Fischer-Tropsch Synthesis over Modified Cobalt Catalysts

The catalysts of Co/Zr-SiO2 were prepared by precipitation and the promoter of Pt was supported by impregnation. The reducibility of the cobalt oxide and the other physicochemical properties of the catalysts were characterized by TPR, TPD, BET and XPS. With the evaluation of the reduction temperature, the reduction degree increased but the surface area of the catalysts and the adsorption property for reactant CO distinctly decreased; The addition of Pt resulted in the improvement of the reducibility by decreasing the reduction temperature of cobalt oxide species. The FT-synthesis has been performed in a quartz fixed-bed reactor, and the experimental results showed that the best activity for promoted catalyst has been found at the reduction temperature of 400℃, in spite of its uncompleted reduction.     

Cobalt Fischer�CTropsch Catalyst Regeneration: The Crucial Role of the Kirkendall Effect for Cobalt Redispersion

Redispersion of cobalt is a key process during Fischer?CTropsch catalyst regeneration. Using model catalysts we show that redispersion is a two step process. Oxidation of supported metallic cobalt nanoparticles produces hollow oxide particles by the Kirkendall effect; reduction leads to break-up of these hollow oxide shells, forming multiple metallic particles. This mechanism is to a large extent independent of the support.     

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.     

Cobalt–silica interaction and the dehydrogenation of 2-propanol

The interaction between silica and cobalt was studied on supported catalysts with low silica loading. Below a threshold cobalt level of 0.41 wt%, the catalysts were inactive for dehydrogenation of 2-propanol at 450 K. Inactivity was attributed to irreducibility of cobalt ions. Samples that were impregnated at a level below the threshold, dried, calcined, then reimpregnated below the threshold level, redried and recalcined such that the total cobalt content exceeded the threshold, were inactive. These results are not consistent with a model in which a portion of the cobalt interacts with specific silica sites, forming an irreducible species. Rather, they suggest that strongly interacting cobalt ions are incorporated into the silica surface.     

Catalytic Combustion of Methane over Cobalt–Magnesium Oxide Solid Solution Catalysts

A series of cobalt–magnesium oxide solid solution catalysts (CoMgO) have been prepared using urea combustion methods, and characterised by X-ray diffraction (XRD) and laser Raman (LR). The catalytic activities for methane combustion have been tested in a continuous-flow microreactor. The Co content has a significant effect on the activity of the cobalt–magnesium oxide solid solution catalysts. The catalysts containing 5 and 10% Co have the lowest light-off temperature in methane combustion. In the preparation of cobalt–magnesium oxide solid solution catalysts, higher urea to metal ratio favors the formation of the catalysts with smaller crystal particles and leads to a better catalytic performance for methane combustion. Addition of lanthanum nitrate to the solution of Co and Mg nitrate depressed the formation of the cobalt–magnesium oxide solid solution and decreased the activity of the catalysts for methane combustion. The cobalt–magnesium oxide solid solution catalysts are very stable when the calcination or reaction temperature is no more than 900°C. However, the catalytic activity decreases rapidly after high temperature (>1000°C) calcination, possibly due to sintering of the catalyst and thus decrease of the surface area.     

Highly Selective and Active Niobia-Supported Cobalt Catalysts for Fischer–Tropsch Synthesis

The performance of Co/Nb₂O₅ was compared to that of Co/γ-Al₂O₃ for the Fischer–Tropsch synthesis at 20 bar and over the temperature range of 220–260 °C. The C₅₊ selectivity of Nb₂O₅-supported cobalt catalysts was found to be very high, i.e. up to 90 wt% C₅₊ at 220 °C. The activity per unit weight cobalt was found to be similar for Nb₂O₅ and γ-Al₂O₃-supported catalysts at identical reaction temperature. However, due to the low porosity of crystalline Nb₂O₅, the cobalt loading was limited to 5 wt% and consequently the activity per unit weight of catalyst was lower than of Co/γ-Al₂O₃ catalysts with higher cobalt loadings. This low activity was largely compensated by increasing the reaction temperature, although the C₅₊ selectivity decreased upon increasing reaction temperature. Due to the high intrinsic C₅₊ selectivity, Nb₂O₅-supported catalysts could be operated up to ~250 °C at a target C₅₊ selectivity of 80 wt%, whereas γ-Al₂O₃-supported catalysts called for an operation temperature of ~210 °C. At this target C₅₊ selectivity, the activity per unit weight of catalyst was found to be identical for 5 wt% Co/Nb₂O₅ and 25 wt% Co/Al₂O₃, while the activity per unit weight of cobalt was a factor of four higher for the niobia-supported catalyst.     

