Xylene isomerization selectivity

The correlation between selectivity and intracrystalline free space can be readily accounted for in terms of the mechanisms of the reactions involved. The acid-catalyzed xylene isomerization occurs via 1,2-methyl shifts in protonated xylenes (Figure 3). A mechanism via two transalkylation steps as proposed for synthetic faujasite (8) can be ruled out in view of the strictly consecutive nature of the isomerization sequence o m p and the low activity for disproportionation. Disproportionation involves a large diphenylmethane-type intermediate (Figure 4). It is suggested that this intermediate can form readily in the large intracrystalline cavity (diameter. 1.3 nm) of faujasite, but is sterically inhibited in the smaller pores of mordenite and ZSM-4 (d -0.8 nm) and especially of ZSM-5 (d -0.6 nm). Thus, transition state selectivity rather than shape selective diffusion are responsible for the high xylene isomerization selectivity of ZSM-5. 

The techniques of monomolecular rate theory easily transform measured reaction data into a form where we can analyze apparent kinetics and the effects of intracrystalline diffusion by the use of selectivity data. Time dependency has been eliminated. Since selectivity is extremely reproducible and is independent of short-term aging effects, the number of experimental runs is reduced while data reliability is maintained. For catalyst evaluation at any temperature, it is necessary to determine the equilibrium composition and the straight-line reaction path. With this information any catalyst can be evaluated at this temperature with simply the additional information from a curved-line reaction path. The approach used in the application of monomolecular rate theory to the xylene isomerization selectivity kinetics is as follows. Reference is made to the composition diagram, Figure 1. 

Applicability of Monomolecular Rate Theory to Xylene Isomerization Selectivity Kinetics over Fresh AP Catalyst. The kinetics of liquid-phase xylene isomerization over fresh zeolite containing AP catalyst are effectively interpreted by pseudomonomolecular rate theory. The agreement between the experimental data (data points) and predicted reaction paths (solid lines) for operation at 400° and 600°F is shown in Figure 2. The catalyst used was in the form of extrudates comprised of the zeolite component and an A1203 binder. Since xylene disproportionation to toluene and trimethylbenzenes was low, selectivity data were obtained by mere normalization of the xylene compositions (2 axyienes = 1.0). 

In shape-selective catalysis, the pore size of the zeoHte is important. For example, the ZSM-5 framework contains 10-membered rings with 0.6-nm pore size. This material is used in xylene isomerization, ethylbenzene synthesis, dewaxing of lubricatius oils and light fuel oil, ie, diesel and jet fuel, and the conversion of methanol to Hquid hydrocarbon fuels (21). 

Mass transport selectivity is Ulustrated by a process for disproportionation of toluene catalyzed by HZSM-5 (86). The desired product is -xylene the other isomers are less valuable. The ortho and meta isomers are bulkier than the para isomer and diffuse less readily in the zeoHte pores. This transport restriction favors their conversion to the desired product in the catalyst pores the desired para isomer is formed in excess of the equUibrium concentration. Xylene isomerization is another reaction catalyzed by HZSM-5, and the catalyst is preferred because of restricted transition state selectivity (86). An undesired side reaction, the xylene disproportionation to give toluene and trimethylbenzenes, is suppressed because it is bimolecular and the bulky transition state caimot readily form. 

Many chemical reactions, especially those involving the combination of two molecules, pass through bulky transition states on their way from reactants to products. Carrying out such reactions in the confines of the small tubular pores of zeolites can markedly influence their reaction pathways. This is called transition-state selectivity. Transition-state selectivity is the critical phenomenon in the enhanced selectivity observed for ZSM-5 catalysts in xylene isomerization, a process practiced commercially on a large scale. 

Since their development in 1974 ZSM-5 zeolites have had considerable commercial success. ZSM-5 has a 10-membered ring-pore aperture of 0.55 nm (hence the 5 in ZSM-5), which is an ideal dimension for carrying out selective transformations on small aromatic substrates. Being the feedstock for PET, / -xylene is the most useful of the xylene isomers. The Bronsted acid form of ZSM-5, H-ZSM-5, is used to produce p-xylene selectively through toluene alkylation with methanol, xylene isomerization and toluene disproportionation (Figure 4.4). This is an example of a product selective reaction in which the reactant (toluene) is small enough to enter the pore but some of the initial products formed (o and w-xylene) are too large to diffuse rapidly out of the pore. /7-Xylene can, however. 

Initial inner acid sites isomerization selectivity is low for 10MR zeolites and high for Mordenite catalysts. This suggests that large 12MR channels of Mordenite are favorable to EB isomerization into xylenes in the zeolite microporosity. 

Parex (1) [Para extraction] A version of the Sorbex process, for selectively extracting p-xylene from mixtures of xylene isomers, ethylbenzene, and aliphatic hydrocarbons. The feedstock is usually a C8 stream from a catalytic reformer, mixed with a xylene stream from a xylene isomerization unit. The process is operated at 177°C the desorbent is usually p-diethylbenzene. The first commercial plant began operation in Germany in 1971 by 1992, 453 plants had been licensed worldwide. Not to be confused with Parex (2). 

Structure-Selectivity Relationship in Xylene Isomerization and Selective Toluene Disproportionation... 

