Thermodynamic Aspects of Dimethoxymethane Conversion into Hydrogen-Rich Gas

Kinetics and Catalysis - A thermodynamic analysis of the conversion of dimethoxymethane by steam reforming and partial oxidation into a hydrogen-rich gas for fuel cell feeding has been carried out....     

Bimetallic Pt<Subscript>0.5</Subscript>Co<Subscript>0.5</Subscript>/SiO<Subscript>2</Subscript> Catalyst: Preparation,Structure, and Properties in Preferential Oxidation of Carbon Monoxide

The Pt_0.5Со_0.5/SiO₂ catalyst has been prepared by the decomposition of a [Pt(NH₃)₄][Co(C₂O₄)₂(H₂O)₂]. 2H₂O binary complex salt supported in the pores of SiO₂ pellets. It has been shown by a complex of physical and chemical methods that Pt_0.5Со_0.5/SiO₂ contains alloy nanoparticles with an average composition Pt0.5Co0.5. The catalytic properties of Pt_0.5Со_0.5/SiO₂ are studied in the preferential oxidation of СО in the reaction mixtures with various compositions. It was found that Pt_0.5Со_0.5/SiO₂ has a high selectivity and makes it possible to decrease the outlet concentration of CO to a level of <10 ppm, and the presence of СО₂ and/or Н₂О in the reaction mixture almost does not affect its catalytic properties. The structure of the catalyst is stable under the conditions of preferential CO oxidation.     

Methane oxidation over mixed-conducting SrFe(Al)O3-delta-SrAl2O4 composite

The steady-state CH4 conversion by oxygen permeating through mixed-conducting (SrFe)0.7(SrAl2)0.3Oz composite membranes, comprising strontium-deficient SrFe(Al)O3-delta perovskite and monoclinic SrAl2O4-based phases, occurs via different mechanisms in comparison to the dry methane interaction with the lattice oxygen. The catalytic behavior of powdered (SrFe)0.7(SrAl2)0.3Oz, studied by temperature-programmed reduction in dry CH4 at 523-1073 K, is governed by the level of oxygen nonstoichiometry in the crystal lattice of the perovskite component and is qualitatively similar to that of other perovskite-related ferrites, such as Sr0.7La0.3Fe0.8Al0.2O3-delta. While extensive oxygen release from the ferrite lattice at 700-900 K leads to predominant total oxidation of methane, significant selectivity to synthesis gas formation, with H2/CO ratios close to 2, is observed above 1000 K, when a critical value of oxygen deficiency is achieved. The steady-state oxidation over dense membranes at 1123-1223 K results, however, in prevailing total combustion, particularly due to excessive oxygen chemical potential at the membrane surface. In combination with surface-limited oxygen permeability, mass transport limitations in a porous layer at the membrane permeate side prevent reduction and enable stable operation of (SrFe)0.7(SrAl2)0.3Oz membranes under air/methane gradient. Taking into account the catalytic activity of SrFeO3-delta-based phases for the partial oxidation of methane to synthesis gas and the important role of mass transport-related effects, one promising approach for membrane development is the fabrication of thick layer of porous ferrite-based catalyst at the surface of dense (SrFe)0.7(SrAl2)0.3Oz composite.     

求解复杂湍流的非线性涡黏性系数模型和代数应力模型

非线性涡黏性系数模型和代数应力模型联系了线性涡黏性系数湍流模型和完整的微分 雷诺应力模型.随着它们受到日益关注,其形式也越来越多样化.本篇综述的目的是对这些模 型加以总结并比较它们之间的共同点及不同之处,指出它们与完整微分雷诺应力模型之间的 关系,以及相对于线性涡黏性系数模型而言它们在预报流场上所具有的优势.     

Gas-Phase Carbonylation of Dimethoxymethane to Methyl Methoxyacetate on Solid Acids: The Effect of Acidity on the Catalytic Activity

The gas-phase carbonylation reaction of dimethoxymethane (DMM) to methyl methoxyacetate on different solid acids was studied. It was established that this reaction was accompanied by the occurrence of a side reaction of DMM disproportionation into dimethyl ether and methyl formate. It was shown that the activity of solid acids in both of the reactions depends on the strength of Brønsted acid sites according to an equation like the Brønsted–Evans–Polanyi–Semenov correlations.     

