Operando sulfur speciation during sulfur poisoning-regeneration of Ru/SiO2 and Ru/Al2O3 using non-resonant sulfur Kα1,2 emission

Abstract

A periodic oxidative regeneration of a sulfur-poisoned methanation catalyst is an alternative to the expensive state-of-the-art process of syngas cleaning using wet scrubbers. Here we have employed operando X-ray emission spectroscopy (XES) to study sulfur speciation on Ru/SiO₂ and Ru/Al₂O₃ during methanation in the presence of H₂S and subsequent regeneration in dilute O₂ at 360 °C. XES allowed us to obtain semi-quantitative sulfur speciation and to monitor changes in the absolute sulfur concentration. It was established that Al₂O₃, in contrast to SiO₂, forms sulfite/sulfate species by reacting with SO₂, which is released from the poisoned Ru surface upon oxidative treatment. The concentration of sulfite/sulfate species is reduced upon switching the feed to H₂/CO while no simultaneous increase in sulfide concentration is observed. For both catalysts, the regenerative treatment removes adsorbed sulfur as SO₂ only partially, which we propose is the main reason for the incomplete activity recovery of the poisoned catalyst after regeneration.