Supported noble-metal catalysts

Another example of catalytic isomerization is the Mobil Vapor-Phase Isomerization process, in which -xylene is separated from an equiHbrium mixture of Cg aromatics obtained by isomerization of mixed xylenes and ethylbenzene. To keep xylene losses low, this process uses a ZSM-5-supported noble metal catalyst over which the rate of transalkylation of ethylbenzene is two orders of magnitude larger than that of xylene disproportionation (12). 

Usually noble metal NPs highly dispersed on metal oxide supports are prepared by impregnation method. Metal oxide supports are suspended in the aqueous solution of nitrates or chlorides of the corresponding noble metals. After immersion for several hours to one day, water solvent is evaporated and dried overnight to obtain precursor (nitrates or chlorides) crystals fixed on the metal oxide support surfaces. Subsequently, the dried precursors are calcined in air to transform into noble metal oxides on the support surfaces. Finally, noble metal oxides are reduced in a stream containing hydrogen. This method is simple and reproducible in preparing supported noble metal catalysts. 

Methanol is a major bulk chemical, and its global annual production exceeds 37 million tons. It is mainly used for the production of formaldehyde and methyl 6butyl ether (MTBE). Especially, formaldehyde is dominantly used for producing resins. At present, methanol and its decomposed derivatives can be oxidized to CO2 and H2O by the proper selection of supported noble metal catalysts such as palladium, platinum, and gold. 

Vinke, H., 1991, Oxidation of Carbohydrates and Derivatives using Carbon Supported Noble Metal Catalysts , Ph.D. Thesis, TU Delft, The Netherlands. 

Simonov PA, Likholobov VA. 2003. Physicochemical aspects of preparation of carbon-supported noble metal catalysts. In Wieckowski A, Savinova ER, Vayenas CG. editors. Catalysis and Electrocatalysis at Nanoparticle Surfaces. New York Marcel Decker. 

Panagiotopoulou, P., and Kondarides, D.I. 2004. Effect of morphological characteristics of Ti02-supported noble metal catalysts on their activity for the water-gas shift reaction. J. Catal. 225 327-36. 

The aqueous phase air oxidation of glycerol with supported noble metal catalysts occurs under mild conditions (60 °C), but is very dependant on the pH of the reaction medium. Relevant data are shown in Fig. 11.3 [48], For Pd, Pt and Bi-promoted Pt the glycerol oxidation rate increases significantly with the pH of the medium, with Pd showing the lower activity. 

It is well established that commercially important supported noble metal catalysts contain small metal crystallites that are typically smaller than a few nanometers. The surface of these crystallites is populated by different types of metal atoms depending on their locations on the surface, such as comers, edges, or terraces. In structure sensitive reactions, different types of surface metal atoms possess quite different properties. For example, in the synthesis of ammonia from nitrogen and hydrogen, different surface crystallographic planes of Fe metal exhibit very different activities. Thus, one of the most challenging aspects in metal catalysis is to prepare samples containing metal particles of uniform shape and size. If the active phase is multicomponent, then it is also desirable to prepare particles of uniform composition. 

Numerous studies have been published on catalyst material directly related to rich catalytic combustion for GTapplications [73]. However, most data are available on the catalytic partial oxidation of methane and light paraffins, which has been widely investigated as a novel route to H2 production for chemical and, mainly, energy-related applications (e.g. fuel cells). Two main types of catalysts have been studied and are reviewed below supported nickel, cobalt and iron catalysts and supported noble metal catalysts. 

Supported noble metal catalysts (Pt, Pd, Ag, Rh, Ni, etc.) are an important class of catalysts. Depositing noble metals on high-area oxide supports (alumina, silica, zeolites) disperses the metal over the surface so that nearly every metal atom is on the surface. A critical property of supported catalysts is that they have high dispersion (fraction of atoms on the surface), and this is a strong function of support, method of preparation, and treatment conditions. Since noble metals are very expensive, this reduces the cost of catalyst. It is fairly common to have situations where the noble metals in a catalyst cost more than 100,000 in a typical reactor. Fortunately, these metals can usually be recovered and recycled when the catalyst has become deactivated and needs to be replaced. 

Due to the absence of electron withdrawing groups the aromatic amines are hydrogenated with difficulty. Supported noble metal catalysts (Pd, Pt, Ru, Rh, Ir) are usually active at elevated temperature and pressure. The perhydrogenation of aromatic amines is mainly accompanied by two side reactions, i.e. the... 

In the case of supported metal particles, experimental studies of particle growth mechanisms can determine the type of ripening. Generally, studies on supported noble metallic catalysts at elevated temperatures (>500°C) indicate atomic diffusion from smaller metal particles across the surface of the support to... 

Ce02-supported noble-metal catalysts such as Pt, Pd and Rh are of interest because of their importance in the so-called three-way converter catalysts (TWC), designed to reduce emissions of CO, NOx and uncombusted hydrocarbons in the environment and to purify vehicle-exhaust emissions. Such catalysts are also of current interest in steam reforming of methane and other hydrocarbons. Conventional practical catalysts for steam reforming consist of nickel supported on a ceramic carrier with a low surface area and are used at high temperatures of 900 C. This catalyst suffers from coke formation which suppresses the intrinsic catalyst activity. Promoters such as Mo are added to suppress coke formation. Recently, Inui etal(l991) have developed a novel Ni-based composite... 

Conventional Ni-based catalysts still dominate in SR applications however, ceria-supported noble metal catalysts have also attracted interest reeently. The study of Rh for both POX and ATR has increased sinee Rh is in general more active for reforming and is less prone to form carbon. H2 and CO selectivities in Rh-based catalysts have been shown to be affected by catalyst geometry. This indicates that feed mixing and mass transfer can play an important role. 

Halogenation. Fluorination, chlorination, and bromination of alkanes catalyzed by superacids have been reported.1,2 Reactions may be carried out in the liquid phase, or in the gas phase over solid superacids or supported noble metal catalysts. High selectivity and relatively mild reaction conditions are the main features of these transformations. 

A comparative study of Ti02-supported noble metal catalysts, which were prepared by impregnation, was carried out for the oxidation of a low concentration of HCHO (100 ppm) by Zhang and He [102], As far as impregnation method is concerned, Au/ Ti02 is less active than Pt/Ti02, giving 90% HCHO conversion at 393 K and 100% conversion at room temperature, respectively. 

Structure and Properties of Supported Noble Metal Catalysts... 

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