n-Pentane Isomerization Over Pt- and Ni–Pt-Promoted Sulfated Zirconia Catalysts Supported on Alumina

Two series of sulfated zirconia catalysts promoted with Pt and Pt–Ni, respectively, were prepared and extruded with different amount of alumina binder (0, 20, 33, and 60 wt%). The catalytic activities of the two series of catalysts, SZPtA and SZNiPtA, were measured for n-pentane isomerization reaction. The reaction reaches its maximum conversion at 20 wt% of alumina for both catalyst series. Adding alumina beyond 20 wt% reduces the overall conversion and modifies the selectivity for both catalysts series from i-C4 towards i-C5 suggesting that the reaction mechanism changed from a monomolecular to a bimolecular one. However, only SZNiPtA catalysts maintain a higher catalytic activity at higher amounts of alumina. Such difference between the two catalyst series can be attributed to the combining effect of Ni and Pt promotion of the SZNiPtA catalysts and not to their acidic properties.     

Alumina and Alumina–Baria Supported Cobalt Catalysts for DeNO x : Influence of the Support and Cobalt Content on the Catalytic Performance

Co/Al₂O₃ and Co/Al₂O₃–BaO catalysts with low cobalt loading (0.1, 0.3 and 1 wt%) for the selective catalytic reduction (SCR) of NO _x by C₃H₆ were prepared. The distribution of cobalt species was investigated by UV–vis diffuse reflectance spectroscopy and by H₂-TPR in order to identify the active cobalt species in hydrocarbons (HC)-selective catalytic reduction (SCR). It was found that the nature of cobalt species strongly depends on the cobalt loading as well as on the properties of the support. The barium addition to the alumina slows down solid state diffusion processes, improving the thermal stability of the support and preventing diffusion of cobalt into the bulk. Highly dispersed surface Co²⁺ species over alumina were identified as active sites in the NO-SCR process. Accordingly, a high concentration of surface Co²⁺ sites in Co 1 wt%/Al₂O₃ improves the catalytic performance in NO-SCR, the long term stability as well as the water tolerance. On the contrary, the formation of Co₃O₄ particles in Co 1 wt%/Al₂O₃–BaO promotes the propylene oxidation by oxygen, decreasing the activity and selectivity of the catalyst in NO reduction.     

Gold Catalysts Supported on Cerium–Gallium Mixed Oxide for the Carbon Monoxide Oxidation and Water Gas Shift Reaction

The synthesis, characterization and catalytic properties of gold supported on ceria, gallia and a cerium–gallium mixed oxide were investigated. The nanostructural characterization of the cerium–gallium support (nominal atomic composition Ce80Ga20) showed that gallium(III) cations are homogenously distributed into the ceria matrix by substituting cerium(IV) cations of the fluorite-type structure of ceria. Au was added to the supports by the deposition–precipitation method using urea. High Au dispersions were achieved for all the fresh materials (D > 60%). The CO oxidation and the water gas shift (WGS) reaction were tested on the whole set of catalysts. All the supported-gold catalysts showed high activity for the CO oxidation reaction. However, those containing gallium in their formulation deactivated due to gold particle sinterization. Au(2%)/CeO₂ was the most active material for the WGS reaction, and the Au(2%)/Ce80Ga20 was as active as a Au(3%)/Ce68Zr32 catalyst for CO oxidation, and even more active than the reference catalyst of the World Gold Council, Au(2%)/TiO₂.     

Preparation of Supported Gold Catalysts for Low-Temperature CO Oxidation via “Size-Controlled” Gold Colloids

Catalytically active gold model catalysts have been designed via “size-controlled” gold colloids of 2-nm mean particle size. They were prepared by reduction of chloroauric acid with tetrakis(hydroxymethyl)phosphonium chloride in an alkaline solution, followed by adsorption of gold colloids on TiO₂and ZrO₂at a pH lower than the isoelectric point of the metal oxides. Investigation of the size of the gold particles in solution by UV-vis spectrophotometry in combination with HRTEM indicated that the gold colloids are rather stable in alkaline solution, during pH-change and purification with dialysis. Ageing of the solutions showed that the particle size slowly increased over a time scale of 4 months. Analysis of the dried catalysts by XRD and HRTEM corroborated that the particle size was nearly preserved during the immobilization process. Only in the case of high loadings (16.6 wt%, compared to the calculated nominal monolayer coverage of 45–55 wt%), incomplete adsorption occurred, affording more inhomogeneous dispersion and some aggregation. After calcination at 673 K, both zirconia- and titania-based catalysts containing 1.7 wt% Au exhibited high activity in low temperature CO oxidation. Although the particle size on both supports was comparable, the Au/TiO₂catalyst showed significantly higher activity than the Au/ZrO₂catalyst. The uncalcined Au/TiO₂also exhibited high activity, whereas the uncalcined Au/ZrO₂was inactive under the same conditions, corroborating that not only the gold particle size but also the support plays a key role in CO oxidation.     

