Influence of H2 availability in the catalytic reduction of nitrates in fixed bed reactors

Abstract The effect of H2 availability in the catalytic reduction of NO3− was studied through experimental tests and theoretical estimations of mass transfer regime for H2, CO2 and NO3−. The experiments were carried out in a fixed bed reactor packed with bimetallic 0.75% (w) Pd-Cu catalysts supported on granular activated carbon at 25 °C. External mass transfer limitations were only significant in the case of H2 and resulted in lower selectivity to NH4+, particularly in the low gas surface velocity range (0.09–0.019 cm/s). Low availability of H2, becoming the limiting reagent for the reaction, contributed to lower selectivity to NH4+ due to lower H:N ratio at the catalyst surface. Decreasing space–time also led to lower selectivity to NH4+, probably due to the neutralization of OH− by the available H+ at catalytic sites, thus controlling local pH and favoring N2 production. Reduction of selectivity to NH4+ was achieved with lower loss of activity and NO3− conversion when gas flow was decreased than when liquid flow was decreased. The results indicate that the design and operation of reactors for the catalytic reduction of NO3− should consider conditions leading to H2 transfer control in order to reduce selectivity to NH4+, even though this could be at the expense of reaction rate and NO3− conversion.