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In petroleum refining, middle distillates are produced via hydroisomerization/hydrocracking processes using bifunctional catalysts often containing ultrastable Y (USY) zeolite. Petroleum fractions serving as feedstock for hydrocracking processes contain a majority of (poly)cyclic hydrocarbon molecules. Few studies on reaction mechanisms of hydrocracking of such polycyclic compounds are available. In this study the tricyclic phenanthrene molecule was used as model compound. Phenanthrene was hydrogenated on a Pt/alumina pre‐catalyst to perhydrophenanthrene, and subsequently hydrocracked over Pt/H‐USY zeolite. The feed consisted of 3 wt.% phenanthrene dissolved in n‐heptane. The reaction was performed at 280 °C and 60 bar, with a molar H2 to total hydrocarbon ratio of 7 mol/mol. The reaction products were analyzed using GCxGC‐FID/MS. This detailed analysis enabled identification of the reaction scheme involving skeletal isomerization, ring opening and fragmentation. New mechanistic insight is gained on relative reactivities of bridged and non‐bridged tricyclic naphthenes. Preferential hydrocracking routes were identified. The study provides insight in the products to be expected from polycyclic hydrocarbon isomerization and hydrocracking. [ABSTRACT FROM AUTHOR]

Keywords: phenanthrene; hydroisomerization; hydrocracking; adamantanes; polycyclic naphthenes; bifunctional catalysis; ultrastable Y zeolite EN phenanthrene hydroisomerization hydrocracking adamantanes polycyclic naphthenes bifunctional catalysis ultrastable Y zeolite 3332 3332 1 07/08/20 20200706 NES 200706 B The Front Cover b shows some of the reaction intermediates involved in the conversion of a tricyclic naphtene, perhydrophenanthrene, over a bifunctional Pt/faujasite (USY) catalyst. In their Full Paper, L. Brito et al. analyze the reaction pathways, which first lead to isomerization products, then to ring-opening and finally to cracking products. Phenanthrene, hydroisomerization, hydrocracking, adamantanes, polycyclic naphthenes, bifunctional catalysis, ultrastable Y zeolite. [Extracted from the article]

Hydroisomerization and hydrocracking of octylcyclohexane (C14H28) were performed over Pt and NiMoS‐supported catalysts, at 300 °C and 60 bar, with a molar H2 to hydrocarbon ratio of 7 mol/mol. The feed, composed of 5 wt.% phenyloctane dissolved in n‐heptane, was initially hydrogenated in situ over a pre‐catalyst, Pt or NiMoS/Al2O3. The C14 naphthene underwent isomerization and cracking under high hydrogen pressure over the bifunctional catalysts, whose acid function was represented by large‐pore zeolities (USY, Beta) or amorphous silica‐alumina (SA). For the Pt‐catalysts, Beta was slightly more active than USY. Both zeolites produced a similar product pattern. Sulfide catalysts were less well equilibrated than Pt ones and hence less active. They led to some over‐cracking, but the cracking selectivity of our naphthene reactant was much less sensitive to the metal‐acid balance than the cracking selectivity of n‐alkanes. The comparison of reactivity of octylcyclohexane with n‐hexadecane and perhydrophenanthrene is also discussed. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

New developments and breakthroughs in the design of hydrotreating (HDT) catalysts for complying with fuel specifications and reduced sulfur contents ask for a continuous improvement in the molecular scale description of the active phase both at the oxide and sulfide states. HDT catalysts are mainly based on alumina-supported molybdenum nanophases and the present contribution is dedicated to review the surface science approaches that have helped gain a molecular-scale insight into the structure of the active-phase (mainly molybdenum) and the role of metal-support (mainly alumina) interactions through the use of well-defined surfaces and surface sensitive analysis techniques. The main focus of this Review is placed on model systems that can bridge the gap with industrial catalysts, that is, oxide-supported active phases prepared in aqueous conditions, as opposed to more traditional surface-science studies that consider metal-supported nanophases prepared in UHV conditions. The synthesis and structure of well-defined alumina surfaces (thin films and single crystal wafers) is first presented before discussing aqueous-deposition of Mo precursors on flat surfaces. The detailed role of the oxide support is then addressed with an emphasis on the genesis and structure of the MoS2 phase namely sulfidation rate, stacking, and orientation. [ABSTRACT FROM AUTHOR]