As a result of steric constraints imposed by the channel structure of ZSM-5, new or improved aromatics conversion processes have emerged. They show greater product selectivities and reaction paths that are shifted significantly from those obtained with constraint-free catalysts. In xylene isomerization, a high selectivity for isomerization versus disproportionation is shown to be related to zeolite structure rather than composition. The disproportionation of toluene to benzene and xylene can be directed to produce para-xylene in high selectivity by proper catalyst modification. The para-xylene selectivity can be quantitatively described in terms of three key catalyst properties, i.e., activity, crystal size, and diffusivity, supporting the diffusion model of para-selectivity. 

Intermediate pore zeolites typified by ZSM-5 (1) show unique shape-selectivities. This has led to the development and commercial use of several novel processes in the petroleum and petrochemical industry (2-4). This paper describes the selectivity characteristics of two different aromatics conversion processes Xylene Isomerization and Selective Toluene Disproportionation (STDP). In these two reactions, two different principles (5,j6) are responsible for their high selectivity a restricted transition state in the first, and mass transfer limitation in the second. 

Early attempts to utilize the high acid activity of faujasite zeolite catalysts for direct xylene isomerization suffered from low selectivity. Considerable improvement was obtained first by using a large pore zeolite (7) catalyst and subsequently in several process modifications that use ZSM-5 as catalyst (2). In the following we will show how these selectivity differences can be related to structural differences of the various zeolites. 

We have examined the rate constants for disproportionation and isomerization for a variety of zeolites, using a commercial-type feed containing 70% m-xylene and 30% o-xylene in a fixed-bed flow reactor. The results, listed in Table I, show the exceptionally low disproportionation/isomerization selectivity of ZSM-5 relative to synthetic faujasite. Synthetic mordenite and ZSM-4 have intermediate selectivities. 

Figure 1. Comparison of the relative disproportionation versus isomerization selectivities of HZSM-5 and synthetic faujasite (8). Feed m-xylene. Temperature 300°C.

Table I. Selectivity in Xylene Isomerization Feed 70% m-/30% o-Xylene, 316°C Pressure 28 bar...

Figure 2. Effect of intracrystalline cavity diameter of several zeolites on selectivity in xylene isomerization.

In commercial xylene isomerization, it is desirable that the necessary ethylbenzene conversion is accompanied by a minimum conversion (transalkylation) of xylenes, since the latter constitutes a downgrading to less valuable products. The ability of ZSM-5 to convert ethylbenzene via transalkylation in high selectivity, as shown in Table II, leads to high ultimate p-xylene yields in a commercial process. With a simulated commercial feed containing 85% m- and o-xylene and 15% ethylbenzene, we have obtained the data shown in Table III. It is seen that for a given ethylbenzene conversion, the xylene loss... 

Table ill. Selectivity in Xylene Isomerization Feed 15% Ethylbenzene, 85% Xylene (63% m, 22% o)... 

We have shown that the high selectivity of ZSM-5 in xylene isomerization relative to larger pore acid catalysts is a result of its pore size. It is large enough to admit the three xylenes and to allow their interconversion to an equilibrium mixture it also catalyzes the transalkylation and dealkylation of ethylbenzene (EB), a necessary requirement for commercial feed but it selectively retards transalkylation of xylenes, an undesired side reaction. 

Selective xylene isomerization over HZSM5 zeolites (no disproportionation)... 

Selective xylenes isomerization and ethylbenzene conversion. US Patent 5,143,941. 

Kurschhner, U., Jerschkewitz, H.-G., Schreier, E., and Volter, J. (1990) Shape selectivity of hydrothermally treated H-ZSM-5 in toluene disproportionation and xylene isomerization. Appl. Catal, 57, 167-177. 

Figure 13.28 Meto-xylene disproportionation isomerization selectivity ratio over various zeolites at 31 7-318°C and 10% conversion [64].

Meta-xylene isomerization to ortho- and para-xylene over 10- and 12-MR zeolites is another illustration of product shape selectivity effects [13]. The two products are essentially equally favorable from the standpoint of thermodynamics. With decreasing pore size, however, kinetics come into play and the selectivity to para-xylene increases, as illustrated in Figure 13.37 for results obtained at 317-318°C, 0.5 kPa meta-xylene pressure (in the presence of He carrier gas) and 10% conversion [64]. While the para ortho ratio is typically 1.0-1.5 with multi-dimensional... 

Coke formation during xylene isomerization has been studied using in situ infrared spectroscopy [78]. A study done on EB isomerization with a bifunctional catalyst containing EUO zeolite indicated that poor initial selectivity of the catalyst improves after a period of fast deactivation, during which micropores are blocked [79]. 

ZSM-5 is a Mobil-proprietary, shape-selective zeolite which is used commercially in synthetic fuels (methanol-to-gasoline), petrochemicals (xylene isomerization, toluene disproportionation, benzene alkylation) and in petroleum refining (lube and... 

Xylenes. Because of the practical significance of xylenes, isomerization of xylenes over zeolites is frequently studied.348 The aim is to modify zeolite properties to enhance shape selectivity, that is, to increase the selectivity of the formation of the para isomer, which is the starting material to produce terephthalic acid. In addition, m-xylene isomerization is used as a probe reaction to characterize acidic zeolites.349,350... 

---