V. V. Chesnokov

Oxidative dehydrogenation of butane over nanocrystalline MgO, Al2O3, and VOx/MgO catalysts in the presence of small amounts of iodine

Abstract High surface area nanocrystalline MgO, Al 2 O 3 , MgO·Al 2 O 3 , commercial MgO, and a series of 10% V/MgO samples were used as catalysts in one-step selective oxidative dehydrogenation of butane to butadiene in the presence of oxygen and iodine. Molecular iodine shifts the equilibrium of the dehydrogenation reactions to the right and makes it possible to achieve high butane conversion with high selectivity to butadiene. When excess oxygen is present in the feed, iodine is successfully regenerated and can be recycled. Butadiene selectivity as high as 64% has been achieved in the presence of small amounts of iodine (0.25 vol%) over a vanadia–magnesia catalyst at 82% butane conversion. The best performance was observed over a catalyst containing the magnesium orthovanadate phase.

Nanocrystalline ultra high surface area magnesium oxide as a selective base catalyst

Nanocyrstals of MgO having 4 nm average crystallite sizes with 450–550 m2/g surface area were prepared by the Aero-gel preparation method (AP-MgO). Dehydrohalogenation of 1-chlorobutane was performed using AP-MgO as a catalyst; And 1-butene is the selective product formed even after several cycles of 1-chlorobutane injections. AP-MgO was allowed to react with Cl2, which resulted in the formation of a highly reactive adduct which has a capability to selectively chlorinate propane.

Effect of the Structure of Carbon Nanofibers on the State of an Active Component and on the Catalytic Properties of Pd/C Catalysts in the Selective Hydrogenation of 1,3-Butadiene

The state of highly dispersed palladium particles supported on filamentous carbon was studied using high-resolution electron microscopy, XPS, and X-ray diffraction analysis. Three types of filamentous carbon were used, in which the basal planes of graphite were arranged along, across, and at an angle to the nanofiber axis. The amount of supported palladium was 0.25–5.8 wt %. The structure of the carbon support was found to affect the properties of the active component. Highly dispersed palladium particles exhibited the strongest interaction with a carbon surface formed by the butt ends of graphite (002) layers. This interaction resulted in electron transfer from the metal to the support and in the stabilization of palladium in the most dispersed state. A change in the properties of palladium particles caused a change in the catalytic properties of Pd/C catalysts in the reaction of selective 1,3-butadiene hydrogenation to butenes. The strong interaction of Pd2+ with the butt ends of graphite resulted in the stabilization of palladium in an ionic state. An increase in the fraction of Pd2+ in the catalysts was responsible for a decrease in both the overall activity and selectivity of Pd/C catalysts in the reaction of 1,3-butadiene hydrogenation to butenes.

Decomposition of Chlorinated Hydrocarbons on Iron-Group Metals

The decomposition of 1,2-dichloroethane and chlorobenzene on nickel–alumina, cobalt–alumina, and iron–alumina catalysts at 400–600°C was studied. Thermodynamic calculations demonstrated that the susceptibility of metals to chlorination under exposure to HCl increases in the order Ni < Co < Fe. The addition of hydrogen to the reaction mixture was found to dramatically decrease the rate of carbon deposition in the decomposition of 1,2-dichloroethane because of the intense hydrogenation of intermediates that are graphite precursors. Two fundamentally different reaction paths were found in the degradation of 1,2-dichloroethane: decomposition via a carbide-cycle mechanism with the formation of carbon as the main product (under conditions of a deficiency of hydrogen) and 1,2-dichloroethane hydrodechlorination accompanied by methanation of the formed carbon (under conditions of an excess of hydrogen). The degradation of chlorobenzene diluted with hydrogen in a molar ratio of 1 : 50 was not accompanied by carbon formation on the catalyst. A comparison between the selectivity for reaction products on nickel–alumina and cobalt–alumina catalysts indicated that the former catalyst is more active in the rupture of C–C bonds and in the methanation reaction of deposited carbon, whereas the latter is more favorable for hydrodechlorination. The optimum conditions and thermal regime for efficient and stable operation of the catalysts were found.

