Zeolites catalyst effectiveness

Soualah, A., Lemberton, J.L., Pinard, L., Chater, M., Magnoux, P., and Moljord, K. (2008) Hydroisomerization of long-chain n-alkanes on bifunctional Pt/zeolite catalysts effect of the zeolite strucmre on the product selectivity and on the reaction mechanism. Appl. Catal. A., 336, 23-28. 

FAU AND EMT ZEOLITE CATALYSTS EFFECT OF STRUCTURE AND ACIDITY ON CATALYTIC PERFORMANCE... 

A good catalyst is also stable. It must not deactivate at the high temperature levels (1300 to 1400°F) experienced in regenerators. It must also be resistant to contamination. While all catalysts are subject to contamination by certain metals, such as nickel, vanadium, and iron in extremely minute amounts, some are affected much more than others. While metal contaminants deactivate the catalyst slightly, this is not serious. The really important effect of the metals is that they destroy a catalyst s selectivity. The hydrogen and coke yields go up very rapidly, and the gasoline yield goes down. While Zeolite catalysts are not as sensitive to metals as 3A catalysts, they are more sensitive to the carbon level on the catalyst than 3A. Since all commercial catalysts are contaminated to some extent, it has been necessary to set up a measure that will reflect just how badly they are contaminated. 

Another patent apphcation (28) describes the use of zeolite/TUD-1 with optionally a metal function for a variety of reactions. In an example, as-synthesized MCM-22 / TUD-1 was tested for acylation of 2-methoxynaphthalene with acetic anhydride to 2-acetyl-6-methoxynaphthalene at 240°C. After reaction for six hours, conversion of 2-methoxynaphthalene reached 56% with 100% selectivity to 2-acetyl-6-methoxynaphthalene. Other zeolite catalysts were similarly tested, but none were nearly as effective. 

Nitrogen adsorption/desorption isotherms on Zeolite and V-Mo-zeolite are very similar and close to a type I characteristic of microporous materials, although the V-Mo-catalysts show small hysterisis loop at higher partial pressures, which reveals some intergranular mesoporosity. Table 1 shows that BET surface area, microporous and porous volumes, decrease after the introduction of Molybdenum and vanadium in zeolite indicating a textural alteration probably because of pore blocking by vanadium or molybdenum species either dispersed in the channels or deposited at the outer surface of the zeolite. The effect is far less important for the catalysts issued from ZSM-5. 

Hydroisomerization of n-hexadecane on Pt/HBEA bifunctional catalysts effect of the zeolite crystallites size on the reaction scheme. 

In recent years, there has been a growing interest in the synthesis and application of nano-scale zeolites. Zeolites with a crystal size smaller than 100 nm are the potential replacement for existing zeolite catalysts and can be used in novel environmentally benign catalytic processes. It is well known that the crystal size of zeolites has a great effect on their catalytic properties. The improved catalytic activity and selectivity as well as lower coke formation and better durability can be obtained over nano-sized zeolite crystals [2]. 

Supported palladium oxide is the most effective catalyst used in total methane oxidation and in catalytic oxidation of VOCs [1-5]. However, the activity of the conventional catalysts is not sufficient [5-6]. Recently, the Pd-zeolite catalysts have attracted considerable attention due to their high and stable CH4 conversion efficiency [4-8]. In this work, the effect of the preparation method, the nature of the charge-balancing cations, the palladium loading and the pre-treatment gas nature on the texture, structure and catalytic activity of the Pd-ZSM-5 solids are investigated. 

A dual-bed catalyst system has been developed to tackle the key problems in benzene product impurity during heavy aromatics transalkylation processing over metal-supported zeolite catalysts. It was found that by introducing zeolite H-Beta as a complementary component to the conventional single-bed Pt/ZSM-12 catalyst, the cascaded dual-bed catalyst shows synergistic effect not only in catalytic stability but also in adjustments of benzene product purity and product yields and hence should represent a versatile catalyst system for heavy aromatics transalkylation. 