Oxidative Dimerization of Methane on Lead Oxide—Alumina Catalysts

PbO-Al₂O₃ catalysts of different composition were investigated for oxidative dimerization of methane. Characterization of the catalysts was carried out by means of X-ray diffraction, IR and temperature-programmed reduction measurements. A maximum of the methane conversion and selectivity was observed on PbO/γ-Al₂O₃ catalysts with PbO contents between 10 and 35 mol-%; PbO, PbAl₂O₄ and Al₂O₃ are catalytically less active. It is suggested that the catalytically active phase exhibits a magnetoplumbite-like structure which is formed, during thermal pretreatment, between PbO and γ-Al₂O₃ or amorphous Al₂O₃. A correlation between reducibility and catalytic activity was found.     

Hydrodechlorination of Tetrachloromethane Over Supported Platinum Catalysts. Effects of Hydrogen Partial Pressure and Catalyst’s Screening Protocol on the Catalytic Performance

Two series of silica- and alumina-supported platinum catalysts were investigated in the hydrodechlorination (HdCl) of tetrachloromethane. During an initial period of reaction carried out at a lower H₂/CCl₄ ratio the catalysts, especially those characterized by high metal dispersion, deactivated with time-on-stream. Two catalyst screening protocols were used. The first one concerned a gradually increased hydrogen partial pressure, whereas during the second one the H₂ pressure was decreased. Although, in general, the hydrogen-rich reaction conditions resulted in improved catalyst performance (higher overall activity and selectivity to CHCl₃), the second protocol led to even better results. Reasons for such a behaviour are suggested. Because of very high activity of a few tested samples, changes in CCl₄ conversion with the hydrogen partial pressure do not reflect real reaction orders in hydrogen. The same reason may lead to falsification of apparent activation energies. In certain cases the relation between conversion and hydrogen pressure showed a maximum, suggesting that HdCl undergoes via a Langmuir?CHinshelwood mechanism, when hydrogen and CCl₄ compete for metal surface sites. Both carbon- and chlorine-containing deposits were found in the post-reaction catalyst samples.     

Comparison of n-Pentane Reforming Over Pt Supported on Amorphous and γ-Al2O3

The n-pentane reforming activity of Pt supported on nonhydrolytic amorphous Al₂O₃ (Pt/NH–Al₂O₃), was investigated and compared to the catalytic activity of Pt supported on crystalline -Al₂O₃. The Pt was introduced by (a) impregnation with either a solution of H₂PtCl₆ in water or a solution of platinum acetylacetonate (PtAcac) in toluene; (b) in situ introduction of a Pt precursor, either PtBr₄ or cis-bis(benzonitrile)platinum dichloride, before gelation of the NH alumina. The rate-controlling step in the reforming of n-pentane for both amorphous and crystalline aluminas was found to be the reaction on the alumina acidic sites. The Pt/-Al₂O₃ catalysts exhibit higher conversions of n-pentane and higher selectivity to isopentane, than the corresponding amorphous alumina samples. After 1.5 h at 400 °C, the highest conversion of the -Al₂O₃-based catalysts was 47% with 20.3% selectivity to isopentane. The highest conversion of the NH–Al₂O₃-based catalysts under the same conditions was only 26% with 13.6% selectivity to isopentane. The high intrinsic Cl content (2.6wt%) of the amorphous alumina was found to have a minor effect on the activity of the alumina, compared to the activity of the more ordered -alumina. Catalysts prepared by impregnation of the NH alumina with aqueous chloroplatinic acid, exhibited higher conversions compared to catalysts prepared by impregnation of the NH alumina with a solution of PtAcac in toluene. This result occurred in spite of the lower surface area and lower Pt dispersions of the chloroplatinic acid-impregnated catalysts, and is explained by the formation of microcrystalline surface structures and existence of surface chlorine.     

