Supported catalysts alumina-based

In a previous study, we found that Pd (lwt%) catalysts supported on finely divided aliunina aerogels were more active, in the oxidation of CO by NO and O2, than both Pd and Pt-Rh supported on commercial aluminas [2], More recently, a study of propane oxidation over Pd supported on alumina-based aerogel catalysts led to the conclusion that favorable ensembles of active sites contituted by Pd° atoms and Pda" " ions might exist for this reaction [3],... 

Organochromium Catalysts. Several commercially important catalysts utilize organ ochromium compounds. Some of them are prepared by supporting bis(triphenylsilyl)chromate on siUca or siUca-alumina in a hydrocarbon slurry followed by a treatment with alkyl aluminum compounds (41). Other catalysts are based on bis(cyclopentadienyl)chromium deposited on siUca (42). The reactions between the hydroxyl groups in siUca and the chromium compounds leave various chromium species chemically linked to the siUca surface. The productivity of supported organochromium catalysts is also high, around 8—10 kg PE/g catalyst (800—1000 kg PE/g Cr). 

Sodium alumiaate is widely used in the preparation of alumina-based catalysts. Aluminosilicate [1327-36-2] can be prepared by impregnating siHca gel with alumiaa obtained from sodium alumiaate and aluminum sulfate (41,42). Reaction of sodium alumiaate with siHca or siHcates has produced porous crystalline alumiaosiHcates which are useful as adsorbents and catalyst support materials, ie, molecular sieves (qv) (43,44). 

While the discovery of the catalytic properties of zeolites was driven by the desire to improve industrial prcKessing, the development of emission control catalysts was necessitated by governmental fiat. The first requirement was for 90+% removal of CO and of hydrocarbons, a goal which could not be met by oxidation with base metal oxides. To achieve the required spedfications during automobile operations, it was necessary to develop supported platinum catalysts. Originally the support was alumina in pellet form. Later platinum on cordierite was used in honeycomb form, containing 200-400 square channels per square inch. 

A recent comparative investigation of the NO + CO reaction shows a significant rate enhancement in the formation of N2 on Ce0.98Pda02O2 8 prepared via a combustion synthesis method in comparison with conventional Pd-based catalysts supported on alumina... 

Previous kinetic investigations dealing with the NO + H2 reaction over supported noble metal-based catalysts showed different kinetic features according to the nature of the support [29,53-58], Initially, this reaction has been described in the absence of oxygen on Rh deposited on silica and alumina by the following mechanism [29],... 

Supported Co, Ni, Ru, Rh, Pd and Pt as well as Raney Ni and Co catalysts were used for the hydrogenation of dodecanenitrile to amines in stirred SS autoclaves both in cyclohexane and without a solvent. The reaction temperature and the hydrogen pressure were varied between 90-140 °C and 10-80 bar, respectively. Over Ni catalysts NH3 and/or a base modifier suppressed the formation of secondary amine. High selectivity (93-98 %) to primary amine was obtained on Raney nickel, Ni/Al203 and Ru/A1203 catalysts at complete nitrile conversion. With respect to the effect of metal supported on alumina the selectivity of dodecylamine decreased in the order Co Ni Ru>Rh>Pd>Pt. The difference between Group VIII metals in selectivity can be explained by the electronic properties of d-band of metals. High selectivity to primary amine was achieved on base modified Raney Ni even in the absence of NH3. 

An alumina-based catalyst will be bound, for the purpose of mechanical strength, with carbon. The alumina-carbon mixture is essentially a composite support for adsorbing the Pt precursor. If it is desired that all metal go onto the alumina phase, which type of carbon (oxidized or unoxidized) and what type of Pt complex should be used and why A sketch of the surface potential vs. pH for alumina and the carbon binder will help. 

The high-density polyethylene is linear and can be manufactured by (i) coordination polymerisation of monomer by triethyl aluminium and tritanium chloride, (ii) polymerisation with supported Metal Oxide Catalysts. Such as chromium or molybdenum oxides supported over alumina-silica bases. 

