Impurities deactivation

Coking is a severe thermal cracking process designed to handle heavy residues with high asphaltene and metal contents. These residues cannot be fed to catalytic cracking units because their impurities deactivate and poison the catalysts. 

Similarly, a [Pd2(dba)3]/dppb catalyst in toluene at 100 °C isomerizes PhC(O)—C=C—Bu into the dienone PhC(0)CH=CH—CH=CHEt in good yields. A variety of dienones has been prepared in this way. " There can be little doubt that all these reactions proceed via Pd Tr-allyl intermediates. The asymmetric isomerization of 4-hydroxycyclopent-2-en-l-one is catalyzed by [(R)-BINAP)Rh(MeOH)2] and gives 4-hydroxycyclopent-3-en-l-one as the primary product. With racemic starting material, the 5 enantiomer is consumed faster, to give a 5 1 enantiomeric discrimination. The primary product can tautomerize to 1,3-cyclopentadione. The same chiral cationic rhodium catalyst is also effective in the asymmetric isomerization of allylamines. Water impurities deactivate the catalyst. One such deactivation product is the air-stable trinuclear cluster (20), which was characterized by X-ray diffreaction. "" ... 

Much of the work done in recent years on polymer mechanochemistry has made use of the high elongational strain rates observed around collapsing cavitation bubbles in sonicated solutions, as outlined in the section on mechanoluminescence [27]. In addition to the distinctive features of sonochemically-induced mechanical reactivity described above, further attention needs to be paid to the sonication conditions in the case of mechanochemical catalysis, because catalyst lifetime and turnover number are reduced by sonochemical byproducts. Implosion of cavitation bubbles is essentially an adiabatic process which leads to formation of local hotspots within the bubble in which temperature and pressure increases drastically. The content of cavitation bubbles pyrolyses under these extreme conditions and results in formation of reactive species, such as radicals and persistent secondary byproducts acidic byproducts may also form from the degradation of the substrates [75]. Chemical impurities deactivate the reactive catalyst partially if not completely. Recent studies in our group have shown that heat capacity of gas... 

Reaction of the active site with polar impurities deactivates the catalyst. Due to the cationic nature of the active sites, nucleophilic groups with a lone pair of elec-... 

When deactivation occurs rapidly (in a few seconds during catalytic cracking, for instance), the fresh activity can be found with a transport reac tor through which both reac tants and fresh catalyst flow without slip and with short contact time. Since catalysts often are sensitive to traces of impurities, the time-deac tivation of the catalyst usually can be evaluated only with commercial feedstock, preferably in a pilot plant. 

Figure 12.7 Cliromatograms of a polycarbonate sample (a) microcolumn SEC ti ace (b) capillary GC ti ace of inti oduced fractions. SEC conditions fused-silica (30 cm X 250 mm i.d.) packed with PL-GEL (50 A pore size, 5 mm particle diameter) eluent, THE at aElow rate of 2.0ml/min injection size, 200 NL UV detection at 254 nm x represents the polymer additive fraction ti ansfeired to EC system (ca. 6 p-L). GC conditions DB-1 column (15m X 0.25 mm i.d., 0.25 pm film thickness) deactivated fused-silica uncoated inlet (5 m X 0.32 mm i.d.) temperature program, 100 °C for 8 min, rising to 350 °C at a rate of 12°C/min flame ionization detection. Peak identification is as follows 1, 2,4-rert-butylphenol 2, nonylphenol isomers 3, di(4-tert-butylphenyl) carbonate 4, Tinuvin 329 5, solvent impurity 6, Ii gaphos 168 (oxidized). Reprinted with permission from Ref. (14).

The activity of catalyst degrades with time. The loss of activity is primarily due to impurities in the FCC feed, such as nickel, vanadium, and sodium, and to thermal and hydrothermal deactivation mechanisms. To maintain the desired activity, fresh catalyst is continually added to the unit. Fresh catalyst is stored in a fresh catalyst hopper and, in most units, is added automatically to the regenerator via a catalyst loader. 

An active matrix can also serve as a trap to catch some of the vanadium and basic nitrogen. The high boiling fraction of the FCr feed usually contains metals and basic nitrogen that poison the zeolite. One of the advantages of an active matrix is that it guards the zeolite from becoming deactivated prematurely by these impurities. 

The space velocity was varied from 2539 to 9130 scf/hr ft3 catalyst. Carbon monoxide and ethane were at equilibrium conversion at all space velocities however, some carbon dioxide breakthrough was noticed at the higher space velocities. A bed of activated carbon and zinc oxide at 149 °C reduced the sulfur content of the feed gas from about 2 ppm to less than 0.1 ppm in order to avoid catalyst deactivation by sulfur poisoning. Subsequent tests have indicated that the catalyst is equally effective for feed gases containing up to 1 mole % benzene and 0.5 ppm sulfur (5). These are the maximum concentrations of impurities that can be present in methanation section feed gases. 

