Ruthenium promoted cobalt-alumina catalysts for the synthesis of high-molecular-weight solid hydrocarbons from CO and hydrogen

The effect of the ruthenium promotion of Fischer–Tropsch (FT) cobalt–alumina catalysts on the temperature of catalyst activation reduction and catalytic properties in the FT process is studied. The addition of 0.2–1 wt % of ruthenium reduces the temperature of reduction activation from 500 to 330–350°C while preserving the catalytic activity and selectivity toward C5+ products in FT synthesis. FT ruthenium-promoted Co–Al catalysts are more selective toward higher hydrocarbons; the experimental value of parameter αASF of the distribution of paraffinic products for ruthenium-promoted catalysts is 0.93–0.94, allowing us to estimate the selectivity toward C20+ synthetic waxes to be 48 wt %, and the selectivity toward C35+ waxes to be 23 wt %. Ruthenium-promoted catalysts also exhibit high selectivity toward olefins

Identifying the Sources of Ferromagnetism in Sol-Gel Synthesized Zn\u3csub\u3e1-x\u3c/sub\u3eCo\u3csub\u3ex\u3c/sub\u3eO (0 ≤ x ≤ 0.10) Nanoparticles

We have carefully investigated the structural, optical and electronic properties and related them with the magnetism of sol-gel synthesized Zn1-xCoxO (0 ≤ x ≤ 0.10) nanoparticles. Samples with x ≤ 0.05 were pure and free of spurious phases, whereas ZnCo2O4 was identified as the impurity phase for samples with x ≥ 0.08. Samples with x \u3c 0.05 were found to be true solid solutions with only high spin Co2+ ions into ZnO structure, whereas sample with x = 0.05, exhibited the presence of high spin Co2+ and low spin Co3+. For the impurity-free samples we found that as Co concentration increases, a and c lattice parameters and Zn–O bond length parallel to the c-axis decrease, the band gap drastically decreases, and the average grain size and distortion degree increases. In all samples there are isolated Co2+ ions that do not interact magnetically at room temperature, bringing about the observed paramagnetic signal, which increases with increasing Co concentration. M vs T curves suggest that some of these disordered Co2+ ions in Zn1−xCoxO are antiferromagnetically coupled. Moreover, we also found that the intensity of the main EPR peak associated to Co2+ varies with the nominal Co content in a similar manner as the saturation magnetizations and coercive fields do. These results point out that the ferromagnetism in these samples should directly be correlated with the presence of Co2+. Bound magnetic polaron model is insufficient to explain the Room temperature ferromagnetism in these Co doped ZnO samples and the charge transfer model seems not influence considerably the FM properties of Zn1-xCoxO nanoparticles. The FM behavior may be originated from a combination of several factors such as the interaction of high spin Co2+ ions, the formation of defect levels close to the valence band edge and grain boundaries effects

EFfect of alumina modification on the structure of cobalt-containing Fischer-Tropsch synthesis catalysts according to internal-field 59Co NMR data

International audienceAn internal-field Co-59 NMR study of cobalt-containing Fischer-Tropsch synthesis catalysts supported on different alumina modifications was reported. The Co/delta-Al2O3 sample was shown to contain single-domain fcc packing and stacking faults, whereas Co/gamma-Al2O3 gave signals from the fcc domain walls, hcp and stacking faults, thus indicating differences in the particle size of the studied samples. T-2 relaxation times were measured; their distribution in a spectrum is non-uniform, which allows signals to be distinguished by their relaxation times. Quantitative measurements of the relative atoms content in different packings revealed that the catalysts have mostly a defect structure. A brief historical background was presented to characterize the internal-field Co-59 NMR technique, the related problems, and different approaches to acquired data interpretation

The effect of ruthenium promotion of the Co/d-Al2O3 catalyst on the hydrogen reduction kinetics of cobalt

