The effects of La, Mg and Ca promoters on carbonaceous surface and bulk iron carbide species formed in the alkali promoted iron catalysts are studied under realistic Fischer–Tropsch synthesis (FTS) conditions. Compositions of bulk iron phase and phase transformations of carbonaceous species during pretreatment and FTS reaction were characterized using the temperature-programmed surface reaction with hydrogen (TPSR-H2) and XRD techniques. Many carbonaceous species on surface and bulk were qualitatively and quantitatively identified by combined TPSR-H2 and XRD spectra of the alkali promoted iron catalyst. These species, sorted by the their reactivity with H2 from high to low, were recognized as (a) adsorbed, atomic carbon; (b) amorphous, lightly polymerized hydrocarbon or carbon surface species; (c) bulk carbides and (d) disordered and moderately ordered graphitic surface carbons. The results revealed that while the surface basicity of the iron catalyst increased the CO dissociation proceeds faster than carbon hydrogenation. This phenomenon leads to excessive carbon deposition and formation of inactive iron carbide phases and graphitic type carbonaceous surface species, and consequently leads to catalyst deactivation.

Keywords