Role of Phosphorus and Triethylene Glycol Incorporation on the Activity of Model Alumina‐Supported CoMoS Hydrotreating Catalysts

• Published in: ChemCatChem Vol. 14; no. 6
• Main Authors: Garcia de Castro, Ricardo, Devers, Elodie, Digne, Mathieu, Lamic‐Humblot, Anne‐Félicie, Pirngruber, Gerhard D., Carrier, Xavier
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley Subscription Services, Inc 22.03.2022; Wiley
• Subjects: Alumina; Aluminum oxide; Catalysis; Catalysts; Catalytic activity; Chemical Sciences; Chemical synthesis; CoMo catalysts; Crystal structure; Hydrodesulfurization; Hydrotreating; Phosphorus; R&D; Research & development; Single crystals; Sulfidation; Surface-science; Triethylene glycol; Volcano plot; X ray photoelectron spectroscopy; Hydrotreating; Surface-science; Volcano plot; Alumina; CoMo catalysts
• ISSN: 1867-3880; 1867-3899; 1867-3899
• DOI: 10.1002/cctc.202101493

Environmental regulations concerning fuel‐related sulfur emissions are currently experiencing worldwide expansion. This is motivating the research and development of improved hydrotreating (HDT) catalysts with carefully engineered synthesis methods that maximize activity as ultimate goal. In this contribution, the effect of phosphorus doping and triethylene glycol (TEG) incorporation on the genesis of the CoMoS phase of model HDT catalysts is assessed. Following a surface‐science approach, α‐Al2O3 single crystals with four orientations: C(0001), A(112‾ 0), M(101‾ 0), and R(11‾ 02) are used as model supports of the traditional γ‐Al2O3 support for the study of active phase‐support interactions at the molecular scale. The model catalysts are prepared by traditional impregnation of a solution containing metal and phosphorus precursors and TEG. The catalysts are characterized in the sulfide phase by XPS, XAS, TEM, and AFM, revealing that the calcination step is key in the emergence of distinctive metal‐support interactions, which are directly related to the nature of alumina surface sorption sites. In addition, TEG incorporation on dried catalysts increases metal sulfidation and enhances promotion with respect to non‐additivated systems, especially at mild sulfidation temperatures. The catalytic activity of the model catalysts is tested in a thiophene hydrodesulfurization reaction, revealing the following activity trend with respect to alumina surface orientations: A112‾0 ≫ M101‾0 >R11‾02 , C(0001). This trend is identical to the one observed for non‐phosphorus doped non‐TEG additivated model systems, confirming the predominance of surface effects on the catalytic activity over those exerted by P and TEG. By transposing these results to the industrial γ‐Al2O3 support, the (100) facet would provide surface sites that lead to better performing catalysts. This could result in the development of novel supports, engineered to expose surface sites that maximize hydrotreating activity. The effect of phosphorus doping and triethylene glycol (TEG) incorporation on the genesis of the CoMoS phase of model HDT catalysts is assessed. The catalytic activity in thiophene hydrodesulfurization of the model catalysts prepared on α‐Al2O3 single crystals with four orientations reveals a volcano‐shaped curve with metal‐support interactions as a key descriptor of the catalytic activity.