Structured catalyst

To be specific let us have in mind a picture of a porous catalyst pellet as an assembly of powder particles compacted into a rigid structure which is seamed by a system of pores, comprising the spaces between adjacent particles. Such a pore network would be expected to be thoroughly cross-linked on the scale of the powder particles. It is useful to have some quantitative idea of the sizes of various features of the catalyst structur< so let us take the powder particles to be of the order of 50p, in diameter. Then it is unlikely that the macropore effective diameters are much less than 10,000 X, while the mean free path at atmospheric pressure and ambient temperature, even for small molecules such as nitrogen, does not exceed... 

Several types of catalysis are described by terms denoting the catalyst structure or function. 

As part of an independent study of catalytic asymmetric cyclopropanation, Denmark et al. described a systematic investigation of the effect of addition order, stoichiometry and catalyst structure on sulfonamide-catalyzed Simmons-Smith cyciopropanations. Although early studies had shown promising levels of enantios-electivity, higher selectivity would be required for this to be a synthetically useful transformation. The principal issues that were addressed by this study included ... 

Enantioselectivities were found to change sharply depending upon the reaction conditions including catalyst structure, reaction temperature, solvent, and additives. Some representative examples of such selectivity dependence are listed in Scheme 7.42. The thiol adduct was formed with 79% ee (81% yield) when the reaction was catalyzed by the J ,J -DBFOX/Ph aqua nickel(II) complex at room temperature in dichloromethane. Reactions using either the anhydrous complex or the aqua complex with MS 4 A gave a racemic adduct, however, indicating that the aqua complex should be more favored than the anhydrous complex in thiol conjugate additions. Slow addition of thiophenol to the dichloromethane solution of 3-crotonoyl-2-oxazolidinone was ineffective for enantioselectivity. Enantioselectivity was dramatically lowered and reversed to -17% ee in the reaction at -78 °C. A similar tendency was observed in the reactions in diethyl ether and THF. For example, a satisfactory enantioselectivity (80% ee) was observed in the reaction in THF at room temperature, while the selectivity almost disappeared (7% ee) at 0°C. 

In these reactions the system is tuned, for example by adjustment of the reaction temperature and time and modification of the catalyst structure to maximize the quantity of the desired dimers produced, and to minimize the production of higher molecular weight oligomers and polymers. In other reactions it is the opposite... 

The metals in the FCC feed have many deleterious effects. Nickel causes excess hydrogen production, forcing eventual loss in the conversion or thruput. Both vanadium and sodium destroy catalyst structure, causing losses in activity and selectivity. Solving the undesirable effects of metal poisoning involves several approaches ... 

Catalyst Structure Monomer Catalyst Structure Monomer... 

In this work, examples are shown of the use of the computerized analytical approach in multicomponent polymer systems. The approach works well for both fractionated and whole polymers. The methodology can (1) permit differentiation to be made as to Whether the given sample conprises one conponent or a mixture of several components (2) allow the NMR spectrum of a polymer mixture to be analyzed in an unbiased fashion (3) give information on mole fractions and reaction probabilities that can be significant variables in understanding catalyst structures or polymerization mechanisms. 

Similar organocatalytic species to those successfully used for the Strecker reaction were used for the asymmetric Mannich reaction. Catalyst structure/ enantioselectivity profiles for the asymmetric Strecker and Mannich reactions were compared by the Jacobsen group [160]. The efficient thiourea... 

Reaction and Mass Transfer in Porous Catalyst Structures... 

Molecular modeling showed that WO3 surface has a structure where p-xylene may adsorb well, explaining the high activity of WO3 in p-xylene conversion. Experimental data in this study show that Sb addition modifies significantly the activity and selectivity properties of WO3 as well as the catalyst structure. Fig. 3 shows the minimum and maximum p-xylene... 

Table 1. Effect of catalyst structure on EC conversion and selectivities to DMC and EG...