Selective Synthesis of Higher Linear α-olefins over Cobalt Fischer–Tropsch Catalyst

An efficient approach for more selective synthesis of higher linear α-olefins was achieved by utilizing suitable reaction media in FTS reaction. About 41.4% average α-olefins content in C₅–C₂₅ fractions was obtained at = 5 g-cat h mol⁻¹ in n-C₁₀ solvent, which is markedly higher than the value (2.5%) obtained in 85% N₂ + 15% n-C₆.     

Low Temperature Water–Gas Shift Reaction Over Alkali Metal Promoted Cobalt Carbide Catalysts

Low temperature water–gas shift (LT-WGS) was performed over various group I alkali metal (Li, Na, K, Rb, Cs) promoted cobalt carbide (Co₂C) catalysts at temperatures ranging from 453 to 573 K and atmospheric pressure. Cobalt carbide (Co₂C) was found to be active for the WGS reaction. The stability of the catalyst is related to the stability of the cobalt carbide phases under reaction conditions. Potassium promoted cobalt carbide catalysts exhibited higher activity and stability compared to the other alkali promoted catalysts for LT-WGS. X-ray diffraction analyses of fresh and used catalysts suggest that the origin of deactivation of the catalysts is primarily due to the chemical transition of cobalt from carbide to metal during WGS.     

Adsorption of Divalent Cobalt from Aqueous Solution onto Chitosan–Coated Perlite Beads as Biosorbent

Abstract

Chitosan coated perlite beads are prepared by drop‐wise addition of a liquid slurry containing chitosan and perlite to an alkaline bath. The resulting beads are characterized using FTIR, SEM, EDXRF, and Surface area analysis and the chitosan content of the beads is 23% as determined by a pyrolysis method. Adsorption of Co (II) metal ions from aqueous solution on chitosan coated perlite beads is studied under both equilibrium and dynamic conditions. In the present investigation, a first order reversible rate equation is used to understand the kinetics of metal removal and to calculate the rate constants at different initial concentrations. The equilibrium characteristics of metal ion on newly developed biosorbent are studied and the experimental adsorption data are well fitted to Freundlich and Langmuir adsorption isotherm models and the model parameters are evaluated. The effect of pH, agitation time, concentration of adsorbate, and amount of adsorbent on the extent of the adsorption are investigated. The sorbent loaded with metal is regenerated with 0.10 mol dm^?3 sodium hydroxide solution. The adsorption desorption cycles indicated that the chitosan coated perlite could be regenerated and reused to remove Co (II) from waste water.     

Cobalt‐catalyzed amination of 1,3‐cyclohexanediol and 2,4‐pentanediol in supercritical ammonia

The onestep procedure of amination of bifunctional secondary alcohols to diamines has been investigated in a continuous fixedbed reactor. Application of supercritical NH₃ as a solvent and reactant suppressed catalyst deactivation and improved selectivities to amino alcohol intermediates, whereas selectivities to diamines remained poor (8–10%). The main reason for the low diamine selectivity of 1,3dihydroxy compounds is water elimination leading to undesired monofunctional products via ,unsaturated alcohol, ketone or amine intermediates. This side reaction does not occur with 1,4dihydroxy compounds which afford high aminol and diamine selectivities under similar conditions. Amination of secondary diols with ammonia was found to be faster, but less selective than that of the corresponding primary 1,3propanediol.     

Electrocatalysis of the Reduction of Dioxygen by π-Conjugated Polymer Complexes with Dinuclear Cobalt Porphyrin

Catalysis of polymer complexes using polyanilines and dinuclear cobalt porphyrin (Co₂P) was investigated by electrochemical measurement. Poly(2,3-dicarboxyaniline) with CoTPPS–CoTMPyP acts as an excellent catalyst for a four-electron reduction of oxygen even under pseudo-neutral conditions. Various polymer complexes were made using synthesized electroresponsive polymers. The selectivity of the four-electron reduction dramatically decreases with an increase in the potential gap between the polymer and the porphyrin. This result indicates that a sequential electron transfer takes place from the polymer to the porphyrin with a potential similar to that of the cobalt porphyrin.     

Preparation of Cobalt Nitride from Co–Al Hydrotalcite and its Application in Hydrazine Decomposition

Alumina supported cobalt nitride [Co₄N–Al₂O₃ (HT)] with high cobalt loading has been prepared for the first time from Co–Al hydrotalcite precursors. The formation of the Co₄N phase was confirmed by XRD, H₂-TPR, and XPS. Compared with Co₄N/Al₂O₃ (IMP) prepared by conventional impregnation and nitriding, the hydrotalcite derived catalyst exhibited a much better activity for hydrazine decomposition as consequence of higher dispersion of active species.     

