Deactivation of the Catalysts

To confirm the inhibition effect of the adsorbed diketone on the acylation of veratrole by acetic anhydride over HBFA and HY zeolites, this product was added to reaction mixtures with both zeolites. Its presence caused a significant decrease in the yield in acylated products. For example, the addition of 3% (by weight with respect to veratrole) of diketone caused a loss in yield of more than 50% in both cases. 

For the acylation of anisole by acetic anhydride over HBFA and HY, the reasons for the deactivation accord with those already reported for the reaction with veratrole. Unfortunately, di- or triketones were not extractible and, also, deactivation of the 

Zeolite C (wt%) Veratrole Acetoveratrole Diketone Triketone Others Adsorbed 

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A significant problem is the dehydrocoupling reaction, which proceeds only at low yields per pass and is accompanied by rapid deactivation of the catalyst. The metathesis step, although chemically feasible, requires that polar contaminants resulting from partial oxidation be removed so that they will not deactivate the metathesis catalyst. In addition, apparendy both cis- and /ra/ j -stilbenes are obtained consequendy, a means of converting the unreactive i j -stilbene to the more reactive trans isomer must also be provided, thus complicating the process. 

Because HCl is constandy present in most parts of the equipment, corrosion is always a potential problem. Chlorine and benzene, or any recycled material, must be free of water to trace amounts to prevent corrosion and deactivation of the catalyst. The reactor product contains HCl and iron. In some plants, the product is neutralized with aqueous NaOH before distillation. In others, it is handled in a suitably-designed distillation train, which includes a final residue from which FeCl can be removed with the high boiling tars. 

An unstabilized high surface area alumina siaters severely upon exposure to temperatures over 900°C. Sintering is a process by which the small internal pores ia the particles coalesce and lose large fractions of the total surface area. This process is to be avoided because it occludes some of the precious metal catalyst sites. The network of small pores and passages for gas transfer collapses and restricts free gas exchange iato and out of the activated catalyst layer resulting ia thermal deactivation of the catalyst. 

Both sulfuric acid and hydrofluoric acid catalyzed alkylations are low temperature processes. Table 3-13 gives the alkylation conditions for HF and H2SO4 processes. One drawback of using H2SO4 and HF in alkylation is the hazards associated with it. Many attempts have been tried to use solid catalysts such as zeolites, alumina and ion exchange resins. Also strong solid acids such as sulfated zirconia and SbFs/sulfonic acid resins were tried. Although they were active, nevertheless they lack stability. No process yet proved successful due to the fast deactivation of the catalyst. A new process which may have commercial possibility, uses... 

Contaminant coke is produced by catalytic activity of metals such as nickel, vanadium, and by deactivation of the catalyst caused by organic nitrogen. 

Catalyst residence time in the stripper is determined by catalyst circulation rate and the amount of catalyst in the stripper. This amount usually corresponds to the quantity of the catalyst from the centerline of a normal bed level to the centerline of the lower steam distributor. A higher catalyst residence time, though it increases hydrothermal deactivation of the catalyst, will improve stripping efficiency. 

Vanadium and sodium neutralize catalyst acid sites and can cause collapse of the zeolite structure. Figure 10-5 shows the deactivation of the catalyst activity as a function of vanadium concentration. Destruction of the zeolite by vanadium takes place in the regenerator where the combination of oxygen, steam, and high temperature forms vanadic acid according to the following equations ... 

The regenerator design, either single-stage or two-stage, should provide uniform catalyst regeneration, increase flexibility for processing a variety of feedstocks, and minimize thermal and hydrothermal deactivation of the catalyst. 

Nickel catalysts were used in most of the methanation catalytic studies they have a rather wide range of operating temperatures, approximately 260°-538°C. Operation of the catalytic reactors at 482°-538°C will ultimately result in carbon deposition and rapid deactivation of the catalysts (10). Reactions below 260°C will usually result in formation of nickel carbonyl and also in rapid deactivation of the catalysts. The best operating range for most fixed-bed nickel catalysts is 288°-482 °C. Several schemes have been proposed to limit the maximum temperature in adiabatic catalytic reactors to 482°C, and IGT has developed a cold-gas recycle process that utilizes a series of fixed-bed adiabatic catalytic reactors to maintain this temperature control. 

Improve Catalyst Life and Steadiness. Regeneration or replacement of a catalyst is expensive both in direct cost and in lost production represented by the down time. Lowering the rate of deactivation of the catalyst whether by fouling, by sintering, or any other irreversible process will improve the economics of a process. 

The kinetic principles operating during the initiation and advance of interface-controlled reactions are identical with the behaviour discussed for the decomposition of a single solid (Chaps. 3 and 4). The condition that overall rate control is determined by an interface process is that a chemical step within this zone is slow compared with the rate of arrival of the second reactant. This condition is not usually satisfied during reaction between solids where the product is formed at the contact of a barrier layer with a reactant. Particular systems that satisfy the specialized requirements can, however, be envisaged for example, rate processes in which all products are volatilized or a solid additive catalyzes the decomposition of a solid yielding no solid residue. Even here, however, the kinetic characteristics are likely to be influenced by changing effectiveness of contact as reaction proceeds, or the deactivation of the catalyst surface. 

Other groups such as esters, silylethers, and imides are also successfully incorporated through ADMET depolymerization with 14 (Fig. 8.21).49 For an ester functionality, at least two methylene spacer units must be present between die olefin site and die functional group in order to achieve depolymerization. This is due to die negative neighboring group effect, a deactivation of the catalyst by coordination of the functionality heteroatoms to die catalyst.50 By physically... 

