Catalyst intrinsic activity

Reduce fresh catalyst loading the fresh catalyst intrinsic activity shonld be adjusted to maintain a constant eqnilibrinm catalyst performance... 

Effects of Metal Deposits on Catalyst Intrinsic Activity... 

The hydroformylation reaction is carried out in the Hquid phase using a metal carbonyl catalyst such as HCo(CO)4 (36), HCo(CO)2[P( -C4H2)] (37), or HRh(CO)2[P(CgH3)2]2 (38,39). The phosphine-substituted rhodium compound is the catalyst of choice for new commercial plants that can operate at 353—383 K and 0.7—2 MPa (7—20 atm) (39). The differences among the catalysts are found in their intrinsic activity, their selectivity to straight-chain product, their abiHty to isomerize the olefin feedstock and hydrogenate the product aldehyde to alcohol, and the ease with which they are separated from the reaction medium (36). 

Figure 10 shows that Tj is a unique function of the Thiele modulus. When the modulus ( ) is small (- SdSl), the effectiveness factor is unity, which means that there is no effect of mass transport on the rate of the catalytic reaction. When ( ) is greater than about 1, the effectiveness factor is less than unity and the reaction rate is influenced by mass transport in the pores. When the modulus is large (- 10), the effectiveness factor is inversely proportional to the modulus, and the reaction rate (eq. 19) is proportional to k ( ), which, from the definition of ( ), implies that the rate and the observed reaction rate constant are proportional to (1 /R)(f9This result shows that both the rate constant, ie, a measure of the intrinsic activity of the catalyst, and the effective diffusion coefficient, ie, a measure of the resistance to transport of the reactant offered by the pore stmcture, influence the rate. It is not appropriate to say that the reaction is diffusion controlled it depends on both the diffusion and the chemical kinetics. In contrast, as shown by equation 3, a reaction in solution can be diffusion controlled, depending on D but not on k. 

The precious metal or metal oxide imparts high intrinsic activity, the carrier provides a stable, high surface area for catalyst dispersion, and the mechanical support gives a high geometric surface area for physical support and engineering design features (20). Only the correct combination of these... 

Before deriving the rate equations, we first need to think about the dimensions of the rates. As heterogeneous catalysis involves reactants and products in the three-dimensional space of gases or liquids, but with intermediates on a two-dimensional surface we cannot simply use concentrations as in the case of uncatalyzed reactions. Our choice throughout this book will be to express the macroscopic rate of a catalytic reaction in moles per unit of time. In addition, we will use the microscopic concept of turnover frequency, defined as the number of molecules converted per active site and per unit of time. The macroscopic rate can be seen as a characteristic activity per weight or per volume unit of catalyst in all its complexity with regard to shape, composition, etc., whereas the turnover frequency is a measure of the intrinsic activity of a catalytic site. 

The molybdenum on alumina catalyst was also tested for activity with and without arsenic. Although this catlyst has a much lower intrinsic activity for HDS, the results in Figure 4 show that 3.6% arsenic almost completely deactivates the catalyst. The small amount of activity remaining is that expected for AI2O3 alone. Thus arsenic also deactivates catalysts without cobalt promoters. 

Intrinsic activities (am) of different catalysts were used to compare catalytic activities a =-Rw/SBET (mol.m. h )... 

The conventional selective reduction of NOx for car passengers still competes but the efficient SCR with ammonia on V205/Ti02 for stationary sources is not available for mobile sources due to the toxicity of vanadium and its lower intrinsic activity than that of noble metals, which may imply higher amount of active phase for compensation. As illustrated in Figure 10.9, such a solution does not seem relevant because a subsequent increase in vanadium enhances the formation of undesirable nitrous oxide at low temperature. Presently, various attempts for the replacement of vanadium did not succeed regarding the complete conversion of NO into N2 at low temperature. Suarez et al. [87] who investigated the reduction of NO with NH3 on CuO-supported monolithic catalysts... 

Intrinsic Activity Poisons. These poisons decrease the activity of the catalyst for the primary chemical reaction by virtue of their direct electronic or chemical influence on the catalyst surface or active sites. The mechanism appears to be one that involves coverage of the active sites by poison molecules, removing the possibility that these sites can subsequently adsorb reactant species. Common examples of this type of poisoning are the actions of compounds of elements of the groups Vb and VIb (N, P, As, Sb, O, S, Se, Te) on metallic catalysts. 

Two points are emphasized (i) zeolites can be successfully operated at the same or higher severities (with respect to P/O (feed alkane/alkene) ratio and OS V (alkene space velocity)) than the liquid acids (ii) the productivities of zeolite catalysts (i.e., the total amount of alkylate produced per mass of catalyst) are roughly the same as of that of sulfuric acid. If the intrinsic activities of zeolites (which have 0.5-3 mmol of acid sites per gram) are compared with that of sulfuric acid (which has 20 mmol of acid sites per gram), zeolites outperform sulfuric acid. Nevertheless, the price of a zeolite catalyst and the high costs of... 

Bertole et al.u reported experiments on an unsupported Re-promoted cobalt catalyst. The experiments were done in a SSITKA setup, at 210 °C and pressures in the range 3-16.5 bar, using a 4 mm i.d. fixed bed reactor. The partial pressures of H2, CO and H20 in the feed were varied, and the deactivation, effect on activity, selectivity and intrinsic activity (SSITKA) were studied. The direct observation of the kinetic effect of the water on the activity was difficult due to deactivation. However, the authors discuss kinetic effects of water after correcting for deactivation. The results are summarized in Table 1, the table showing the ratio between the results obtained with added water in the feed divided by the same result in a dry experiment. The column headings refer to the actual experiments compared. It is evident that adding water leads to an increase in the overall rate constant kco. The authors also report the intrinsic pseudo first order rate-coefficient kc, where the overall rate of CO conversion rco = kc 6C and 0C is the coverage of active... 

It has also been shown that the selectivity features of para-selective catalysts can be readily understood from an interplay of catalytic reaction with mass transfer. This interaction is described by classical diffusion-reaction equations. Two catalyst properties, diffusion time and intrinsic activity, are sufficient to characterize the shape selectivity of a catalyst, both its primary product distribution and products at higher degrees of conversion. In the correlative model, the diffusion time used is that for o-xylene adsorption at... 

The activity, which may be defined as the net rate of S02 oxidation in moles/s/m3 catalyst according to reaction (1), depends on the intrinsic activity of the catalyst material, the diffusion properties of the catalyst material, the size of the catalyst pellets, and the shape of the pellets. 

The phosphinated ligands 135 and 136 prepared from poly(acrylic acid) and from poly(ethyleneimine), respectively, gave active hydroformylation catalysts in reaction with [Rh(acac)(CO)2]. Under the conditions of Table 4.6 low conversions were observed in aqueous/organic biphasic systems, due to the low solubility of 1-octene. Addition of a surfactant (SDS) or an organic co-solvent (MeOH) led to dramatic increases in the yield of aldehydes, revealing the high intrinsic activity of the catalyst [120]. 

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