Abstract: Deactivation of commercially relevant cobalt catalysts for Low Temperature Fischer-Tropsch (LTFT) synthesis is discussed with a focus on the two main long-term deactivation mechanisms proposed: Carbon deposits covering the catalytic surface and re-oxidation of the cobalt metal. There is a great variety in commercial, demonstration or pilot LTFT operations in terms of reactor systems employed, catalyst formulations and process conditions. Lack of sufficient data makes it difficult to correlate the deactivation mechanism with the actual process and catalyst design. It is well known that long term catalyst deactivation is sensitive to the conditions the actual catalyst experiences in the reactor. Therefore, great care should be taken during start-up, shutdown and upsets to monitor and control process variables such as reactant concentrations, pressure and temperature which greatly affect deactivation mechanism and rate. Nevertheless, evidence so far shows that carbon deposition is the main long-term deactivation mechanism for most LTFT operations. It is intriguing that some reports indicate a low deactivation rate for multi-channel micro-reactors. In situ rejuvenation and regeneration of Co catalysts are economically necessary for extending their life to several years. The review covers information from open sources, but with a particular focus on patent literature.
Abstract: When using heteropolycompounds in the selective oxidation of isobutane to methacrolein and methacrylic acid, both the keeping of the primary structure (Keggin units) and the presence of acidic sites are necessary to obtain the desired products. The structural evolution of supported (NH4)3HPMo11VO40 (APMV) catalysts under preliminary thermal oxidizing and reducing treatments was investigated. Various techniques, such as TGA/DTG (Thermo-Gravimetric Analysis/Derivative Thermo-Gravimetry), H2-TPR (Temperature Programed Reduction), in situ XRD (X-Ray Diffraction) and XPS (X-ray Photoelectron Spectroscopy), were applied. It was clearly evidenced that the thermal stability and the reducibility of the Keggin units are improved by supporting 40% APMV active phase on Cs3PMo12O40 (CPM). The partial degradation of APMV takes place depending on temperature and reaction conditions. The decomposition of ammonium cations (releasing NH3) leads to the formation of vacancies favoring cationic exchanges between vanadium coming from the active phase and cesium coming from the support. In addition, the vanadium expelled from the Keggin structure is further reduced to V4+, species, which contributes (with Mo5+) to activate isobutane. The increase in reducibility of the supported catalyst is assumed to improve the catalytic performance in comparison with those of unsupported APMV.
Abstract: Cobalt nanostructures with different size and morphology, i.e., spherical nanoparticles, nanorods, and particles arranged into elongated structures, were prepared using micelles and microemulsions as confined reaction media. The syntheses were carried out using three types of systems: aqueous surfactant solutions, oil-in water (O/W), and water-in-oil (W/O) microemulsions. The influence of the surfactant and the precipitating agent used for synthesis was also investigated. For this purpose, cobalt nanostructures were prepared using different non-ionic surfactants, namely Synperonic® 10/6, Pluronic® P123 and a mixture of SPAN 20–TWEEN 80. Three different precipitating agents were used: sodium borohydride, sodium hydroxide, and oxalic acid. Our findings revealed that by changing the type of reaction media as well as the precipitating agent it is possible to modify the shape and size of the cobalt nanostructures. Moreover, the use of O/W microemulsion generates better results in terms of colloidal stability and uniformity of particle size with respect to W/O microemulsion. The different cobalt nanostructures were supported on commercial and mesoporous silica; transmission electron microscopy (TEM) images showed that after deposition the Co nanocrystals remain well dispersed on the silica supports. This behavior suggests their great potential in catalytic applications.
Abstract: Molybdenum carbide was supported on three types of carbon support—activated carbon; multi-walled carbon nanotubes; and carbon nanofibers—using ammonium molybdate and molybdic acid as Mo precursors. The use of activated carbon as support afforded an X-ray amorphous Mo phase, whereas crystalline molybdenum carbide phases were obtained on carbon nanofibers and, in some cases, on carbon nanotubes. When the resulting catalysts were tested in the hydrodeoxygenation (HDO) of guaiacol in dodecane, catechol and phenol were obtained as the main products, although in some instances significant amounts of cyclohexane were produced. The observation of catechol in all reaction mixtures suggests that guaiacol was converted into phenol via sequential demethylation and HDO, although the simultaneous occurrence of a direct demethoxylation pathway cannot be discounted. Catalysts based on carbon nanofibers generally afforded the highest yields of phenol; notably, the only crystalline phase detected in these samples was Mo2C or Mo2C-ζ, suggesting that crystalline Mo2C is particularly selective to phenol. At 350 °C, carbon nanofiber supported Mo2C afforded near quantitative guaiacol conversion, the selectivity to phenol approaching 50%. When guaiacol HDO was performed in the presence of acetic acid and furfural, guaiacol conversion decreased, although the selectivity to both catechol and phenol was increased.
Abstract: We investigated the structural evolution of molybdenum carbides subjected to hot aqueous environments and their catalytic performance in low-temperature hydroprocessing of acetic acid. While bulk structures of Mo carbides were maintained after aging in hot liquid water, a portion of carbidic Mo sites were converted to oxidic sites. Water aging also induced changes to the non-carbidic carbon deposited during carbide synthesis and increased surface roughness, which in turn affected carbide pore volume and surface area. The extent of these structural changes was sensitive to the initial carbide structure and was lower under actual hydroprocessing conditions indicating the possibility of further improving the hydrothermal stability of Mo carbides by optimizing catalyst structure and operating conditions. Mo carbides were active in acetic acid conversion in the presence of liquid water, their activity being comparable to that of Ru/C. The results suggest that effective and inexpensive bio-oil hydroprocessing catalysts could be designed based on Mo carbides, although a more detailed understanding of the structure-performance relationships is needed, especially in upgrading of more complex reaction mixtures or real bio-oils.
Abstract: Platinum catalysts supported on carbon xerogel and carbon black (Vulcan) were synthesized with the aim of investigating the influence of the characteristics of the support on the electrochemical performance of the catalysts. Three synthesis methods were compared: an impregnation method with two different reducing agents, sodium borohydride and formic acid, and a microemulsion method, in order to study the effect of the synthesis method on the physico-chemical properties of the catalysts. X-ray diffraction and transmission electron microscopy were applied. Cyclic voltammetry and chronoamperometry were used for studying carbon monoxide and methanol oxidation. Catalysts supported on carbon xerogel presented higher catalytic activities towards CO and CH3OH oxidation than catalysts supported on Vulcan. The higher mesoporosity of carbon xerogel was responsible for the favored diffusion of reagents towards catalytic centers.