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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]

Abstract: The hydrothermal stability of WIE-based Fe-ZSM-5 and Fe-BEA for N2O decomposition in the presence of NO, H2O and O2 was studied at 723K. Catalysts were characterized with UV–vis, IR and Al-XANES. The N2O conversion remains at a constant level with Fe–H-BEA even in the presence of large amounts of H2O. Deactivation was, however, observed with Fe–H-ZSM-5 already in the presence of 0.5vol.% water. The analysis of deactivated samples indicated that steam-dealumination and clustering of iron occurred during the reaction with Fe-ZSM-5. Replacement of protons for sodium in Fe-ZSM-5 slowed down the rate of catalyst deactivation significantly. Steam-dealumination is likely to precede the clustering of iron in Fe–H-ZSM-5. The excellent hydrothermal stability of WIE-based Fe–H-BEA relates to the high initial degree of dealumination in the as-received BEA. [Copyright &y& Elsevier]

Abstract: Fe-FER is an active catalyst for the abatement of N2O in the tail gas of nitric acid plants. The activity of Fe-FER can be increased if Ru is added as a second active component. This is a surprising finding, because noble metals are usually strongly inhibited by NO, which is always present in tail gas. Yet the bimetallic FeRu-FER catalyst is more active than the sum of the components, Fe-FER and Ru-FER. A synergy between Fe and Ru can explain this phenomenon. This work discusses the role of Fe and Ru in the reaction mechanism as well as the interplay of these two components. In situ IR measurements show that the preferential adsorption of NO and its reaction products on Fe in the bimetallic catalyst reduces the inhibiting effect of NO on the Ru component; this effect largely contributes to the synergy between Fe and Ru. Moreover, in situ X-ray absorption data are presented, which allow for tracing the average oxidation state of the two active components Fe and Ru under reaction conditions. [Copyright &y& Elsevier]

Abstract: NO-assisted N2O decomposition over four different Fe-ZSM-5 samples prepared by wet ion exchange (WIE) or chemical vapor deposition (CVD) of FeCl3 was investigated by steady-state kinetics, in situ infrared (IR) spectroscopy, and transient response methods. Despite their lower iron loading, the samples prepared by WIE had the highest activity for N2O decomposition in the presence of NO. The in situ IR experiments showed that the most active sample was characterized by a high concentration of adsorbed NO, as well as adsorbed NO2 under reaction conditions. Step response experiments proved that NO2 is an intermediate of the catalytic cycle and functions as intermediate oxygen storage. IR and transient kinetic experiments showed that WIE catalysts behave qualitatively different in NO-assisted N2O decomposition than CVD catalysts. These differences are discussed in terms of the different structure of the iron species in the two types of samples. [Copyright &y& Elsevier]

The reaction of Fe-zeolites prepared by sublimation of FeCl3 with N2O was studied by step- and pulse-response experiments. Steps from 0 to 5000 ppm N2O were performed at 673 K, after pretreatment of the catalyst in H2, He, or O2. When the catalysts were prereduced in H2, N2O was first consumed for the reoxidation of the catalyst, before steady-state N2O decomposition started. Also pretreatment in He reduced the catalyst. This autoreduction was not spontaneous, but caused by a small amount of hydrocarbons adsorbed on the catalyst. Prereduced catalysts had a higher steady-state activity, indicating that the incorporation of oxygen from N2O changed the structure of the active sites. Pulse responses proved that O2 desorption is the rate-limiting step of N2O decomposition. O2 desorption was relatively fast from a small fraction of sites, while a second oxygen pool desorbed only slowly from the catalyst. Only the former is responsible for catalytic activity. [Copyright &y& Elsevier]

The nitration of toluene and 2-nitrotoluene with acetyl nitrate was investigated using several solid acid catalysts. In the nitration of toluene, enhanced para-selectivity was observed only with zeolite BEA. For the nitration of 2-nitrotoluene, all the catalysts displayed good para-selectivity, but only BEA led to high yields. The superior performance of BEA was due to the fact that only with this zeolite did the heterogeneously catalyzed reaction compete successfully with the homogeneous nitration in the liquid phase. Geometrical considerations showed that the high para-selectivity of BEA was not caused by classical transition-state selectivity but was induced by the reaction of the arene with a surface-bound acetyl nitrate complex. The existence of this complex was supported by NMR measurements, which showed that its formation is a specific property of zeolite BEA. [Copyright &y& Elsevier]

