Evaluation of Catalyst Deactivation during Catalytic Steam Reforming of Biomass-Derived Syngas

Mitigation of tars produced during biomass gasification continues to be a technical barrier to developing systems. This effort combined the measurement of tar-reforming catalyst deactivation kinetics and the production of syngas in a pilot-scale biomass gasification system at a single steady-state condition with mixed woods, producing a gas with an H ₂-to-CO ratio of 2 and 13% methane. A slipstream from this process was introduced into a bench-scale 5.25 cm diameter fluidized-bed catalyst reactor charged with an alkali-promoted Ni-based/Al ₂O ₃ catalyst. Catalyst conversion tests were performed at a constant space time and five temperatures from 775 to 875°C. The initial catalyst-reforming activity for all measured components (benzene, toluene, naphthalene, and total tars) except light hydrocarbons was 100%. The residual steady-state conversion of tar ranged from 96.6% at 875°C to 70.5% at 775°C. Residual steady-state conversions at 875°C for benzene and methane were 81% and 32%, respectively. Catalytic deactivation models with residual activity were developed and evaluated based on experimentally measured changes in conversion efficiencies as a function of time on stream for the catalytic reforming of tars, benzene, methane, and ethane. Both first-and second-order models were evaluated for the reforming reaction and for catalyst deactivation. Comparison of experimental and modeling results showed that the reforming reactions were adequately modeled by either first-order or second-order global kinetic expressions. However, second-order kinetics resulted in negative activation energies for deactivation. Activation energies were determined for first-order reforming reactions and catalyst deactivation. For reforming, the representative activation energies were 32 kJ/g·mol for ethane, 19 kJ/g·mol for tars, 45 kJ/g·mol for tars plus benzene, and 8-9 kJ/g·mol for benzene and toluene. For catalyst deactivation, representative activation energies were 146 kJ/g·mol for ethane, 121 kJ/g·mol for tars plus benzene, 74 kJ/g·mol for benzene, and 19 kJ/g·mol for total tars. Methane was also modeled by a second-order reaction, with an activation energy of 18.6 kJ/g·mol and a catalyst deactivation energy of 5.8 kJ/g·mol.