Cobalt supported on carbon nanotubes — A promising novel Fischer–Tropsch synthesis catalyst

An extensive study of Fischer–Tropsch synthesis (FTS) on carbon nanotubes (CNT) supported and γ–alumina-supported cobalt catalysts with different amounts of cobalt are reported. Up to 40 wt.% of cobalt is added to the supports by the impregnation method. The effect of the support on the reducibility of the cobalt oxide species, dispersion of the cobalt, average cobalt clusters size, water–gas shift (WGS) activity and activity and selectivity of FTS is investigated. Using carbon nanotubes as cobalt catalyst support was found to cause the reduction temperature of cobalt oxide species to shift to lower temperatures. The strong metal-support interactions are reduced to a large extent and the reducibility of the catalysts improved significantly. CNT aided in well dispersion of metal clusters and average cobalt clusters size decreased. Results are presented showing that the hydrocarbon yield obtained by inventive CNT supported cobalt catalyst is surprisingly much larger than that obtained from cobalt on alumina supports. The maximum concentration of active surface Co° sites and FTS activity for alumina and CNT supported catalysts are achieved at 34 wt.% and 40 wt.% cobalt loading respectively. CNT caused a slight decrease in the FTS product distribution to lower molecular weight hydrocarbons.     

Cobalt Schiff base complexes: Synthesis characterization and catalytic application in Suzuki–Miyaura reaction

3-Methoxysalicylaldehyde was condensed with the amines 4-aminoacetophenone and 2-amino-5-bromopyridine to obtain Schiff base ligands, 1 and 2, which were coordinated to cobalt salts as complex 1 and complex 2, respectively. The synthesized ligands and complexes were characterized by spectroscopic (FT-IR, UV-Vis, ¹H-NMR and mass spectrometry), thermal (TGA) and elemental analysis. The structures of the complexes were verified by evaluating their magnetic susceptibility and spectroscopic evidences. Synthesized complexes were studied for their catalytic activity in the Suzuki-Miyaura cross-coupling of aryl halides with phenylboronic acid. Optimized reaction yields 90% of the cyanobiphenyl for complex 1 and 91% for complex 2 with 0.1 mmol of catalyst loading thereby substantiating the C-C coupling efficiency of the synthesized complexes, 1 and 2.     

Selective Oxidation of Diphenylmethane Over Cobalt Doped Mesoporous Titania–Silica Catalyst with High Ti Content

Cobalt doped mesoporous titania–silica with Ti/Si molar ratio of 0.5 (Co–TiO₂–SiO₂) was synthesized for the oxidation of diphenylmethane in acetic acid using aqueous hydrogen peroxide as oxidant for the first time. Fast hot catalyst filtration experiment proved that the catalyst acted as a heterogeneous one. Recycling of the catalyst indicates that the catalyst can be used a number of times without losing its activity to a greater extent. The effects of reaction time and reaction temperature on the performance of the catalyst were investigated. Moreover, cobalt doped mesoporous titania with a crystalline structure and cobalt doped mesoporous titania–silica with different molar ratio were also studied. It was found that Co–TiO₂–SiO₂ with Ti/Si molar ratio of 0.5 showed the highest activity.     

Detailed Kinetics of the Fischer�CTropsch Synthesis on Cobalt Catalysts Based on H-Assisted CO Activation

A complete mechanistic kinetic model of the Fischer?CTropsch synthesis (FTS) over a Co/Al₂O₃ state-of-the-art catalyst is developed here under conditions relevant to industrial operation. On the basis of the most recent findings on the reaction mechanism, here described according to the H-assisted CO dissociation theory and the alkyl chain growth mechanism, and on the basis of the latest indications available on the rate determining step involved in the CO activation process, rate expressions for all the steps leading to CO and H₂ consumption and n-paraffins, ??-olefins and H₂O formation are derived. Such expressions are functions of the molar fraction of CO, H₂ and olefins in the liquid phase surrounding the catalyst pellets, that in turn are related to the gas-phase pressure and composition, and of the surface coverage of the adsorbed species. Thermodynamic and kinetic parameters involved in the model are estimated by non-linear multi-response regression on a complete set of FTS experimental data collected in a lab-scale tubular reactor at steady-state conditions (P = 8?C25 bar, T = 210?C235 °C, H₂/CO feed ratio = 1.8?C2.7 mol mol^?1, GHSV = 2,000?C7,000 cm³(STP) h^?1 g _cat ^?1 ). Both the experimental CO conversion and the hydrocarbon distribution (up to N = 50) in FTS are well predicted by the model with 13 adaptive parameters, without the need of introducing any empirical parameter. Analysis of the model offers insight in the rates of the elementary steps associated with the reaction mechanism and in the surface coverages of the adsorbed species. Such information explains the peculiar reactivity observed over cobalt-based Fischer?CTropsch catalysts, and can provide guidelines for the design of more active and selective catalytic materials.