewable energy in the form of synthetic natural gas. A range of process parameters suitable for the target application (4720h-1 to 84,000h-1 and from 160°C to 320°C) have been investigated at 1bar and H2/CO2=4 over a 10% Ru/γ-Al2O3 catalyst. Thermodynamic equilibrium was reached at T≈280°C at a GHSV of 4720h-1. Cyclic and thermal stability tests specific to a renewable energy storage application have also been conducted. The catalyst showed no sign of deactivation after 8 start-up/shut-down cycles (from 217°C to RT) and for total time on stream of 72h, respectively. In addition, TGA-DSC was employed to investigate adsorption of reactants and suggest implications on the mechanism of reaction. Cyclic TGA-DSC studies at 265°C in CO2 and H2, being introduced consecutively, suggest a high degree of short term stability of the Ru catalyst, although it was found that CO2 chemisorption and hydrogenation activity was lowered by a magnitude of 40% after the first cycle. Stable performance was achieved for the following 19 cycles. The CO2 uptake after the first cycle was mostly restored when using a H2-pre-treatment at 320°C between each cycle, which indicated that the previous drop in performance was not linked to an irreversible form of deactivation (sintering, permanent poisoning, etc.). CO chemisorption on powder Ru/γ-Al2O3 was used to identify metal sintering as a mechanism of deactivation at temperatures higher than 320°C. A 10% Ru/γ-Al2O3//monolith has been investigated as a model for the design of a catalytic heat exchanger. Excellent selectivity to methane and CO2 conversions under low space-velocity conditions were achieved at low hydrogenation temperatures (T=240°C). The use of monoliths demonstrates the possibility for new reactor designs using wash-coated heat exchangers to manage the exotherm and prevent deactivation due to high temperatures. © 2014 Elsevier B.V.