Catalyst deactivation time effect

Table 43.3. Effect of reaction time on catalyst deactivation ...

This result supports the idea that counterion addition to the epoxide also occurred with this material. The longer the exposure time of the catalyst to the HKR reagents (mainly epichlorohydrin), the greater is the extent of deactivation. Nevertheless, this oligomeric catalyst is certainly more effective than the monomeric catalyst as it can be used for shorter times to achieve comparable conversion and ee, thus reducing the influence of the reaction time on catalyst deactivation. 

Catalyst deactivation refers to the loss of catalytic activity and/or product selectivity over time and is a result of a number of unwanted chemical and physical changes to the catalyst leading to a decrease in number of active sites on the catalyst surface. It is usually an inevitable and slow phenomenon, and occurs in almost all the heterogeneous catalytic systems.111 Three major categories of deactivation mechanisms are known and they are catalyst sintering, poisoning, and coke formation or catalyst fouling. They can occur either individually or in combination, but the net effect is always the removal of active sites from the catalyst surface. 

Fig. 2 Long time effect of the catalyst deactivation, Cc, on the concentrations Ca and Cp.

An ideal system would enable continuous operation with separation under conditions similar to those of the reaction itself, as a result of which all the catalyst remains in its active state for all times. Use of SCCO2 as a reaction medium would not only allow for reaction and separation under similar conditions to reduce the problems of catalyst deactivation, but would also have a considerable effect on the plant design. Its total lack of flammabihty, contrary to conventional organic solvents, reduces safety problems and makes SCCO2 attractive for homogeneously catalyzed reactions, particularly for oxidation and epoxidation reactions [143]. 

Figure 21.6 Effectiveness factor increases with time as catalyst deactivates batch S/plug flow G.

A maximum phenol conversion of 65% was reached, due to the fact that the consumption of benzoic acid was higher than that of phenol. Indeed, despite the 1/1 load ratio, the selectivity to those products the formation of which required two moles of benzoic acid per mole of phenol, made the conversion of benzoic acid approach the total one more quickly than phenol. A non-negligible effect of catalyst deactivation was present in fact, when the catalyst was separated from the reaction mixture by filtration, and was then re-loaded without any regeneration treatment, together with fresh reactants, a conversion of 52% was obtained after 2.5 h reaction time, lower than that one obtained with the fresh catalyst, i.e., 59% (Figure 1). The extraction, by means of CH2CI2, of those compounds that remained trapped inside the zeolite pores, evidenced that the latter were mainly constituted of phenol, benzoic acid and of reaction products, with very low amount of heavier compounds, possible precursors of coke formation. 

It is well known, even from old literature data (ref. 1) that the presence of metal promotors like molybdenum and chromium in Raney-nickel catalysts increases their activity in hydrogenation reactions. Recently Court et al (ref. 2) reported that Mo, Or and Fe-promoted Raney-nickel catalysts are more active for glucose hydrogenation than unpromoted catalysts. However the effects of metal promotors on the catalytic activity after repeated recycling of the catalyst have not been studied so far. Indeed, catalysts used in industrial operation are recycled many times, stability is then an essential criterion for their selection. From a more fundamental standpoint, the various causes of Raney-nickel deactivation have not been established. This work was intended to address two essential questions pertinent to the stability of Raney-nickel in glucose hydrogenation namely what are the respective activity losses experienced by unpromoted or by molybdenum, chromium and iron-promoted catalysts after recycling and what are the causes for their deactivation ... 

In several experiments, in particular the study by Temkin and co-workers [224] of the kinetics in ethylene oxidation, slow relaxations, i.e. the extremely slow achievement of a steady-state reaction rate, were found. As a rule, the existence of such slow relaxations is ascribed to some "side reasons rather than to the purely kinetic ("proper ) factors. The terms "proper and "side were first introduced by Temkin [225], As usual, we classify as slow "side processes variations in the chemical or phase composition of the surface under the effect of reaction media, catalyst deactivation, substance diffusion into its bulk, etc. These processes are usually considered to require significantly longer times to achieve a steady state compared with those characterizing the performance of chemical reactions. The above numerical experiment, however, shows that, when the system parameters attain their bifurcation values, the time to achieve a steady state, tr, sharply increases. 

However, several assumptions are inherent in this interpretation of the data. First, it is assumed that the change in the observed effect (such as conversion of 850°F+, percentage denitrogenation, etc.) is linear with respect to time. Thus a linear delta-effect per period of time could be established and intermediate data could be adjusted to a MfreshM activity corresponding to that observed at the reference period and at any desired temperature. Second, it is assumed that the intermediate process parameter variations had no adverse effect on the catalyst deactivation function. For example, operation at constant temperature for a given interval of time would produce the same catalyst deactivation as varying temperatures (within limits) over the same interval of time. 

This study describes the results of processing both conventional solvent refined coal extract (SRC-I) and short contact time coal extract. Both coal extracts have been run at several space velocities, temperatures, and total reactor pressures for comparative purposes. The effect of catalyst deactivation has also been considered. The short residence time coal extract was run in both a deashed and non-deashed mode of operation. 

Instead, they proposed a time on stream theory to model the catalyst deactivation. However, in an earlier work by Voorhies (2), a linear correlation between conversion and coke on catalyst for fixed-bed catalytic cracking was derived. Rudershausen and Watson (3) also observed the similar behavior. Coke on catalyst can reduce the activity by covering the active sites and blocking the pores. The effects of pore size on catalyst performance during hydrotreating coal oils in trickle-bed reactors have been studied experimentally by Ahmed and Crynes (4) and by Sooter (5). The pore size effects in other studies are also reported 7, 8). Prasher et al. (9) observed that the effective diffusivities of oils in aged catalysts were severely reduced by coke deposition. 

The total acidity deterioration and the acidity strength distribution of a catalyst prepared from a H-ZSM-5 zeolite has been studied in the MTG process carried out in catalytic chamber and in an isothermal fixed bed integral reactor. The acidity deterioration has been related to coke deposition. The evolution of the acidic structure and of coke deposition has been analysed in situ, by diffuse reflectance FTIR in a catalytic chamber. The effect of operating conditions (time on stream and temperature) on acidity deterioration, coke deposition and coke nature has been studied from experiments in a fixed integral reactor. The technique for studying acidity yields a reproducible measurement of total acidity and acidity strength distribution of the catalyst deactivated by coke. The NH3 adsorption-desorption is measured by combination of scanning differential calorimetry and the FTIR analysis of the products desorbed. 

A recapitulation of the catalyst stability data reported indicates that within the time scale of the hydrotreating runs, the UOP-filtered SRC filter feed gave relatively stable performance. SRC itself caused substantial catalyst deactivation Synthoil gave stable performance after an initial deactivation. Since dissolved metals and particulate matter are known to have an adverse effect on catalysts, a correlation was sought based on an analysis for these components. 

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