Upon discovery of this mechanism, new catalysts have been developed, now presenting alkylidene ligands in the metal coordination sphere, such as [(=SiO) Ta(=CH Bu)Np2 and [(=SiO)Mo(=NAr)(=CH Bu)Np] [43, 88]. Table 11.4 presents results obtained with several catalysts prepared by SOMC. Although [(=SiO) Ta(CH3)3Cp (=SiOSi=)] is not active in alkane metathesis (the tantalum site would not be as electrophilic as required) [18], results obtained with [(=SiO)Mo(=NAr) (=CH Bu)Np] show that ancillary ligands are not always detrimental to catalytic activity this species is as good a catalyst as tantalum hydrides. Tungsten hydrides supported on alumina or siHca-alumina are the best systems reported so far for alkane metathesis. The major difference among Ta, Mo and W catalysts is the selectivity to methane, which is 0.1% for Mo and less than 3% for W-based catalysts supported on alumina, whereas it is at least 9.5% for tantalum catalysts. This... 

The same authors (77) also investigated the Michael addition of nitromethane to a,/l-unsaturated carbonyl compounds such as methyl crotonate, 3-buten-2-one, 2-cyclohexen-l-one, and crotonaldehyde in the presence of various solid base catalysts (alumina-supported potassium fluoride and hydroxide, alkaline earth metal oxides, and lanthanum oxide). The reactions were carried out at 273 or 323 K the results show that SrO, BaO, and La203 exhibited practically no activity for any Michael additions, whereas MgO and CaO exhibited no activity for the reaction of methyl crotonate and 3-buten-2-one, but low activities for 2-cyclohexen-l-one and crotonaldehyde. The most active catalysts were KF/alumina and KOH/alumina for all of the Michael additions tested. 

The ATR of glycerol has also been examined over Pt- and Rh-based catalysts supported on alumina foams [298]. High selectivity to H2 can be achieved by adjusting the fuel-to-air and fuel-to-steam feed ratios, and also the catalyst formulation. The addition of ceria to AI2O3 provides a catalyst vhich shows high fuel conversion and high selectivity to H2. 

SMSI is also thought to affect methanation catalysts (normally transition metal or noble metals supported on alumina), which are used in the producton of substitute natural gas (SNG). In general, heating in H2 causes sintering on alumina and silica supports and heating in O2 or steam can cause dispersion and particle coalescence at 200 °C (Rukenstein and Lee 1984,1987, Nakayama et al 1984). The data have been based on ex situ EM studies. Here EM methods, especially under dynamic reaction conditions, can provide a wealth of new insights into metal-support interactions under reaction conditions. 

When controlled nitridation of surface layers is required, as for example in the modification of the chemical properties of the surface of a support, the atomic layer deposition (ALD) technique can be applied." This technique is based upon repeated separate saturating reactions of at least two different reactants with the surface, which leads to the controlled build-up of thin films via reaction of the second component with the chemisorbed residues of the first reactant. Aluminium nitride surfaces have been prepared on both alumina and silica supports by this method wherein reaction cycles of trimethylaluminium and ammonia have been performed with the respective supports, retaining their high surface areas." This method has been applied to the modification of the support composition for chromium catalysts supported on alumina." ... 

Catalysts. - Group VIII metals, conventional base metal catalysts (Ni, Co, and Fe) as well as noble metal catalysts (Pt, Ru, Rh, Pd) are active for the SR reaction. These are usually dispersed on various oxide supports. y-Alumina is widely used but a-alumina, magnesium aluminate, calcium aluminate, ceria, magnesia, pervoskites, and zirconia are also used as support materials. The following sections discuss the base metal and noble metal catalysts in detail, focusing on liquid hydrocarbon SR for fuel cell applications. 

Noble Metal Catalysts. Rh-based catalysts have been investigated on different supports, resulting in different H2 and CO yields. Gasoline and naphtha POX over a supported Rh catalyst were reported by Fujitani et al. For y-alumina supported Rh catalyst, maximum yields of 96% of both H2 and CO were reported with 0.2 wt% Rh loading at 700°C, an air equivalence ratio of 0.41, and a liquid hourly space velocity (LHSV) of 2 h A 0.05 wt% Rh supported on zirconia yielded 98% H2 and 85% CO at 725°C, an... 

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