The catalytic oxidation of ammonia: influence of water and sulfur on selectivity to nitrogen over promoted copper oxide/alumina catalysts

Abstract

The CuO/Al 2O 3 system is active for ammonia oxidation to nitrogen and water. The principal by-products are nitrous oxide and nitric oxide. Nitrous oxide levels increase with the addition of various metal oxides to the basic copper oxide/alumina system. Addition of sulfur dioxide to the reaction stream sharply reduces the level of ammonia conversion, but has a beneficial effect on selectivity to nitrogen. Added water vapour has a lesser effect on activity but is equally beneficial in terms of selectivity to nitrogen. The CuO/Al 2O 3 is also active for the selective catalytic reduction of nitric oxide by ammonia, but this reaction is not effected by sulfur dioxide addition. A mechanism for ammonia oxidation to nitrogen is proposed wherein part of the ammonia fed to the catalyst is converted into nitric oxide. A pool of monoatomic surface nitrogen species of varying oxidation states is established. N 2 or N 2O are formed depending upon the average oxidation state of this pool. An abundance of labile lattice oxygen species on the catalyst surface leads to overoxidation and to N 2O formation. On the other hand, reduced lability of surface lattice oxygen species favours a lower average oxidation state for the monoatomic surface nitrogen pool and leads to N 2 formation.