The oxidative dehydrogenation of ethylbenzene (EB) into styrene (ST) has been proposed as an alternative to the conventional energy-consuming synthesis of styrene. Various types of catalysts have been reported as promising for the reaction under industrially-relevant conditions. However, they show a complex deactivation behaviour. The EB conversion and the ST selectivity decay, with an increased CO_x selectivity. This phenomenon was investigated by means of experimental data and reaction model analysis, using two reference inorganic catalysts. The active catalyst is the deposited coke (ODH-coke) and not directly the inorganic material. The coke is formed in the initial reaction phase and promoted by the Lewis acid sites of the inorganic material. The reaction shows an activation period in which the ODH-coke is deposited and the EB conversion reaches a maximum where O₂ is fully converted. From that point onwards, the reaction model is applicable and the experimental data fit very well with low standard deviations. The model explains that the EB conversion′s decay with time on stream is associated to changes in the selectivity. Hence, EB conversion is not an independent parameter. This simplifies the understanding of this complex deactivation; the deactivating parameter is the selectivity. At this moment, we cannot discriminate between increased CO_x and decreased ST, or both effects, because both routes are competitive. This case represents a new type of catalyst deactivation behaviour, in which selectivity affects conversion.

Deposition of carbonaceous species on a solid catalyst́s surface during a catalysed processes is quite usual. This causes fouling, or depletion of the textural features, with a performance decay. In this work, preliminary results for an ex situ thermal oxidative reactivation of a fouled MWCNT are presented. The coke is nearly completely removed and, as a side effect, some of the MWCNT is combusted. Remarkably, the textural features are improved; 23 % higher BET area and 29 % higher total pore volume, while maintaining the isotherm shape. These improvements are attributed to two factors. Firstly, the removal during reactivation of non-porous (or less-porous) carbon domains present in the starting MWCNT, that positively influences the porosity in various ways; a control experiment employing the fresh MWCNT strongly suggests this hypothesis. Secondly, the new microporosity also contributes to the better BET.

This work reports initial results on the effect of low concentrations (ppm level) of a stabilizing agent (2,6-di-tert-butyl-4-methylphenol, BHT) present in an off-the-shelf solvent on the catalyst performance for the hydrogenolysis of γ-butyrolactone over Cu-ZnO-based catalysts. Tetrahydrofuran (THF) was employed as an alternative solvent in the hydrogenolysis of γ-butyrolactone. It was found that the Cu-ZnO catalyst performance using a reference solvent (1,4-dioxane) was good, meaning that the equilibrium conversion was achieved in 240 min, while a zero conversion was found when employing tetrahydrofuran. The deactivation was studied in more detail, arriving at the preliminary conclusion that one phenomenon seems to play a role: the poisoning effect of a solvent additive present at the ppm level (BHT) that appears to inhibit the reaction completely over a Cu-ZnO catalyst. The BHT effect was also visible over a commercial Cu-ZnO-MgO-Al2O3 catalyst but less severe than that over the Cu-ZnO catalyst. Hence, the commercial catalyst is more tolerant to the solvent additive, probably due to the higher surface area. The study illustrates the importance of solvent choice and purification for applications such as three-phase-catalyzed reactions to achieve optimal performance.

Deactivation of a Pd/alumina catalyst has been observed during the hydrogenation of α-methylstyrene and styrene. In both feedstocks, deactivation is caused by an additive, 4-tert-butylcatechol (TBC), a polymerization inhibitor, commonly employed at the ppm concentration level in the formulation of commercial monomers. It was found that the reaction rate in the α-methylstyrene fluctuated notably among the reactant vendors, and this was ascribed to the varying concentration of TBC, although other factors, such as the concentration of water, may play a role. The study was extended into the hydrogenation of styrene using a trickle bed reactor. The negative impact of the TBC present at the ppm level was obvious. The deactivation mechanism was complex to rationalize. A two-stage behavior was observed: a first stage of a relatively fast deactivation followed by a second stage of slow deactivation. A tentative explanation considers the presence of two types of Pd-sites, which are poisoned by TBC: the more active α-Pd-H sites and the less active β-Pd-H sites. Finally, in practical terms, it is important to emphasize that such an additive must be removed from the reactant to maximize the catalyst performance. This can be achieved by adsorption using a commercial F-200 Alcoa alumina.

Abstract: Mn and Li promoted Rh catalysts supported on SiO₂ with a thin TiO₂ layer were synthesized by stepwise incipient wetness impregnation approach. The thin TiO₂ layer on the surface of SiO₂ was proved to stabilize those small Rh nanoparticles and hinder their agglomeration. The reducibility of Rh on these catalysts depends on Rh particle size as well as the position of manganese oxide, and large Rh nanoparticles with MnO on Rh nanoparticles can be only reduced at an elevated temperature. Catalyst with large Rh particles exhibits a higher CO conversion and higher products selectivity towards long chain hydrocarbons and C2-oxygenates at the expense of decreasing methane formation than a similar catalyst with smaller Rh particles. This was attributed to the synergistic effect of Mn and Li promotion and molar ratio between Rh⁰ and Rh^δ+ sites on the surface of Rh nanoparticles. Moreover, Rh nanoparticles on MnO are proved to be more efficient in promoting hydrogenation of acetaldehyde to ethanol than its counterpart with MnO on Rh nanoparticles. Finally, in order to target high C2-oxygenates selectivity, low reaction temperature together with a low H₂/CO ratio in the feed is recommended. Graphic Abstract: [Figure not available: see fulltext.].