Copper-cerium oxide catalysts for the selective oxidation of carbon monoxide in hydrogen-containing mixtures: I. Catalytic activity

A series of copper-cerium oxide catalysts were prepared, and their properties toward the reaction of CO oxidation in hydrogen-containing gas mixtures were studied. It was found that the copper-cerium oxide catalysts are stable, active, and selective in this reaction. The conditions under which these catalysts decreased the concentration of CO from 1 to <10^?3 vol % in hydrogen containing water vapor and carbon dioxide were determined.     

Selective oxidation of hydrocarbons into synthesis gas at short contact times: Design of monolith catalysts and main process parameters

This review summarizes the main achievements of the Boreskov Institute of Catalysis (Siberian Division, Russian Academy of Sciences) in the development of efficient and stable monolith catalysts for selective oxidation of hydrocarbons into synthesis gas at short contact times. Research in this field has included (1) design of new types of active component based on metal oxides, (2) design of new types of monolith support and development of supporting procedures for active components, and (3) optimization of process parameters for different types of fuel (natural gas, isooctane, and gasoline) and oxidant (air oxygen, including its mixtures with water and carbon dioxide), including the start-up regime. Design of active components (platinum, nickel, or their combination) supported on fluorite-like solid solutions based on cerium dioxide and rare-earth (samarium, gadolinium, and praseodymium) or zirconium cations has been aimed at separating hydrocarbon activation (on metal sites) and oxidation (on the support) and conjugating the separated steps of hydrocarbon oxidation at the metal-oxide interface. Optimization of oxygen mobility in the support lattice by varying the nature and concentration of doping cation along with optimization of hydrocarbon activation on supported metal clusters allow hydrocarbons to be completely converted into synthesis gas by selective oxidation or dry or steam reforming at contact times of a few milliseconds, ruling out undesirable carbon build-up on the catalyst surface. The development of new types of monolith support has targeted the enhancement of thermal shock resistance, including testing of supports based on thermally stable metal foils and composites (cermets). The main steps of the production of these supports have been refined, including unique technologies of blast dusting and hydrothermal treatment. The electric conductivity of these systems allows a quick startup of selective oxidation to be performed by passing electric current, and their thermal conductivity minimizes the temperature gradient arising from heat transfer in the bed. Procedures for loading monolith supports with active components have been developed, including impregnation, washcoating, or encapsulation in cermet matrices. The catalysts produced show a high efficiency and an operational stability adequate to the above tasks in the selective oxidation and steam-air autothermal reforming of natural gas (including processes under pressure), isooctane, and gasoline into synthesis gas.__________Translated from Kinetika i Kataliz, Vol. 46, No. 2, 2005, pp. 243–268.Original Russian Text Copyright © 2005 by Sadykov, Pavlova, Bunina, Alikina, Tikhov, Kuznetsova, Frolova, Lukashevich, Snegurenko, Sazonova, Kazantseva, Dyatlova, Usoltsev, Zolotarskii, Bobrova, Kuzmin, Gogin, Vostrikov, Potapova, Muzykantov, Paukshtis, Burgina, Rogov, Sobyanin, Parmon.     

Kinetic model and mechanism of the selective oxidation of CO in the presence of hydrogen on platinum catalysts

The reaction kinetics of the selective oxidation of carbon monoxide in the presence of hydrogen on a Pt/carbon support catalyst was studied. It was found that this catalyst exhibited high activity and decreased the concentration of CO in a hydrogen-containing gas from 0.6–1.0 vol % to less than 10 ppm at the inlet concentration ratio O₂/CO = 1.0–1.5. A kinetic model of the reaction was proposed to describe quantitatively the experimental results.     

Bimetallic Rh-Co/ZrO<Subscript>2</Subscript> catalysts for ethanol steam reforming into hydrogen-containing gas

The properties of supported bimetallic Rh-Co/ZrO₂ catalysts in ethanol steam reforming into hydrogen-containing gas were studied. The particles of Rh-Co solid solutions on the catalyst surface were prepared by the thermal decomposition of the double complex salt [Co(NH₃)₆][Rh(NO₂)₆] and the solid solution Na₃[RhCo(NO₂)₆]. It was found that the bimetallic Rh-Co/ZrO₂ catalysts exhibited high activity in the reaction of ethanol steam reforming. The equilibrium composition of reaction products was attained at 500–700°C and a reaction mixture space velocity of 10000 h⁻¹.