The effect of ruthenium content on the reductive activation of the Co/δ-Al2O3 catalyst was investigated using thermal analysis and in situ synchrotron radiation X-ray diffraction. Data of thermal analysis and phase transformations can be described by a kinetic scheme consisting of three sequential steps: Co³⁺ → Co²⁺ → (Co⁰Co²⁺) → Co⁰. The first step is the generation of several CoO clusters within one Co3O4 crystallite followed by their further growth obeying the Avrami–Erofeev kinetic equation (An1) with dimensional parameter n1 < 1, which may indicate the diffusion control of the growth. The second step is the kinetically controlled sequential process of the metallic cobalt phase nucleation (An2), which is followed by the third step of slow particle growth limited by mass transport according to the Jander model (D). Ruthenium promotion of Co/δ-Al2O3 catalysts significantly accelerates the reduction of cobalt. As the ruthenium content is raised to 1 wt%, the characteristic temperature of metal phase formation decreases by more than 200 °C and Ea for An2 step decreases by 25%. For step D, a joint decrease in activation energy and pre-exponential factor in case of ruthenium promotion corresponds to a weaker diffusion impediment at the final step of cobalt reduction. In the case of unmodified Co/δ-Al2O3, the characteristic temperature of the metal phase formation reaches very high values, the metallic nuclei rapidly coalesce into larger ones, and the further process is inhibited by diffusion of the reactants through the product layer. For ruthenium promoted catalysts, each CoO crystallite generates one metal crystallite; thus, ruthenium enhances the dispersion of the active component

Ruthenium promoted cobalt-alumina catalysts for the synthesis of high-molecular-weight solid hydrocarbons from CO and hydrogen

The effect of the ruthenium promotion of Fischer–Tropsch (FT) cobalt–alumina catalysts on the temperature of catalyst activation reduction and catalytic properties in the FT process is studied. The addition of 0.2–1 wt % of ruthenium reduces the temperature of reduction activation from 500 to 330–350°C while preserving the catalytic activity and selectivity toward C5+ products in FT synthesis. FT ruthenium-promoted Co–Al catalysts are more selective toward higher hydrocarbons; the experimental value of parameter αASF of the distribution of paraffinic products for ruthenium-promoted catalysts is 0.93–0.94, allowing us to estimate the selectivity toward C20+ synthetic waxes to be 48 wt %, and the selectivity toward C35+ waxes to be 23 wt %. Ruthenium-promoted catalysts also exhibit high selectivity toward olefins

The effect of ruthenium promotion of the Co/d-Al2O3 catalyst on the hydrogen reduction kinetics of cobalt

The effect of ruthenium content on the reductive activation of the Co/δ-Al2O3 catalyst was investigated using thermal analysis and in situ synchrotron radiation X-ray diffraction. Data of thermal analysis and phase transformations can be described by a kinetic scheme consisting of three sequential steps: Co³⁺ → Co²⁺ → (Co⁰Co²⁺) → Co⁰. The first step is the generation of several CoO clusters within one Co3O4 crystallite followed by their further growth obeying the Avrami–Erofeev kinetic equation (An1) with dimensional parameter n1 < 1, which may indicate the diffusion control of the growth. The second step is the kinetically controlled sequential process of the metallic cobalt phase nucleation (An2), which is followed by the third step of slow particle growth limited by mass transport according to the Jander model (D). Ruthenium promotion of Co/δ-Al2O3 catalysts significantly accelerates the reduction of cobalt. As the ruthenium content is raised to 1 wt%, the characteristic temperature of metal phase formation decreases by more than 200 °C and Ea for An2 step decreases by 25%. For step D, a joint decrease in activation energy and pre-exponential factor in case of ruthenium promotion corresponds to a weaker diffusion impediment at the final step of cobalt reduction. In the case of unmodified Co/δ-Al2O3, the characteristic temperature of the metal phase formation reaches very high values, the metallic nuclei rapidly coalesce into larger ones, and the further process is inhibited by diffusion of the reactants through the product layer. For ruthenium promoted catalysts, each CoO crystallite generates one metal crystallite; thus, ruthenium enhances the dispersion of the active component

