Showing papers in "Catalysis Reviews-science and Engineering in 2002"

Catalytic combustion of methane over palladium-based catalysts

Abstract: Palladium-based catalysts are widely applied in exhaust catalytic converter and catalytic combustion systems. The mechanism for methane oxidation on a Pd-based catalyst is complex. Catalyst activity is influenced by variations in the process pressure and temperature, by the gas mixture composition, by the type of support and various additives, and by pretreatment under reducing or oxidizing atmospheres. In this paper, we review the literature on supported Pd catalysts for combustion of methane. The mechanisms involved are discussed taking into consideration the oxidation/reduction mechanisms for supported palladium, poisoning, restructuring, the form of oxygen on the surface, methane activation over Pd and PdO phases, and transient behavior. Our review helps explain the array of experimental results reported in the literature.

Acid-catalyzed synthesis of mono- and dialkyl benzenes over zeolites: active sites, zeolite topology, and reaction mechanisms

Abstract: This review describes mechanisms of catalytic reactions leading to mono- and dialkyl benzenes over zeolites, which represent an important part of petrochemical products. The emphasis is given to the effect of the type of acid sites, zeolite structure, and reaction conditions on the activity and selectivity of these complex reactions, and particularly to the individual products with respect to their iso- vs. n- and ortho-, meta-, and para-isomers. The first part of the paper deals with the description and analysis of the structure and properties of the acid sites, and zeolite pore inner structure applied in synthesis of alkyl benzenes. Individual reactions leading to the synthesis of propyl benzene, xylenes, ethyl toluenes, diethyl benzenes, and transformation of trimethyl benzenes to xylenes from the view point of the reaction mechanism, function of the acid sites, and inner pore geometry of zeolites are described in the second part.

Multiphase catalytic reactors: a perspective on current knowledge and future trends

Abstract: Conventional and emerging processes that require the application of multiphase reactors are reviewed with an emphasis on catalytic processes. In the past, catalyst discovery and development preceded and drove the selection and development of an appropriate multiphase reactor type. This sequential approach is increasingly being replaced by a parallel approach to catalyst and reactor selection. Either approach requires quantitative models for the flow patterns, phase contacting, and transport in various multiphase reactor types. This review focuses on these physical parameters for various multiphase reactors. First, fixed-bed reactors are reviewed for gas-phase catalyzed processes with an emphasis on unsteady state operation. Fixed-bed reactors with two-phase flow are treated next. The similarities and differences are outlined between trickle beds with cocurrent gas–liquid downflow, trickle-beds with countercurrent gas–liquid flow, and packed-bubble columns where gas and liquid are contacted in coc...

BINARY MgO-BASED SOLID SOLUTION CATALYSTS FOR METHANE CONVERSION TO SYNGAS

Abstract: The excellent catalytic performance and high stability of MgO–NiO solid solution catalysts in CH4 conversion to syngas generated the recent outburst of interest for the binary MgO-based solid solutions. This review will focus on the relationship between the catalytic performance of the binary MgO-based solid solution and its properties in the CO2 reforming, the partial oxidation and the steam reforming of methane. First, the development of methane conversion to syngas will be summarized. Second, the role of the basicity and of the solid solution in the design of a catalyst that can inhibit carbon deposition and active metal sintering will be examined. Third, the main results regarding the catalytic performance of the MgO-based solid solutions will be presented. Fourth, detailed information regarding the effects of the NiO/MgO composition, surface area, pore distribution, crystal lattice parameter, precursors, and preparation condition on its catalytic behavior will be provided.

Lipases and lipase-catalyzed esterification reactions in nonaqueous media

Abstract: Enzymatic reactions in nonaqueous solvents offer new possibilities for the biotechnological production of many useful chemicals using reactions that are not feasible in aqueous media. In the recent years, the use of enzymes in nonaqueous media has found applications in organic synthesis, chiral synthesis or resolution, modification of fats and oils, synthesis of sugar-based polymers, etc. The use of lipases in esterification reactions to produce industrially important products such as emulsifiers, surfactants, wax esters, chiral molecules, biopolymers, modified fats and oils, structured lipids, and flavor esters is well documented. The interest in using lipases as biotechnological vectors for performing various reactions in both macro- and microaqueous systems has picked up tremendously during the last decade. This review covers important features of lipases and lipase-catalyzed esterification reactions including the kinetics and stability of lipases, and modeling aspects.

