Gel catalysts

Preparation. Thiophosgene forms from the reaction of carbon tetrachloride with hydrogen sulfide, sulfur, or various sulfides at elevated temperatures. Of more preparative value is the reduction of trichi oromethanesulfenyl chloride [594-42-3] by various reducing agents, eg, tin and hydrochloric acid, staimous chloride, iron and acetic acid, phosphoms, copper, sulfur dioxide with iodine catalyst, or hydrogen sulfide over charcoal or sihca gel catalyst (42,43). 

Extensive research has been conducted on catalysts that promote the methane—sulfur reaction to carbon disulfide. Data are pubhshed for sihca gel (49), alurnina-based materials (50—59), magnesia (60,61), charcoal (62), various metal compounds (63,64), and metal salts, oxides, or sulfides (65—71). Eor a sihca gel catalyst the rate constant for temperatures of 500—700°C and various space velocities is (72)... 

The kinetics of the ethylene hydration reaction have been investigated for a tungstic oxide—siHca gel catalyst, and the energy of activation for the reaction deterrnined to be 125 kJ/mol (- 30 kcal/mol) (106,120). The kinetics over a phosphoric acid-siHca gel catalyst have been examined (121). By making some simplifying assumptions to Taft s mechanism, a rate equation was derived ... 

A platinum on silica gel catalyst was prepared by impregnation of silica gel (BDH, for chromatographic adsorption) by a solution containing 0.5% (wt.) of sodium hydroxide and 0.5% (wt.) of chloroplatinic acid (both of analytical grade). The dried catalyst contained 1% (wt.) of platinum and a corresponding amount of the alkaline component. The BET surface area of the catalyst was 40 m2/g, the mean pore radius 150 A. The catalyst was always reduced directly in the reactor in a stream of hydrogen at 200°C for 2 hr. 

A platinum-iron on silica gel catalyst was prepared by impregnating silica gel (BDH, for chromatographic adsorption) with an aqueous solution of chloroplatinic acid (analytical grade) and sodium hydroxide (analytical grade). The dry product was then impregnated by a ferrous sulfate solution (C.P. grade) and the water was removed in a rotating evaporator. The prepared catalyst contained 1% Pt, 0.7% Fe, and 2% NaOH (by... 

A procedure similar to that used in the investigation of the hydro-demethylation of xylenes was also employed in a study of the consecutive hydrogenation of phenol via cyclohexanone to cyclohexanol in gaseous phase on a platinum on silica gel catalyst (p. 27) at 150°C [scheme (VI)] at this temperature both reactions were irreversible under the excess hydrogen used. 

From the study of the influencing of single reactions by products and by other added substances and from the analysis of mutual influencing of reactions in coupled systems, the following conclusions can be drawn concerning adsorption of the reaction components. (1) With the exception of crotyl alcohol on the platinum-iron-silica gel catalyst, all the substances present in the coupled system, i.e. reactants, intermediate products, and final products, always adsorbed on the same sites of the catalytic surface (competitive adsorption). This nonspecificity was established also in our other studies (see Section IV.F.2) and was stated also by, for example, Smith and Prater (32), (2) The adsorption of starting reactants and the desorption of the intermediate and final products appeared in our studies always as faster, relative to the rate of chemical transformations of adsorbed substances on the surface of the catalyst. 

According to detailed XRD analyses, the two catalyst preparation procedures under study formed solid solutions. The application of sol-gel method led to improved selectivity to olefins in the reaction of propane ODH, compared to the simple procedure of evaporation and decomposition. However, the propane conversion on the sol-gel catalysts was lower at the same experimental conditions, while the catalysts surface area was higher. Moreover, the sol-gel samples presented higher basicity as shown by C02 TPD. It could be explained by a better incorporation of Nd into the AEO lattice, creating cationic vacancies for attaining electroneutrality and thus rendering the nearby oxide anions coordinatively unsaturated and more basic. 

Alumina, silica, clays, and zeolites are increasingly used as acidic or basic supports [26], Cycloaddition reactions often require Lewis-acid catalysts if good yields are to be obtained. Clay and doped silica gel catalysts have emerged as useful alternatives to the use of Lewis acids. Cycloaddition offuran (5) under solvent-free conditions, catalyzed by K10 montmorillonite, results in a decrease in the reaction time the endo-exo relationship is no different that obtained by use of classical heating (Scheme 9.2) [27]. 

For several silica-supported catalysts in condensed phase, including the SAPC system, the rates are disappointing. This can be assigned to slow mass transfer, and perhaps to incomplete rhodium hydride formation as we have discussed and observed. The sol-gel catalyst is relatively fast and is sometimes only a few times slower than the homogeneous one. Since only limited ways of preparation were tested, there is probably more scope for sol-gel catalysts. Space-time yields are promising at the present state of affairs. 

In general, sol-gel catalysts are heterogeneous materials employing solid-liquid or solid-gaseous interphases. A mobile and a stationary component penetrate each other at the molecular level with the catalytic species being well-defined, highly mobile and homogeneously distributed... 

