Batch reactor catalyst deactivation

The liquid phase Friedel-Crafts acylation of thioanisole with iso-butyric anhydride to produce 4-methyl thiobutyrophenone has been studied using supported silicotungstic acid catalysts. Reaction is rapid, giving the para-acylation product in high yield. Reactions have been performed in both batch slurry and trickle bed reactors. In both reactors catalyst deactivation due to strong adsorption of product was observed. 

Batchwise operating three-phase reactors are frequently used in the production of fine and specialty chemicals, such as ingredients in drags, perfumes and alimentary products. Large-scale chemical industry, on the other hand, is often used with continuous reactors. As we developed a parallel screening system for catalytic three-phase processes, the first decision concerned the operation mode batchwise or continuous. We decided for a continuous reactor system. Batchwise operated parallel sluny reactors are conunercially available, but it is in many cases difficult to reveal catalyst deactivation from batch experiments. In addition, investigation of the effect of catalyst particle size on the overall activity and product distribution is easier in a continuous device. 

The acetylation over protonic zeolites of aromatic substrates with acetic anhydride was widely investigated. Essentially HFAU, HBEA, and HMFI were used as catalysts, most of the reactions being carried out in batch reactors, often in the presence of solvent. Owing to the deactivation effect of the acetyl group, acetylation is limited to monoacetylated products. As could be expected in electrophilic substitution, the reactivity of the aromatic substrates is strongly influenced by the substituents, for example, anisole > m-xylene > toluene > fluorobenzene. Moreover, with the poorly activated substrates (m-xylene, toluene, and fluoroben-zene) there is a quasi-immediate inhibition of the reaction. It is not the case with activated substrates such as anisole and more generally aromatic ethers. It is why we have chosen the acetylation of anisole and 2-methoxynaphtalene as an example. 

Aldol condensation of acetone is a well-known base-catalyzed reaction, and barium hydroxide is one of the catalysts for this reaction mentioned in textbooks. A family of barium hydroxide samples hydrated to various degress determined by the calcination temperature (473, 573, 873, and 973 K) of the starting commercial Ba(OH)2 8H2O were reported to be active as basic catalysts for acetone aldol condensation (282,286). The reaction was carried out in a batch reactor equipped with a Soxhlet extractor, where the catalyst was placed. The results show that Ba(OH)2 8H2O is less active than any of the other activated Ba(HO)2 samples, and the Ba(OH)2 calcined at 473 K was the most active and selective catalyst for formation of diacetone alcohol, achieving nearly 58% acetone conversion after 8h at 367 K in a batch reactor. When the reaction temperature was increased to 385 K, 78% acetone conversion with 92% selectivity to diacetone alcohol was obtained after 8h. The yield of diacetone alcohol was similar to that described in the literature in applications with commercial barium hydroxide, but this catalyst required longer reaction times (72-120 h) (287). No deactivation of the catalyst was observed in the process, and it could be used at least 9 times without loss of activity. 

Consider the operational problem. For rather slow deactivation we can use a batch of catalyst with a choice of running the reactor in one of three ways, as shown in Fig. 21.8. Whatever policy is chosen the performance equations for the rates of Eqs. 41 and 42 are obtained by solving the following expressions ... 

Industrially relevant consecutive-competitive reaction schemes on metal catalysts were considered hydrogenation of citral, xylose and lactose. The first case study is relevant for perfumery industry, while the latter ones are used for the production of sweeteners. The catalysts deactivate during the process. The yields of the desired products are steered by mass transfer conditions and the concentration fronts move inside the particles due to catalyst deactivation. The reaction-deactivation-diffusion model was solved and the model was used to predict the behaviours of semi-batch reactors. Depending on the hydrogen concentration level on the catalyst surface, the product distribution can be steered towards isomerization or hydrogenation products. The tool developed in this work can be used for simulation and optimization of stirred tanks in laboratory and industrial scale. 

Reaction was also investigated in a fixed bed reactor under trickle flow conditions to investigate whether reaction under flow conditions would affect the rate of catalyst deactivation. Conversions and selectivities are shown in Table 5. Rapid deactivation of the catalyst was observed with concomitant progressive darkening of the catalyst bed indicative of strong adsorption (retention) of material on the catalyst and resulted in a lower catalyst productivity compared to equivalent reaction in a batch slurry reactor. 

Supported catalysts could be reused once with little loss of activity further reuse led to a significant drop in activity, as a result of strong absorption of products and by-products on the catalyst surface (indicated by colour change of the catalyst). More rapid catalyst deactivation was observed in a trickle bed reactor than in a batch slurry reactor. 