Arc Plasma Processing of Pt and Pd Catalysts Supported on γ-Al2O3 Powders

Direct deposition of Pt and Pd nanoparticles onto γ-Al₂O₃ powders was studied by using a pulsed arc plasma process under vacuum to use them as an automotive catalyst. As deposited Pt catalyst exhibited a higher metal dispersion and thus a higher catalytic activity for CO oxidation, compared to the conventional Pt/Al₂O₃ prepared by wet impregnation. In contrast, Pd/Al₂O₃ prepared by the arc plasma method was less active because of its metallic state of Pd with a lower dispersion. A weak interaction between precious metals and γ-Al₂O₃ is not enough for thermal stabilization of as deposited nanoparticles during ageing in a stream of 10% H₂O in air at 900 °C.     

Promotion Effects of Platinum and Ruthenium on Carbon Nanotube Supported Cobalt Catalysts for Fischer–Tropsch Synthesis

Abstract  

Carbon nanotube supported nano-size monometallic and noble metal (Pt and Ru) promoted cobalt catalysts were prepared by incipient wetness impregnation (IWI) using solution of cobalt nitrate and characterized by nitrogen adsorption isotherm, X-ray diffraction (XRD), temperature programmed reduction, in situ magnetic method and TEM. Analysis of the magnetization and H₂-TPR data suggested promotion with platinum and ruthenium significantly decreased the cobalt species reduction temperature. TEM and XRD results showed that the presence of noble metal promoters had no significant effect on the size of cobalt for carbon naotube as catalytic support. Promotion of cobalt carbon nanotube-supported catalysts with small amounts of Pt and Ru resulted in slight increase in Fischer–Tropsch cobalt time yield. The Pt and Ru promoted cobalt catalyst exhibited carbon monoxide conversion of 37.1 and 31.4, respectively. C₅+ hydrocarbon selectivity was attained at 80.0%. The Pt promoted cobalt supported on carbon nanotube yielded better catalytic stability than that of the monometallic cobalt catalyst.     

Sugar Hydrogenation Over Supported Ru/C—Kinetics and Physical Properties

The hydrogenation kinetics of some natural sugars to corresponding sugar alcohols in aqueous solutions was investigated on Ru/C catalysts in a pressurized slurry reactor. The kinetic data were well described by a Langmuir-Hinshelwood model assuming that the hydrogenation step on the catalyst surface is rate determining. The density, viscosity and hydrogen solubility of the reacting liquid were measured. This information was used to estimate the liquid-phase diffusion coefficients, which were utilized in a reaction-diffusion-catalyst deactivation model for porous catalyst layers. The model indicated that diffusional resistance becomes severe for rather small catalyst particles and the model described the movement of the reactive front inside the particle during the reaction. The simulation results indicate that structured reactors would provide a better approach than the conventional fixed bed technology, if continuous operation is desired.     

Aqueous-Phase Processing of Bio-oil Model Compounds Over Pt–Re Supported on Carbon

The aqueous-phase processing (APP) of biomass-derived bio-oil model compounds such as ethanol, acetaldehyde, formic acid and acetic acid over Pt?CRe/C was examined. For the APP of ethanol at 250?°C, the product distribution was determined and quantified. H₂, CO₂, CH₄, C₂H₆, acetaldehyde, ethyl ether, ethyl acetate, acetic acid were found to be primary products and C₃H₈, methanol, butanol and acetal were found to be minor products. By also exploring the product distributions of acetaldehyde, acetic acid and formic acid under APP conditions with the Pt?CRe/C, the reaction network associated with the APP conversion of ethanol was determined. Using this reaction network, flux analysis was performed on the ethanol reaction system to determine the reaction pathway and relative rates (v₁?Cv₈) for each step. From this analysis, it was found that the dehydrogenation of the ethanol was the most active reaction in the reaction system.     