Catalyst Structure Particle Size BET Surface Area Isoelectric Point pH... 

In our previous work [8], we rqjorted the synthesis of (2-oxo-l,3-dioxolan-4-yl)methacrylate (DOMA) finrn carbon dioxide and glycidyl methacrylate (GMA) using quaternary salt catalysts. In the present work, we studied the catalytic pra rmance of alkyhnethyl imidazolium salt ionic liquid in the synthesis of polycarbonate from the copolyraerization of CO2 with GMA. The influences of copolymerization variable like catalyst structure and reaction tenperature on the conversion of GMA and the yield of the polycarbonate have been discussed. 

A head-to-head dimerization of a-olefin catalyzed by a bis(imino)pyridine iron complex has been reported by Small and Marcucci [126]. This reaction delivers linear internal olefins (up to 80% linearity) from a-oleftns. The linearity of products, however, depends on the catalyst structure and the reaction conditions. 

Partial oxidations over complex mixed metal oxides are far from ideal for singlecrystal like studies of catalyst structure and reaction mechanisms, although several detailed (and by no means unreasonable) catalytic cycles have been postulated. Successful catalysts are believed to have surfaces that react selectively vith adsorbed organic reactants at positions where oxygen of only limited reactivity is present. This results in the desired partially oxidized products and a reduced catalytic site, exposing oxygen deficiencies. Such sites are reoxidized by oxygen from the bulk that is supplied by gas-phase O2 activated at remote sites. 

The results of the EXAFS studies on supported bimetallic catalysts have provided excellent confirmation of earlier conclusions (21-24) regarding the existence of bimetallic clusters in these catalysts. Moreover, major structural features of bimetallic clusters deduced from chemisorption and catalytic data (21-24), or anticipated from considerations of the miscibility or surface energies of the components (13-15), received additional support from the EXAFS data. From another point of view, it can also be said that the bimetallic catalyst systems provided a critical test of the EXAFS method for investigations of catalyst structure (17). The application of EXAFS in conjunction with studies employing ( mical probes and other types of physical probes was an important feature of the work (25). 

The purpose of this work was to increase the A3 selectivity at low conversion through a catalyst modification. Previous studies of phenol alkylation with methanol (the analogue reaction) over oxides and zeolites showed that the reaction is sensitive to acidic and basic properties of the catalysts [3-5]. It is the aim of this study to understand the dependence of catalyst structure and acidity on activity and selectivity in gas phase methylation of catechol. Different cations such as Li, K, Mg, Ca, B, incorporated into y-Al203 can markedly modify the polarisation of the lattice and consequently influence the acidic and basic properties of the surface [5-8] which control the mechanism of this reaction. 

For the studied catechol methylation reaction the catalyst structure and surface properties can explain the catalytic behaviour As mentioned above, the reaction at 260-350°C has to be performed over the acid catalysts. Porchet et al. [2] have shown, by FTIR experiments, the strong adsorption of catechol on Lewis acid/basic sites of the Y-AI2O3 surface. These sites control the reaction mechanism. 

Figure 3.23 Photograph of the catalyst structure inserted in the ceramic support. Close-up of the holes in the platinum catalyst strip [63],...

Unfortunately, complexes 39 and 40 are still more prone to decomposition than catalyst 16. Therefore, Grubbs sought to investigate a series of new ruthenium catalysts bearing NHCs with varying degrees of iV-heterocyclic backbone and aryl side chain substitution, and catalysts 16 and 30a were chosen as basic catalyst structures [57]. In 2009, complexes 41a-c and 42a-c were prepared to attempt to understand how the degree of substitution on the backbone influences catalyst activity and lifetime (Fig. 3.15). 

This work demonstrates that selectivity is related to catalyst structure in a very complex way. In the case of Ch hydrogenation/dehydrogenation, it is the interaction of hydrogen rather than Ch that dictates the observed... 

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