The condensation of methyl N—phenyl carbamate witli IICHO to methylene diphenyl diurethane has been studied in a batch reactor in the presence of cation exchanged resins. Unlike conventional H0SO4 catalyst, fresh resin catalysts did not form a byproduct N—benzyl compound. However, accumulation of water from repeated uses of the catalyst caused a decreased activity and the formation of the byproduct. The deactivated catalyst could be completely regenerated by drying in vacuo. Ethylacetate and toluene were found to be efficient solvents with the resin catalysts. 

A comparative study of nanocomposites (16% Nafion-silica and commercial SAC-13) has been performed by Hoelderich and co-workers169 in the alkylation of isobutane and Raffinate II. Raffinate II, the remaining C4 cut of a stream cracker effluent after removal of dienes, isobutane, propane, and propene, contains butane, isobutylene, and butenes as main components. High conversion with a selectivity of 62% to isooctane was found for Nafion SAC-13 (batch reactor, 80°C). Both the quality of the product and the activity of the catalysts, however, decrease rapidly due to isomerization and oligomerization. Treating under reflux, the deactivated catalysts in acetone followed by a further treatment with aqueous hydrogen peroxide (80°C, 2 h), however, restores the activity. 

Just like chemical processes, biocatalytic reactions are performed most simply in batch reactors (Figure 5.5a). On a lab scale and in the case of inexpensive or rapidly deactivating biocatalysts, this is the optimal solution. If the biocatalyst is to be recycled, but the mode of repeated batches is to be maintained, a batch reactor with subsequent ultrafiltration is recommended (batch-UF reactor Figure 5.5b). The residence times of catalyst and reactants are identical in all batch reactor configurations. 

Figure 2.5 Relative occupancy (%) of the intracrystalline volume of a H-BEA zeolite during the transformation of a 2 1 molar anisole - acetic anhydride mixture in a batch reactor, assuming no adsorption of acetic acid and full occupancy of the micropores. Anisole ( ), acetic anhydride (o) and 4-methoxyacetophenone (x). Reprinted from Journal of Catalysis, Vol. 187, Derouane et al., Zeolite catalysts as solid solvents in Fine Chemicals synthesis 1. Catalyst deactivation in the Friedel-Crafts acetylation of anisole, pp. 209-218, copyright (1999), with permission from Elsevier...

Samples of used residue hydrodemetallization catalysts prepared by hydrotreating a Safanyia atmospheric residue have been characterized and tested using model compounds in order to investigate the initial deactivation of the catalyst Samples containing 4 to 10 wt % carbon and less than 200 wt ppm V or 10 to 15 wt % carbon and 1.3 wt % V have been obtained from tests in batch and continuous flow reactors respectively. It is shown that in the early stage of the catalyst deactivation a small amount of vanadium is more deactivating than a large amount of carbon. 

In a study of the deactivation by coking of an atmospheric residue HDM catalyst, we have been able to obtain coked catalysts almost free from metal deposits in batch reactor and coked catalysts containing small amounts of metal sulfide deposits in continuous flow reactor using a Safaniya atmospheric residue under similar experimental conditions (30). We report in this paper a study of the deactivating effects of the deposits using toluene hydrogenation, cyclohexane isomerization and thiophene hydrodesulfurization reactions. 

The used catalysts of the TS series contain low metal contents. However in view of the possible deactivating effect of 0.7 or 1.3 wt % of vanadium, samples containing even less vanadium were required. These samples have been prepared in batch reactor where the catalyst/oil ratio determines the maximum amount of metal deposited. In this work, with a catalyst/oil ratio of 0.4 and an the SAR containing 106 wt ppm Ni + V, the maximum amount of metal which could be deposited on the catalyst surface is 265 wt ppm Ni + V. ... 

In fine chemicals industries the batch reactor is used almost exclusively. For catalytic hydrogenations the batch reactor has a number of inconveniences in case a slurry catalyst is used. The complicated cooling coils, dead spaces behind baffles, etc. are difficult to clean if the catalyst has to be removed from the vessel. After each batch the vessel has to be emptied, which also implies that the catalyst falls dry. It is known that specially in this period all reactants and products, still contained in the pores of the catalyst, rapidly may deteriorate via unwanted side reactions and so deactivate the catalyst. Usually deactivation starts as soon as the catalyst is no more protected by the solvent. As a production series of one product consists of a number of batches, the exposure of the catalyst to deactivation conditions is frequent. 

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