It is seen that to identify the impurities, the column appeared to be significantly overloaded. Nevertheless, the impurities were well separated from the main component and the presence of a substance was demonstrated in the generic formulation that was not present in the Darvocet . The mobile phase was 98.5% dichloromethane with 1.5% v/v of methanol containing 3.3% ammonium hydroxide. The ammoniacal methanol deactivated the silica gel but the interaction of the solutes with the stationary phase would still be polar in nature. In contrast solute interactions with the methylene dichloride would be exclusively dispersive. 

Some deactivation processes are reversible. Deactivation by physical adsorption occurs whenever there is a gas-phase impurity that is below its critical point. It can be reversed by eliminating the impurity from the feed stream. This form of deactivation is better modeled using a site-competition model that includes the impurities—e.g., any of Equations (10.18)-(10.21)— rather than using the effectiveness factor. Water may be included in the reaction mixture so that the water-gas shift reaction will minimize the formation of coke. Off-line decoking can be... 

Palladium is known to be a metal that works catalytically in the system. Various supports can be used for Pd, such as active carbon, mesoporous materials, and polymers. All of them deactivate in the sitosterol hydrogenation, most probably because of sulfur and phosphorus impurities present in the raw material, which originates from the tall oil production, a side process of chemical pulping. 

Determine the stability of the catalyst How fast does it lose its activity and what is the cause of the deactivation How sensitive is the catalyst to various impurities that may be present in the feedstock under realistic conditions ... 

Chemical deactivation. In chemical deactivation the active surface area changes by strong chemisorption of impurities in the feed, by blocking of active sites by heavy products formed in parallel or sequential reactions, etc. The most important chemical causes of deactivation are poisoning by impurities in the feed and deposition of carbonaceous material, usually referred to as coke . 

Stability tests of catalyst. All catalysts deactivate during their life by various causes (see Chapter 3). The aim of stability tests is to examine the cause and rate of deactivation. These experiments are usually performed at conditions similar to those planned for the commercial unit. In some cases, accelerated tests are carried out using a feedstock with an elevated level of impurities or at a temperature significantly higher than that anticipated for the full-scale reactor. A laboratory reactor used for such tests is usually a down-scaled reactor or a part of the full-scale-reactor. Standard analytical equipment is used. 

The selectivity in a system of parallel reactions does not depend much on the catalyst size if effective diffusivities of reactants, intermediates, and products are similar. The same applies to consecutive reactions with the product desired being the final product in the series. In contrast with this, for consecutive reactions in which the intermediate is the desired product, the selectivity much depends on the catalyst size. This was proven by Edvinsson and Cybulski (1994, 1995) for. selective hydrogenations and also by Colen et al. (1988) for the hydrogenation of unsaturated fats. Diffusion limitations can also affect catalyst deactivation. Poisoning by deposition of impurities in the feed is usually slower for larger particles. However, if carbonaceous depositions are formed on the catalyst internal surface, ageing might not depend very much on the catalyst size. 

TLC plates coated with the layer of polar adsorbent should be prewetted with a nonpolar solvent, such as benzene or n-heptane (n-hexane), to prevent deactivation of the adsorbent surface and to avoid glue up as a result of the penetration of the pores by lipid molecules and other impurities (i.e., wax). 

Retard efficiently oxidation of polymers catalysed by metal impurities. Function by chelation. Effective metal deactivators are complexing agents which have the ability to co-ordinate the vacant orbitals of transition metal ions to their maximum co-ordination number and thus inhibit co-ordination of hydroperoxides to metal ions. Main use of stabilisation against metal-catalysed oxidation is in wire and cable applications where hydrocarbon materials are in contact with metallic compounds, e.g. copper. 

The ideal electropolymerization scheme (Eq. (5.5.39)) is further complicated by the fact that lower oligomers can react with nucleophilic substances (impurities, electrolyte anions, and solvent) and are thus deactivated for subsequent polymerization. The rate of these undesired side reactions apparently increases with increasing oxidation potential of the monomer, for example, in the series ... 

If the activity of the catalyst is slowly modified by chemisorption of materials that are not easily removed, the deactivation process is termed poisoning. It is usually caused by preferential adsorption of small quantities of impurities (poisons) present in the feedstream. Adsorption of extremely small amounts of the poison (a small fraction of a monolayer) is often sufficient to cause very large losses in catalytic activity. The bonds linking the catalyst and poison are often abnormally strong and highly specific. Consequently, the process is often irreversible. If the process is reversible, a change in the temperature or the composition of the gas to which it is exposed may be sufficient to restore catalyst... 

However, residuum hydrotreating catalysts themselves are susceptible to irreversible deactivation caused by the accumulation of sulfided metal impurities. The gradual buildup of these impurities in the pores of a hydroprocessing catalyst causes plugging and deactivation. 

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