The Relationship between the State of Active Species in a Ni/Al2O3Catalyst and the Mechanism of Growth of Filamentous Carbon

The formation of active particles and their changes in the course of 1,3-butadiene decomposition on a Ni/Al2O3catalyst at temperatures from 400 to 800°C were studied by high-resolution electron microscopy. It was found that carbon filaments of different types were formed at 400–800°C. The growth of thin filaments (20–30 nm in diameter) takes place at 400–600°C on a conical Ni particle located at the growing end of the filament, whereas di-symmetrical filaments 50–100 nm in diameter grow on biconical metal particles. As the carbonization temperature was increased to 700–800°C, graphite nanotubes 5–20 nm in diameter were formed. It was found that the mechanism of formation and the structure of filaments are related to the state of catalytically active species, which consist of a solid solution of carbon in the metal. It is suggested that the metastable surface nickel carbide Ni3C1 – xis an intermediate compound in the catalytic formation of graphite filaments from 1,3-butadiene. Upon termination of the reaction, the metastable Ni3C1 – xmicrophase is decomposed with the formation of hexagonal nickel microinclusions. The role of epitaxy in the nucleation and growth of a graphite phase on the metal is discussed. Models are presented for the growth of structurally different carbon filaments depending on the formation of active metal species at various temperatures. Considerable changes in the structure of carbon and the formation of nanotubes at 700–800°C are related to the appearance of a viscous-flow state of metal–carbon particles.

Morphology and structure of carbon resulting from decomposition of chlorohydrocarbons on nickel and cobalt containing catalysts

Morphology of carbons deposited from chlorohydrocarbons on Ni(Co)/Al2O3 has been investigated. It has been established that carbon filaments consist of imperfect graphite layers and possess high adsorption capacity towards hydrogen.

New data on gas-phase radical reactions in the steam reforming of methane in the presence of catalysts: I. Nickel catalysts

Methane pyrolysis and steam reforming were studied over a series of nickel catalysts (Ni-Al2O3, Ni/MgO, and Ni/LiAlO2) under the same conditions (650-750°C, PCH4 = 0.001-0.03 MPa). Unlike heterogeneous reaction of pyrolysis, some of the steps of steam reforming of methane occur in the gas phase. When gasphase reactions were suppressed, the rate and activation energy of steam reforming are close to the corresponding kinetic characteristics for pyrolysis. Hypothetically, the rate-limiting step of the process is the dissociative adsorption of methane on nickel in this case.

CO Oxidation over Pd/ZrO2 Catalysts: Role of Support′s Donor Sites

A series of supported Pd/ZrO2 catalysts with Pd loading from 0.2 to 2 wt % was synthesized. The ZrO2 material prepared by a similar technique was used as a reference sample. The samples have been characterized by means of transmission electron microscopy (TEM), X-ray diffraction analysis (XRD), X-ray photoelectron spectroscopy (XPS), temperature-programmed reduction (TPR), testing reaction of ethane hydrogenolysis (HGE), N2 adsorption, and electron paramagnetic resonance (EPR) spectroscopy. 1,3,5-trinitrobenzene was used as a probe molecule for the EPR spin probe method. The catalytic performance of samples was tested in the model reaction of CO oxidation. It was shown that the concentration of donor sites of support measured by EPR spin probe correlates with catalytic behavior during light-off tests. Low concentration of donor sites on a support’s surface was found to be caused by the presence of the specific surface defects that are related to existence of coordinately unsaturated structures.

Catalytic Steam Reforming of Methane: New Data on the Contribution of Homogeneous Radical Reactions in the Gas Phase: II. A Ruthenium Catalyst

AbstractThe kinetics of methane steam reforming and pyrolysis on Ru/Al2O3(T= 650–750°C,