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]

• An accelerated deactivation protocol at the pilot plant scale was developed to study hydrocracking catalyst deactivation in a short time of 30 days. • The organic nitrogen content of the feedstock to the hydrocracking process deactivates the catalyst acid function permanently by coke deposition. In contrast, nitrogen compounds have just an inhibitory effect on the metal function. The deactivation of the metal function is mainly due to nickel depromotion. • The balance in the ratio of the metal/acid sites determines the amount and the type of formed coke. The lower the ratio, the higher the coke production rate with a more aromatic structure. • Along the catalytic bed, the metal/acid balance decreases from bed inlet to bed outlet, the bed outlet contains a higher amount of coke, which is more aromatic. A representative accelerated experimental deactivation procedure was developed to understand the activity loss of bifunctional vacuum gasoil (VGO) hydrocracking catalysts over time. Experiments were performed in an up-flow fixed-bed pilot unit with a typical vacuum gas oil feedstock. The deactivation was measured by tracking the decrease of VGO conversion (370 °C+) with time on stream. The catalyst consisted of nickel-molybdenum sulfide particles dispersed on a carrier containing USY zeolite. The impact of temperature, liquid hourly space velocity (LHSV), hydrogen to hydrocarbon (H 2 /HC) ratio and organic nitrogen (N org) on the catalyst deactivation rate was first studied. The variables with the most significant impact on conversion loss were temperature and space velocity. Temperature directly influences the production rate of coke precursors, whereas space velocity affects the local concentration of feed contaminants along the reactor. Based on these results, the following operating conditions were selected to establish the final accelerated deactivation experimental protocol: T = 418 °C, LHSV = 3 h−1, H 2 /HC = 1500NL/L, P = 14 MPa, organic nitrogen content (Norg) = 150 ppm weight, total nitrogen content = 2500 ppm weight and a total time on stream of 30 days. Spent samples from this procedure presented similar properties to some industrial catalysts submitted to cycle lengths between 12 and 18 months. Both types of samples yield similar values of surface area and pore volume loss as well as a similar amount and nature of coke deposits. These results led to the qualitative validation of the protocol representativeness. This experimental procedure was then used to get more insight into the deactivation phenomenon. It was found that the organic nitrogen content of the feedstock is crucial, as it determines the ratio between available metal and acid sites. This ratio determines the reactions that take place and, therefore, the type of coke produced. [ABSTRACT FROM AUTHOR]

The role of the oxide support on the structure of the MoS2 active phase (size, morphology, orientation, sulfidation ratio, etc.) remains an open question in hydrotreating catalysis and biomass processing with important industrial implications for the design of improved catalytic formulations. The present work builds on an aqueous-phase surface-science approach using four well-defined a-alumina single crystal surfaces (C (0001), A (1120), M (lOlO), and R (1102) planes) as surrogates for y-alumina (the industrial support) in order to discriminate the specific role of individual support facets. The reactivity of the various surface orientations toward molybdenum adsorption is controlled by the speciation of surface hydroxyls that determines the surface charge at the oxide/water interface. The C (0001) plane is inert, and the R (1102 ) plane has a limited Mo adsorption capacity while the A (1120) and M (1010) surfaces are highly reactive. Sulfidation of model catalysts reveals the highest sulfidation degree for the A (1120) and M (1010) planes suggesting weak metal/support interactions. Conversely, a low sulfidation rate and shorter MoS2 slabs are found for the R (1102) plane implying stronger Mo-O-Al bonds. These limiting cases are reminiscent of type I/type II MoS2 nanostructures. Structural analogies between α-and γ-alumina surfaces allow us to bridge the material gap with real Al203-supported catalysts. Hence, it can be proposed that Mo distribution and sulfidation rate are heterogeneous and surfacedependent on industrial γ-Al203-supported high-surface-area catalysts. These results demonstrate that a proper control of the γ-alumina morphology is a strategic lever for a molecular-scale design of hydrotreating catalysts. [ABSTRACT FROM AUTHOR]

Review: 158 refs. [ABSTRACT FROM AUTHOR]