Preparation and use of hybrid organic–inorganic catalysts

Abstract: Various approaches towards the immobilization of molecular homogeneous catalysts are introduced, focusing on catalysts where an organic molecule is attached to the surface of an inorganic support material via a covalent bond forming the so-called hybrid organic–inorganic catalysts. The application of this new class of catalysts in a wide variety of organic reactions is reviewed.

Hydrogen activation by transition metal sulfides

Abstract: The activity of the conventional catalysts during hydroprocessing results from the ability of Mo(W)S2 to adsorb and activate hydrogen. The optimum of hydrogen adsorption occurs at the S/Mo(W) ratio of about 1.95. This is consistent with removal of the corner and edge sulfur atoms leading to the formation of the sulfur anion vacancies. The heterolytic dissociation, involving both metal and sulfur ions, is the predominant mode of hydrogen activation. It leads to the formation of metal–H and S–H moieties. The homolytic dissociation, occurring on the sulfur ion pairs, is much less evident. For the supported catalysts, the amount of the adsorbed hydrogen per unit of Mo(W) is significantly greater. This results from the spillover of the active hydrogen from the active phase on the support. The surface hydrogen can migrate back from the support to the active phase. Promoters, such as Ni and Co, increase the rate of adsorption, whereas their effect on the total amount of the adsorbed hydrogen is much less pronoun...

Catalytic oxidative dehydrogenation of n-butane

Abstract: This review deals with the catalytic conversion of n-butane by oxidative dehydrogenation as an alternative process to direct dehydrogenation, making special reference to the catalytic systems used, kinetic studies performed and reaction mechanisms proposed. Particular attention is also focused on the hydrocarbon activation process and on the main factors governing catalytic efficiency. Finally, after some general conclusions, future trends are analyzed.

XANES analysis of catalytic systems under reaction conditions

Abstract: The article gives an overview of the XANES technique contribution to the analysis of multicomponent catalysts. The theoretical basis of the technique, the interpretation of the energy position and intensity of XANES features, and the numerical methods developed to interpret XANES data on catalytic systems are described and discussed in the first part. In the second part, the most recent XANES studies of catalytic samples are reviewed, giving particular attention to the solid state chemistry information extracted under real, in-situ conditions. This concerns structural and redox properties of the systems during preparation stages, activation treatments like reduction, oxychlorination, or sulfidation, and reaction conditions. Additional effort was made to describe the use of XANES to gain insight on electronic properties of catalysts. The influence of all these redox, geometrical and electronic properties on catalytic behavior, particularly as a function of particle size and active metal-support in...

Activation of methane by oxygen and nitrogen oxides

Abstract: A n transition state of species n CSTR continuous stirred tank reactor DFT density-functional theory E a apparent activation energy FT Fischer–Tropsch synthesis H° enthalpy of formation JSR jet sti...

Etherification on Zeolites: MTBE synthesis

Abstract: Although the use of methyl-tert butyl ether (MTBE) in reformulated gasoline has raised concerns due to its detection in ground water and has led to its gradual phase out in parts of the United States, the use of heavier ethers in gasoline in the future is possible. The synthesis of MTBE provides us with an insight into etherification reactions in general. This article reviews the extensive findings over the past 15 years on the application of acidic zeolites as alternative catalysts for etherification reactions and, in particular, MTBE synthesis, and compares the results with those of the commercially used ion-exchange resins. Although the resin catalysts are very active, they have some significant drawbacks (i.e., thermal fragility, sensitivity to methanol/isobutene ratios, and corrosive/disposal problems). Zeolites have been considered to be potential alternative catalysts for MTBE synthesis due to their excellent properties such as high thermal stability and modifiable acidity. The impact of various ze...

Recent advances and future aspects in the low-temperature conversion of saturated hydrocarbons

Abstract: A brief review on the advances and future aspects in the low-temperature activation of carbon–hydrogen and carbon–carbon bonds in hydrocarbons is presented. Particular attention is given to a catalyst formulation for low-temperature conversion of hydrocarbons. An efficient catalyst design method for low-temperature activation of saturated hydrocarbons has been worked out using metal evaporation techniques. The characteristic property of such catalysts is the presence of metal particles on the surface in an atomically dispersed state. Some of the prepared catalysts cause complete hydrocracking of alkanes and cycloalkanes at 423–463K.