Hydroxylation of benzene with hydrogen peroxide in the presence of solid zeolite catalyst (titan-silicate-zeolite) was chosen by Radoiu et al. [57] as a model heterogeneous liquid-phase reaction for study of microwave effects, Scheme 10.12. 

An increased selectivity for phenol in the oxidation of benzene by H202 with TS-1 catalyst in sulfolane solvent was attributed to the formation of a bulky sulfolane-phenol adduct which cannot enter the pores of TS-1. Further oxidation of phenol to give quinones, tar, etc. is thus avoided. Removal of Ti ions from the surface regions of TS-1 crystals by treatment with NH4HF2 and H202 was also found to improve the activity and selectivity (227). The beneficial effects of removal of surface Al ions on the catalytic performance of zeolite catalysts for acid-catalyzed reactions have been known for a long time. 

In principle, the same rules hold true when zeolitic alkylation catalysts are used. A detailed study of the influence of PO and OSV on the performance of zeolite H-BEA in a backmix reactor was reported by de Jong et al. (80). The authors developed a simple model of the kinetics, which predicted catalyst lifetimes as a function of P/O and OSV. Catalyst lifetime (which is equivalent to the catalyst productivity, the reciprocal of acid consumption) increased with increasing P/O ratio and decreasing OSV. Furthermore, the authors persuasively demonstrated the superiority of a backmix reactor over a plug flow reactor. Qualitatively similar results were obtained by Taylor and Sherwood (222) employing a USY zeolite catalyst in a backmix reactor. The authors stressed the detrimental effect of unreacted alkene on the catalyst lifetime and product quality. Feller et al. (89) tested LaX zeolites in a backmix reactor and found the catalyst productivity to be nearly independent of the OSV within the examined OSV range. At higher values of OSV, the catalyst life was shorter, but in this shorter time the same total amount of product was produced. The P/O ratio had only a moderate influence on the catalyst performance. 

The reason for the high selectivity of zeohte catalysts is the fact that the catalytic reaction typically takes place inside the pore systems of the zeohtes. The selectivity in zeohte catalysis is therefore closely associated to the unique pore properties of zeohtes. Their micropores have a defined pore diameter, which is different from all other porous materials showing generally a more or less broad pore size distribution. Therefore, minute differences in the sizes of molecules are sufficient to exclude one molecule and allow access of another one that is just a little smaller to the pore system. The high selectivity of zeolite catalysts can be explained by three major effects [14] reactant selectivity, product selectivity, and selectivity owing to restricted size of a transition state (see Figure 4.11). 

An additional way to effect the shape/size selectivity of zeolite catalysts was developed which entailed deposition of various silicon-containing deposits on the external surfaces of zeolites to create an additional diffusion barrier [131, 138]. 

Aromatization activity of gallium containing MEl and TON zeolite catalysts in n-butane conversion effects of gallium and reaction conditions. Appl. Catal. A, 316, 61-67. 

Landau, M.V., Vradman, L Valtchev, V., Lezervant, J., Liubich, E and Talianker, M. (2003) Hydrocracking of heavy vacuum gas oil with a Pt/H-beta/ A1203 catalyst effect of zeolite crystal size in the nanoscale range. Ind. Eng. Chem. Res., 42, 2773-2782. 

Micropore mass transfer resistance of zeoUte crystals is quantified in units of time by r /Dc, where is the crystal radius and Dc is the intracrystalline diffusivity. In addition to micropore resistance, zeolitic catalysts may offer another type of resistance to mass transfer, that is resistance related to transport through the surface barrier at the outer layer of the zeoHte crystal. Finally, there is at least one additional resistance due to mass transfer, this time in mesopores and macropores Rp/Dp. Here Rp is the radius of the catalyst pellet and Dp is the effective mesopore and macropore diffusivity in the catalyst pellet [18]. 

Dewaxing is the final example of a reaction illustrated here with possibly multiple restricted transition state shape selectivity effects. Bifunctional zeolitic catalysts... 

Erecan, C., Dautzenberg, F., Yeh, C.Y., and Bamer, H.E. (1998) Mass transfer effects in liquid phase alkylation of benzene with zeolite catalysts. Ind. 

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