Pd (1?wt%)/LaMn0.4Fe0.6O3 Catalysts Supported Over Silica SBA-15: Effect of Perovskite Loading and Support Morphology on Methane Oxidation Activity and SO2 Tolerance

Catalysts of palladium (1?wt%) deposited over silica SBA-15 supported LaMn_0.4Fe_0.6O₃ perovskite (with perovskite loading of 10, 30 and 40?wt%), characterized by several techniques (BET, SAXS, XRD, TPR) are tested in the combustion of methane. Bulk LaMn_0.4Fe_0.6O₃ with the corresponding supported Pd catalyst are also considered for comparison purpose. Dispersing LaMn_0.4Fe_0.6O₃ oxide over silica SBA-15 improves the activity of the supported palladium catalysts to an extent depending on the perovskite loading. After ageing at 600?°C for 14?h, Pd catalysts supported over SBA-15 loaded with 30 and 40?wt% of LaMn_0.4Fe_0.6O₃, deactivate less as compared to Pd over bulk perovskite. Moreover, during catalytic tests carried out in the presence of 10?vol. ppm SO₂ these catalysts exhibit better sulphur tolerance and higher regeneration capability as compared to the Pd/LaMn_0.4Fe_0.6O₃. The superior performance of such catalysts is attributed to the good dispersion of the LaMn_0.4Fe_0.6O₃ over the SBA-15, with consequent increase of the perovskite surface area with respect to bulk perovskite. In addition, the porous structure of the silica contributes to a better stabilization of the active species against sintering and acts as a chemical sink during the catalyst exposure to SO₂.     

Comparative Study on the Mechanisms of Partial Oxidation of Methane to Syngas Over Rhodium Supported on SiO2 and γ-Al2O3

A comparative study on the mechanisms of the partial oxidation of methane (POM) to syngas over SiO₂- and -Al₂O₃-supported Rh catalysts was carried out using in situ time-resolved FTIR spectroscopy to follow the primary products of POM reaction over the catalysts. Experiments of catalytic performance evaluation and temperature-programmed reduction (TPR) characterization of the catalysts, as well as the in situ FTIR spectroscopic study using CO to probe the oxidation state of Rh species over the catalysts were performed. It was found that the direct oxidation of CH₄ to syngas is the main pathway of the POM reaction over Rh/SiO₂ catalysts, while the combustion--reforming mechanism is the dominant pathway of syngas formation over Rh/-Al₂O₃ catalysts. The results of TPR characterization indicate that Rh supported on -Al₂O₃ is more difficult to reduce than Rh supported on SiO₂. The IR experiments of CO adsorption over Rh/SiO₂ and Rh/-Al₂O₃ after the POM reaction reveal that the surface of the Rh/-Al₂O₃ catalyst contains more partially oxidized rhodium (Rh⁺) species as compared to the Rh/SiO₂ catalyst. These results suggest that the significant difference in the mechanisms of the POM reaction over Rh/SiO₂ and Rh/-Al₂O₃ catalysts can be related to the difference in the surface concentration of O^2- species over the catalysts under the reaction conditions mainly due to the difference in oxygen affinity of the Rh species on the two supports.     

CO Methanation Over Ru�CAl2O3 Catalysts: Effects of Chloride Doping on Reaction Activity and Selectivity

The selective CO methanation (CO-SMET) process via Ru?CAl₂O₃ catalysts was investigated as a tool for complete CO removal in fuel processors, when the H₂-rich gas so produced is employed for PEM-FCs applications to vehicles, boats, yachts and residential co-generators. CO-SMET seems, in fact, to be a good alternative to the most widely used CO preferential oxidation (CO-PROX) process. The performance of Ru-based catalysts on alumina carrier for efficient CO removal through CO-SMET was studied, exploring the role of two different Ru precursors (chloride and nitrate), and the doping effect of chloride and of Ru load (1%, 3% and 5%). First, two catalytic families (Ru?CAl₂O₃_Cl and Ru?CAl₂O₃_NO₃) were prepared by incipient wetness impregnation of alumina powder synthesized via solution combustion synthesis, by varying the Ru load. Then, based on the best obtained results, a third catalytic family was prepared adding chloride to Ru?CAl₂O₃_NO₃ catalysts by impregnation. The CO removal performance was determined at catalyst powder level in a fixed bed micro reactor. Better performances were exhibited when Ru was deposited from chloride precursor, but the post-addition of chlorine to fresh Ru?CAl₂O₃ catalysts prepared with nitrate precursor tremendously improved their selectivity toward CO methanation. In particular, with both 1% and 3% Ru?CAl_NO₃ catalyst chlorine doped, complete CO conversion was reached in a proper temperature range where the CO₂ methanation was suitably kept at a low acceptable level.