The Genesis and Development of the Commercial BP Doubly Promoted Catalyst for Ammonia Synthesis

In the 1970s BP started developing a new catalyst for ammonia synthesis which in final form comprises ruthenium, two promoters and a graphitised carbon support. This became the first new catalyst for ammonia synthesis to be commercialised since Fritz Haber's promoted iron catalyst. The catalyst is commercialised in the KBR Advanced Ammonia Process (KAAP). We describe the development of the catalyst, starting in the 1960s with studies to elucidate the mechanism of selective hydrogenation catalysts using nickel single crystals and LEED. These identified a phenomenon dubbed surface reorientation, in which an adsorbate such as sulphur causes the structure of the surface monolayer of a metal to change e. g. from fcc [111] to [100]. These ideas led to discovery of an active platinum/alkali metal/carbon catalyst for the dehydrocyclisation of hexane. That catalyst was not commercial, but it led in turn to the identification of highly active ruthenium/alkali metal/carbon catalysts for ammonia synthesis. The best new catalyst is about 20 times more active than a commercial Haber catalyst. The special carbon support is mesoporous and graphitic. Scale up of catalyst production and testing are described briefly, as are some process considerations.