Catalysts, general powdered

As discussed later, this factor is more commonly of concern in flow reaction systems. The catalysts generally used with batch reactors are fine powders with which these diffusion limitations are minimal. 

Catalytic materials for MRs have some particular requirements compared to a conventional tube flow reactor. The catalytic material should be in a form that can be inserted easily into the membrane reactor, and the catalyst should not have any mechanical failure or properties which are not suitable for a MR. Very hne powder form catalysts cannot be used, as the small particulates may block the pores of the membrane however, small particulates (>0.2 mm) have been considered (e.g., Li et al., 2010). Thus, in many cases, the catalysts generally used in MRs are pellets, extrudates or tablets. In addition to these forms, novel hbre type or foam catalysts have been studied as support materials for active metals. Li et al., (2010) have presented in their study one kind of a method of encapsulating the catalyst particles (diameter 0.2-1.7 mm) which combines a catalyst particulate with a membrane layer. This has been reported to increase the selectivity of the reaction, and thus the separation process is much easier. 

The main by-products of the Ullmaim condensation are l-aniinoanthraquinone-2-sulfonic acid and l-amino-4-hydroxyanthraquinone-2-sulfonic acid. The choice of copper catalyst affects the selectivity of these by-products. Generally, metal copper powder or copper(I) salt catalyst has a greater reactivity than copper(Il) salts. However, they are likely to yield the reduced product (l-aniinoanthraquinone-2-sulfonic acid). The reaction mechanism has not been estabUshed. It is very difficult to clarify which oxidation state of copper functions as catalyst, since this reaction involves fast redox equiUbria where anthraquinone derivatives and copper compounds are concerned. Some evidence indicates that the catalyst is probably a copper(I) compound (28,29). 

The catalysts most frequently used are based on noble metals (mainly palladium and platinum) on various supports, or on nickel catalysts (mainly Raney type). Hydrogenations are generally performed in the liquid phase, under relatively mild conditions of temperature and pressure (1—40 bar). Most processes are performed batch-wise using powder catalysts in stirred tank or loop-type reactors with sizes up to 10 m . 

Improved Filtration Rate Filterability is an important powder catalyst physical property. Sometimes, it can become more important than the catalyst activity depending on the chemical process. When a simple reaction requires less reaction time, a slow filtration operation can slow down the whole process. From a practical point of view, an ideal catalyst not only should have good activity, but also it should have good filtration. From catalyst development point of view, one should consider the relationship between catalyst particle size and its distribution with its catalytic activity and filterability. Smaller catalyst particle size will have better activity but will generally result in slower filtration rate. A narrower particle size distribution with proper particle size will provide a better filtration rate and maintain good activity. 

Catalyst powders with carefully specified particle size distribution have been known to possess good fluidization characteristics. Generally, addition of fine particles to coarse particles tends to improve the latter s fluidization characteristics. Experiments were thus conducted on binary particle mixtures, each consisting of a fairly close particle size distribution. 

Cr-ZSM-5 catalysts prepared by solid-state reaction from different chromium precursors (acetate, chloride, nitrate, sulphate and ammonium dichromate) were studied in the selective ammoxidation of ethylene to acetonitrile. Cr-ZSM-5 catalysts were characterized by chemical analysis, X-ray powder diffraction, FTIR (1500-400 cm 1), N2 physisorption (BET), 27A1 MAS NMR, UV-Visible spectroscopy, NH3-TPD and H2-TPR. For all samples, UV-Visible spectroscopy and H2-TPR results confirmed that both Cr(VI) ions and Cr(III) oxide coexist. TPD of ammonia showed that from the chromium incorporation, it results strong Lewis acid sites formation at the detriment of the initial Bronsted acid sites. The catalyst issued from chromium chloride showed higher activity and selectivity toward acetonitrile. This activity can be assigned to the nature of chromium species formed using this precursor. In general, C r6+ species seem to play a key role in the ammoxidation reaction but Cr203 oxide enhances the deep oxidation. 

Catalytic asymmetric epaxidation (13, 51-53). Complete experimental details are available for this reaction, carried out in the presence of heat-activated crushed 3A or powdered 4A molecular sieves. A further improvement, both in the rate and enantioselectivity, is use of anhydrous oxidant in isoctane rather than in CH2C12. The titanium-tartrate catalyst is not stable at 25°, and should be prepared prior to use at -20°. Either the oxidant or the substrate is then added and the mixture of three components should be allowed to stand at this temperature for 20-30 min. before addition of the fourth component. This aging period is essential for high enantioselectivity. Epoxidations with 5-10 mole % of Ti(0-/-Pr)4 and 6-12% of the tartrate generally proceed in high conversion and high enantioselectivity (90-95% ee). Some increase in the amount of catalyst can increase the enantioselectivity by 1-5%, but can complicate workup and lower the yield. Increase of Ti(0-i-Pr)4 to 50-100 mole % can even lower the enantioselectivity. 

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