On the other hand, it can be inferred from Fig. 1 that the NO removal efficiency will decrease as the reaction proceeds. The NO removal declines from 100% at the very beginning to 93% after 4 hours with 5.2% O2 present in the gas phase. This phenomenon may be due to the oxidation of Co(NH3)6 into Co(NH3)6 meaning deactivation of the catalyst. 

The fluorination of CF3CH2CI into CF3CH2F over chromium oxides is accompanied by a dehydrofluorination reaction (formation mainly of CF2=CHC1). This dehydrofluorination is responsible for the deactivation of the catalyst. A study of the dehydrofluorination reaction of CF3CH2CI proves that the reaction is favoured when the degree of fluorination of chromium oxide increases. Consequently it would be favoured on strong acid sites. Adding nickel to chromium oxide decreases the formation of alkenes and increases the selectivity for fluorination while the total activity decreases. Two kinds of active sites would be present at the catalyst surface. The one would be active for both the reactions of dehydrofluorination and of fluorination, the other only for the fluorination reaction. 

The F / Cl exchange in chloroalkanes is a route to HFCs. For example, different routes can be possible for the synthesis of CF3CH2F [1,2 ]. Our focus is on its preparation from CF3CH2CI and HF with chromium (HI) oxide as a catalyst. This fluorination is accompanied by a dehydrofluorination which produces chloroalkenes (mainly CF2=CHC1) resulting in a deactivation of the catalyst Indeed this haloalkene could polymerise and thus lead to coke formation. The reactions involved are ... 

The transformation of CF3CH2CI was studied at 320 C in a pulse flow reactor. Indeed, in a dynamic reactor, the agnificant alkene formation leads to a rapid deactivation of the catalyst. The reaction is carried out in absence of HF in order to favour the dehydrofluorination reaction. Products distribution is shown in Fig. 1. 

This data also suggests that operating at 100% CO conversion could only provide transient data, and provide no information on the deactivation of the catalyst. As Figure 1 shows, the catalyst has a high enough activity at the low space velocity of... 

OS 58] ]R 15] ]P 41] When operating continuously for more than 100 h, deactivation of the catalyst occurs [122]. This seems not to be reversible, as calcinations by air do not bring back catalyst activity. 

GL 18] ]R 1] ]P 19a] For a sputtered palladium catalyst, low conversion and substantial deactivation of the catalyst were foimd initially (0.04 mol 1 60 °C 4 bar 0.2 ml min ) [60, 62]. Selectivity was also low, side products being formed after several hours of operation (Figure 5.25). After an oxidation/reduction cycle, a slightly better performance was obtained. After steep initial deactivation, the catalyst activity stabilized at 2-4% conversion and about 60% selectivity. After reactivation, the selectivity approached initially 100%. As side products, all intermediates except phenylhydroxylamine were identified. 

It was elegantly shown later that the hydroamination of ethylene with piperidine or Et2NH can be greatly improved using cationic rhodium complexes at room temperature and atmospheric pressure to afford a high yield of hydroaminated products (Eq. 4.10) [111]. However, possible deactivation of the catalyst can be questioned [17]. 

ESCA studies were also performed on the partially deactivated recycled carbon supported 5%Pd-0.3%Sn catalyst presented in Table 15.3. The sulfur detection limit for this study was -0.5%. Therefore these data implied that there was no obvious Pd-S formation on the used catalyst, but a large amount of nitrogen was present as shown in Table 15.5. We assign this as a possible Pd-CN species. These data suggested that the presence of HCN rather than H2S might be the predominant factor for the deactivation of the catalyst. 

Figures 44.1 and 44.2 report the performance in the gas-phase phenol methylation of the H-mordenite and of the Mg/Fe/O catalyst, respectively. The differences between the two catalysts concerned both the transformations occurring on methanol and the type of phenolic products obtained. The H-mordenite was very active at 350°C the conversion of phenol was 80%. A further increase of temperature led to a decrease of conversion. This can be attributed to a progressive deactivation of the catalyst, due to...

If deactivation of the catalyst is very short, then moving-or fluidized-bed reactors are required so that the catalyst can be withdrawn continuously, regenerated and returned to... 

The related dihydride-dichloro complex OsH2Cl2(P Pr3)2 is also an active catalyst for the hydrogenation of olefins, diolefms, and a-(3-unsaturated ketones,14 but attempts to hydrogenate phenylacetylene show a rapid deactivation of the catalyst due to formation of a hydride-carbyne complex.54... 

For the Ti(OiPr)4/silica system, the advantage of MCM-41 (a mesoporous silica) over an amorphous silica is not evident either in terms of activity or selectivity for the epoxidation of cyclohexene with H202 in tert-butyl-alcohol.148 Nevertheless, deactivation of the catalysts seems slower, although the selectivity of the recovered catalysts is also lower (allylic oxidation epoxidation = 1 1). Treatment of these solids with tartaric acid improves the properties of the Ti/silica system, but not of the Ti/MCM-41 system, although NMR,149 EXAFS,150 and IR151 data suggest that the same titanium species are present on both supports. 

An increase in the crystallites size of the HBEA zeolite brings a neat increase in the activity of the corresponding Pt-exchanged catalyst for n-C.% transformation (Table 1). However, this increase in activity is accompanied by a significant deactivation of the catalyst 90% with the 10-15 pm crystallite size, 60% with the 1-1.5 pm crystallite size, while no deactivation is observed with the 0.02 pm crystallite size. 

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