Support of metal catalysts

On the other hand the carbon materials are widely known supports of metal catalysts from of old. It has been shown, that the carbon supports increase the dehydrogenative properties of the metal catalysts due to the epitaxial changing of metal crystal structure providing their structural relevance with reacting molecules [8],... 

Intentional doping with alkali metal ions is widely used to reduce the activity of alumina in supported catalysts. It has also been shown that doping with cations of alkali metals, alkaline earth metals, and rare-earth metals increases the stabihty of alumina with respect to phase transitions and loss of surface area. To reduce the surface activity and to increase the stabihty of alumina for use as a support of metal catalysts in commercial appHcations, phases that have already gone through most of the possible structural evolution (0-AI2O3 or a-Al203) with moderate to low surface area (100 to 5 m g ) are needed doping with alkah metal, alkahne-earth metal, or rare earth metal cations may also be useful. Other impurities may be present in... 

Regarding the use of TiOj-SiOj gels as supports of metal catalysts the textural properties of the aerogels are particularly favorable. The lack of microporosity joints to the very high values of specific surface areas and, as pointed out in the results, their porous structure can resist a conventional impregnation treatment without severe changes in texture. 

Alkali moderation of supported precious metal catalysts reduces secondary amine formation and generation of ammonia (18). Ammonia in the reaction medium inhibits Rh, but not Ru precious metal catalyst. More secondary amine results from use of more polar protic solvents, CH OH > C2H5OH > Lithium hydroxide is the most effective alkah promoter (19), reducing secondary amine formation and hydrogenolysis. The general order of catalyst procUvity toward secondary amine formation is Pt > Pd Ru > Rh (20). Rhodium s catalyst support contribution to secondary amine formation decreases ia the order carbon > alumina > barium carbonate > barium sulfate > calcium carbonate. 

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). 

Abstract—Carbon nanotubules were produced in a large amount by catalytic decomposition of acetylene in the presence of various supported transition metal catalysts. The influence of different parameters such as the nature of the support, the size of active metal particles and the reaction conditions on the formation of nanotubules was studied. The process was optimized towards the production of nanotubules having the same diameters as the fullerene tubules obtained from the arc-discharge method. The separation of tubules from the substrate, their purification and opening were also investigated. 

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. 

Table 3.1 Catalytic activity of supported lb metal catalysts for MeOH oxidation [53]. ...

The immobilization of metal catalysts onto sohd supports has become an important research area, as catalyst recovery, recycling as well as product separation is easier under heterogeneous conditions. In this respect, the iron complex of the Schiff base HPPn 15 (HPPn = iVA -bis(o-hydroxyacetophenone) propylene diamine) was supported onto cross-linked chloromethylated polystyrene beads. Interestingly, the supported catalyst showed higher catalytic activity than the free metal complex (Scheme 8) [50, 51]. In terms of chemical stability, particularly with... 

GP 9] [R 16] The reaction rate and activation energy of metal catalysts (Rh, Pt or Pd) supported on alumina particles ( 3 mg 53-71 pm) were determined for conversions of 10% or less at steady state (1% carbon monoxide 1% oxygen, balance helium 20-60 seem up to 260 °C) [7, 78]. The catalyst particles were inserted into a meso-channel as a mini fixed bed, fed by a bifurcation cascade of micro-channels. For 0.3% Pd/Al203 (35% dispersion), TOF (about 0.5-5 molecules per site... 

Besides supported (transition) metal catalysts, structure sensitivity can also be observed with bare (oxidic) support materials, too. In 2003, Hinrichsen et al. [39] investigated methanol synthesis at 30 bar and 300 °C over differently prepared zinc oxides, namely by precipitation, coprecipitation with alumina, and thermolysis of zinc siloxide precursor. Particle sizes, as determined by N2 physisorpt-ion and XRD, varied from 261 nm for a commercial material to 7.0 nm for the thermolytically obtained material. Plotting the areal rates against BET surface areas (Figure 3) reveals enhanced activity for the low surface area zinc... 

A hypothesis that edge and corner sites work as active sites can explain why turn over frequency (TOF), which is defined as the reaction rate per one active site, in the case of metal catalysts, per surface exposed metal atom, increases with a decrease in the diameter of gold particles. However, it fails to explain the significant contribution of support materials and the contact structure of gold NPs. It seems to be reasonable that those edges and corners act as the sites for adsorption of one of the reactants, for example, CO in its oxidation. 

Polycondensation pol5mers, like polyesters or polyamides, are obtained by condensation reactions of monomers, which entail elimination of small molecules (e.g. water or a hydrogen halide), usually under acid/ base catalysis conditions. Polyolefins and polyacrylates are typical polyaddition products, which can be obtained by radical, ionic and transition metal catalyzed polymerization. The process usually requires an initiator (a radical precursor, a salt, electromagnetic radiation) or a catalyst (a transition metal). Cross-linked polyaddition pol5mers have been almost exclusively used so far as catalytic supports, in academic research, with few exceptions (for examples of metal catalysts on polyamides see Ref. [95-98]). 

From the discussion in the previous sections, it is apparent that whatever the morphology of the CFP, macroreticular or gel-type, the metal nanoclusters in polymer-supported heterogeneous metal catalysts are... 

A wide variety of solid materials are used in catalytic processes. Generally, the (surface) structure of metal and supported metal catalysts is relatively simple. For that reason, we will first focus on metal catalysts. Supported metal catalysts are produced in many forms. Often, their preparation involves impregnation or ion exchange, followed by calcination and reduction. Depending on the conditions quite different catalyst systems are produced. When crystalline sizes are not very small, typically > 5 nm, the metal crystals behave like bulk crystals with similar crystal faces. However, in catalysis smaller particles are often used. They are referred to as crystallites , aggregates , or clusters . When the dimensions are not known we will refer to them as particles . In principle, the structure of oxidic catalysts is more complex than that of metal catalysts. The surface often contains different types of active sites a combination of acid and basic sites on one catalyst is quite common. 

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. 

Superficially the Oryx GTL refinery design has much in common with the SMDS process, but there are important differences. There is no separate hydrotreater, which limits production of chemicals, such as waxes. The hydrocracker employs the Chevron Isocracking technology, which is based on a sulfided supported base-metal catalyst that was designed for crude oil conversion. The operating conditions of the hydrocracker are also more severe (>350°C, 7 MPa) than those required by the SMDS process (300-350°C, 3-5 MPa). Only intermediate products are produced (Table 18.13),5 with the naphtha slated as cracker feed and the distillate as blending component for diesel fuel. 

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. 

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