Zr—P-modification of the γ-Al2O3 support of cobalt-containing catalysts for the Fischer—Tropsch synthesis

The cobalt-containing catalysts based on alumina modified by zirconium and phosphorus additives were synthesized for the Fischer—Tropsch synthesis. Zirconium cations and phosphate anions are adsorbed onto the surface of the support oxide phase (γ-Al2O3) or incorporated into cobalt-containing oxide. The modification of the support probably prevents the insertion of cobalt cations into γ-Al2O3and favors the formation of larger Co—Al oxide particles with the spinel-like structure. The cobalt systems based on the unmodified support have the highest catalytic activity in the Fischer—Tropsch synthesis at 230 °С (~10 mmolСО (gcat h)–1 at a СО conversion of 20–23%)

Zr—P-modification of the γ-Al2O3 support of cobalt-containing catalysts for the Fischer—Tropsch synthesis

The cobalt-containing catalysts based on alumina modified by zirconium and phosphorus additives were synthesized for the Fischer—Tropsch synthesis. Zirconium cations and phosphate anions are adsorbed onto the surface of the support oxide phase (γ-Al2O3) or incorporated into cobalt-containing oxide. The modification of the support probably prevents the insertion of cobalt cations into γ-Al2O3and favors the formation of larger Co—Al oxide particles with the spinel-like structure. The cobalt systems based on the unmodified support have the highest catalytic activity in the Fischer—Tropsch synthesis at 230 °С (~10 mmolСО (gcat h)–1 at a СО conversion of 20–23%)

The state of absorbed hydrogen in the structure of reduced copper chromite from the vibration spectra

Khassin, Alexander A. Kustova, Galina N. Jobic, Herve Yurieva, Tamara M. Chesalov, Yury A. Filonenko, Georgii A. Plyasova, Lyudmila M. Parmon, Valentin N.The reduction of copper chromite, CuCr2O4, is followed by means of thermogravimetric analysis. The reduced state is studied by means of FT IR spectroscopy, Raman spectroscopy and inelastic neutron scattering. The reduction of copper occurs in two stages: absorption of hydrogen at 250-400 degrees C and dehydration of the reduced state at above 450 degrees C. The measured vibrational spectra prove that a considerable amount of hydrogen is absorbed by the oxide structure with absorbed protons stabilized in OH and HOH-groups (geminal protons). Three groups of vibration bands are observed in the INS spectra, which can be assigned to stretching, bending and libration vibrations. An increase in the reduction temperature of copper chromite results in softening of the stretching and hardening of the bending vibrations, what can be related to the strengthening of hydrogen bonding

Interaction of hydrogen with Cu-Zn mixed oxide model methanol synthesis catalyst

ENERGIE:MATERIAUX+HJOInteraction of hydrogen with model Cu-Zn methanol synthesis catalyst prepared by decomposition of mixed hydroxicarbonate is studied by inelastic neutron scattering, in situ FTIR/MS, and thermal analysis. Reduced (Cu-0.08,Zn-0.92)O mixed oxide accumulates 6H/Cu, mainly as hydride, hydroxyl and formate species. The reduction of copper in the (Cu,Zn)O mixed oxide occurs via a reversible redox interaction with H-2 and absorption of protons as OH--groups with nu =3250 cm(-1) and delta approximate to 1430-1480 cm(-1). Kinetic and thermodynamic parameters of this process are evaluated. The weight loss during the reduction is due to the decomposition of the residual carbonate groups to CO2 via formate intermediates, which occurs in the presence of hydrogen. Exposure of (Cu,Zn)O to air prior to the reduction strongly affects the kinetic parameters of the reduction process. (C) 2013 Elsevier B.V. All rights reserved