State of the components of (K)(Ni)W/γ-Al2O3 catalysts as oxide precursors and after water-gas shift reaction in the presence of sulphur

• The components do not strongly change the primary mesoporous texture of γ-Al2O3.
• The nature and bond strength of the oxide precursors generate different S species.
• Both tungsten reducibility and sulphur stability to oxidation determine the activity.
• The KNiW system exhibits both features to moderate extent and the highest activity.

A W/γ-Al2O3 system doped with K and/or Ni has been synthesized by consecutive incipient wetness impregnation. The state of the components was characterized by XRD, UV–vis–NIR, XPS, and EPR spectroscopy as well as by means of N2 physisorption. A variety of surface species was available after calcination, such as monotungstate (WO4) and polymeric monolayers (WO6)n with incorporated Ni2+ or K+ ions or more complex NiWO(Al) and KNiWO(Al). Presulphided samples were investigated in the water-gas shift (WGS) reaction in presence of sulphur in the feed. In case of H2S-free feed, catalyst deactivation readily occurred. W4+, W5+, and W6+ oxidation states as well as different sulphur-containing species like paramagnetic sulphur, sulphide sulphur, oxysulphides and sulphate sulphur were registered on the surface after catalytic activity tests with sulphur present in the feed. Both tungsten reducibility and sulphur stability to oxidation represent informative indices related to the catalytic properties of γ-Al2O3-supported tungsten system, doped with Ni and K, in the WGS reaction. The tricomponent KNiW system exhibited these features to a moderate extent thus leading to its highest catalytic performance that allowed attaining equilibrium values at high temperatures.

Catalytic performance of pre-sulphided (K,Ni)W/γ-Al2O3 systems with S-presence in the feed; steam/gas = 0.3; GHSV 4000 h−1.Figure optionsDownload high-quality image (81 K)Download as PowerPoint slide