Along with hydrophobicity, large amounts of both water (to promote hydrolysis) and methanol employed as co-solvent in the catalyst preparation (to promote homogeneity) are needed to ensure optimal reactivity, showing the number of experimental parameters of the sol-gel synthesis which can be controlled independently to optimize the performance of the resulting catalyst. Finally, in contrast to zeolites and other crystalline porous materials, amorphous sol-gel materials show a distribution of porosity which does not restrict the scope of application of sol gel catalysts to substrates under a threshold molecular size. 

The resulting sol-gel catalysts usually proved more stable and versatile under ambient conditions than their homogeneous analogues. For example, a remarkable asymmetric hydrogenation of prochiral itaconic acid over sol-gel entrapped (—)-Ru-BINAP in water becomes possible which simply cannot be done with non-entrapped, water-insoluble catalysts. 

Another important highly selective and stable hydroformylation sol gel catalyst is made of silica-supported rhodium covalently bound to supported Xantphos family of ligands.36 By incorporating monoliths of the sol-gel doped material into the paddles of an autoclave stirrer, the catalyst (Rotacat) can be used in a continuous liquid flow process. A single sample of this catalyst was used for a variety of different hydroformylation reactions under widely varying conditions over a period of more than a year, still retaining its selective activity. 

R. Ciriminna, L. M. Ilharco, A. Fidalgo, S. Campestrini and M. Pagliaro, The structural origins of superior performance in sol-gel catalysts, Soft Matter, 2005, 1, 231. 

As shown, for instance, by the lack of any sol-gel catalyst cited in a recent, thorough review covering tens of industrial applications of sol-gel hybrid materials C. Sanchez, B. Julian, P. Belleville and M. Popall, Applications of hybrid organic-inorganic nanocomposites, J. Mater. Chem., 2005, 15, 3559. 

The reactor effluent is distilled and unreacted EB is recycled. The EB hydroperoxide is then reacted with propylene at 250°F and pressure in the range of 250-700 psi in the presence of a metal catalyst to produce propylene oxide and methylbenzyl alcohol B in Figure 8-7). The reactor mixture is separated by multiple fractionators. Unreacted propylene and EB are recycled. PO is recovered overhead. The methyl benzyl alcohol is easily dehydrated in the vapor stage at 450—500° F and 500 psi pressure over a titanium dioxide or silica gel catalyst to form styrene. Acephenone is one of the by-products. 

Example 7-1 Consider a silica gel catalyst that has been peUetized into spherical peUets 4 mm diameter. The surface area is measured to be 100 m /g, and the density of sUica is 3 g/cm Find the ratio of the area of the catalyst to the external surface area of the pellet. 

Rh > Ir > Ni > Pd > Co > Ru > Fe A plot of the relation between the catalytic activity and the affinity of the metals for halide ion resulted in a volcano shape. The rate determining step of the reaction was discussed on the basis of this affinity and the reaction order with respect to methyl iodide. Methanol was first carbonylated to methyl acetate directly or via dimethyl ether, then carbonylated again to acetic anhydride and finally quickly hydrolyzed to acetic acid. Overall kinetics were explored to simulate variable product profiles based on the reaction network mentioned above. Carbon monoxide was adsorbed weakly and associatively on nickel-activated-carbon catalysts. Carbon monoxide was adsorbed on nickel-y-alumina or nickel-silica gel catalysts more strongly and, in part, dissociatively,... 

Hajek, Jan Murzin, Dmitry Yu. Liquid-Phase Hydrogenation of Cinnamaldehyde over a Ru-Sn Sol-Gel Catalyst. E Evaluation of Mass Transfer via a Combined ExperimentaFTheoretical Approach, Industrial Engineering Chemistry Research 2004), 43(9), 2030-2038... 

Intraparticle diffusion limits rates in triphase catalysis whenever the reaction is fast enough to prevent attaiment of an equilibrium distribution of reactant throughout the gel catalyst. Numerous experimental parameters affect intraparticle diffusion. If mass transfer is not rate-limiting, particle size effects on observed rates can be attributed entirely to intraparticle diffusion. Polymer % cross-linking (% CL), % ring substitution (% RS), swelling solvent, and the size of reactant molecule all can affect both intrinsic reactivity and intraparticle diffusion. Typical particle size effects on the... 

Kellogg MoOs on AliOs gel catalyst, mid-continent heavy naphtha)... 

F. mid-continent heavy naphtha Kellogg M0O3 on AI2O3 gel catalyst 1 0-lb. RVP gasoline yield vs. leaded research octane Mid-continent feed stock... 

F. virgin naphtha (predominantly East Texas). Kellogg MoOi on AlsOt gel catalyst]... 

In another type of process, oximes can be obtained by passing a mixture of ketone vapor, NH3, and 02 over a silica-gel catalyst.213 Ketones can also be converted to oximes by treatment with other oximes, in a transoximation reaction.214... 

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