Catalysts para selectivity

The influence of interchannel dlffusional limitation may be estimated by a comparison of catalyst para-selectivities to separate product molecules, the diameters of which are different. As is known, the kinetic diameter of molecules increases in the sequence para-XYI para-selectivities to dial-... 

Traditional methods for bromination of toluene with bromine and a catalyst result in relatively low / ara-selectivity. For example, bromine in acetic acid gives rise to approximately a 4 1 mixture of the para- and ort/to-bromotoluenes (ref. 4). The para-selectivity is enhanced in trifluoroacetic acid so that approximately 90 % of the para-isomer is produced, but greater selectivity than this is unusual. 

Our own earlier work on the chlorination of toluene had been subject to similar constraints. In this case, chlorination with ferf-butyl hypochlorite had proved to be advantageous. In the presence of silica gel as catalyst the yield of chlorotoluenes was quantitative but the regioselectivity was more or less statistical (ref. 8). However, the use of proton-exchanged zeolite X allowed the production of chlorotoluenes with a para-selectivity of more than 90 % (Fig. 4) (ref. 9). No HCl is generated in this process since the by-product is tert-butanol, and there is no inhibition of the catalyst. Indeed, the catalyst can be reused if necessary. 

As an example of the selective removal of products, Foley et al. [36] anticipated a selective formation of dimethylamine over a catalyst coated with a carbon molecular sieve layer. Nishiyama et al. [37] demonstrated the concept of the selective removal of products. A silica-alumina catalyst coated with a silicalite membrane was used for disproportionation and alkylation of toluene to produce p-xylene. The product fraction of p-xylene in xylene isomers (para-selectivity) for the silicalite-coated catalyst largely exceeded the equilibrium value of about 22%. 

As described in the previous section, the silica-alumina catalyst covered with the silicalite membrane showed exceUent p-xylene selectivity in disproportionation of toluene [37] at the expense of activity, because the thickness of the sihcahte-1 membrane was large (40 pm), limiting the diffusion of the products. In addition, the catalytic activity of silica-alumina was not so high. To solve these problems, Miyamoto et al. [41 -43] have developed a novel composite zeohte catalyst consisting of a zeolite crystal with an inactive thin layer. In Miyamoto s study [41], a sihcahte-1 layer was grown on proton-exchanged ZSM-5 crystals (silicalite/H-ZSM-5) [42]. The silicalite/H-ZSM-5 catalysts showed excellent para-selectivity of >99.9%, compared to the 63.1% for the uncoated sample, and independent of the toluene conversion. 

The excellent high para-selectivity can be explained by the selective escape of p-xylene from the H-ZSM-5 catalyst and inhibition of isomerization on the external surface of catalysts by silicalite-1 coating. In addition to the high para-selectivity, toluene conversion was still high even after the silicalite-1 coating because the silicalite-1 layers on H-ZSM-5 crystals were very thin. 

The zeohte overgrowth has been reported for FAU on EMT zeohte [44] and MCM-41 on FAU zeohte [45]. On the other hand, in this study, zeohte layers were grown on the zeohte with the same framework structure, resulting in high coverage of ZSM-5 crystals with silicalite layers and high para-selectivity. The zeohte crystals with oriented thin layer on their external surface are expected to form a new class of shape-selective catalysts. 

Keggin type H3PW)2O40 is a stable, recyclable and effective catalyst for H2S04-free liquid phase nitration of bezene, chlorobenzene and toluene with nitric acid as a nitration agent. Higher para-selectivity of nitrotoluene was obtained, and the result implies that HPA can effectively catalyze the liquid phase nitration of various aromatics as an environmentally friendly nitration process. 

Entry 5 is an example of nitration in acetic anhydride. An interesting aspect of this reaction is its high selectivity for the ortho position. Entry 6 is an example of the use of trifluoroacetic anhydride. Entry 7 illustrates the use of a zeolite catalyst with improved para selectivity. With mixed sulfuric and nitric acids, this reaction gives a 1.8 1 para ortho ratio. Entry 8 involves nitration using a lanthanide catalyst, whereas Entry 9 illustrates catalysis by Sc(03SCF3)3. Entry 10 shows nitration done directly with N02+BF4, and Entry 11 is also a transfer nitration. Entry 12 is an example of the use of the N02—03 nitration method. 

Selectivity to p-isopropyl toluene being close to 30 % was achieved with SSZ-33, SSZ-35 and Beta zeolites. This is connected with the 12-MR channels in SSZ-33 and Beta. In the case of SSZ-35 the presence of 18-MR cavities decreased the differences in the rate of transport of individual isopropyl toluene isomers. In contrast, ZSM-5 zeolite behaves as para-selective catalyst in this alkylation reaction, the selectivity to p-isopropyl toluene reached 76 % after 180 min of T-O-S. 

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. 

Various ways to modify ZSM-5 catalyst in order to induce para-selectivity have been described. They include an increase in crystal size (15,17,20) and treatment of the zeolite with a variety of modifying agents such as compounds of phosphorus (15,18), magnesium (15), boron (16), silicon (21), antimony (20), and with coke (14,18). Possible explanations of how these modifications may account for the observed selectivity changes have been presented (17) and a mathematical theory has been developed (22). A general description of the effect of diffusion on selectivity in simple parallel reactions has been given by Weisz (23). 

We find that the degree of para-selectivity obtainable depends uniquely on the activity and diffusion characteristics of the catalyst, independent of how these properties are obtained. While we will discuss these relationships with regard to STDP, the principles involved are generally applicable to those reactions over ZSM-5 where dialkylaromatic products are formed. 

The general characteristics of toluene disproportionation are summarized by the data presented in Figure 8. With standard HZSM-5 catalyst, as indicated by the lowest curve, the xylenes produced contain essentially an equilibrium concentration of the para isomer (24%) and exceed it only slightly at low conversion. The other curves result from a variety of HZSM-5 catalysts modified in different ways and to different degrees. It is apparent that a wide range of para-selectivities can be obtained. At increasing toluene conversions, the para-selectivity decreases for all catalysts. 

In view of the difficulty of measuring the diffusivity of o-xylene at the reaction temperature, 482°c, we have used the diffusivity determined at 120°C. For a series of ZSM-5 catalysts, the two D-values should be proportional to each other. Para-xylene selectivities at constant toluene conversion for catalysts prepared from the same zeolite preparation (constant r) with two different modifiers are shown in Figure 11. The large effect of the modifier on diffusivity, and on para-selectivity, is apparent. 

Para-selectivity for a wide variety of ZSM-5 preparations of comparable activity are shown in Figure 12. These data include results for unmodified HZSM-5 s of varying crystal size as well as chemically modified HZSM-5 s. Since the activity of these catalysts is nearly identical, these data clearly establish the major role of diffusion in the para-xylene content of the xylenes produced in TDP. We have examined in more detail the effect of the concentration of one of these chemical modifiers, MgO. 

The beneficial effect of catalyst activity, k, can also be seen from the temperature dependence of the para-selectivity. Comparing the selectivity for the same, unmodified ZSM-5 catalyst at 550°C and 600 °C in Figure 10 shows the advantage of the... 

If the data in Figure 13 are replotted against a.t0.3 as a pseudo Thiele-modulus, a single curve describing all the catalysts (Figure 15) results. Thus, the para-selectivity of a catalyst can be readily predicted from this empirical correlation and a knowledge of two basic catalyst properties, activity and diffusion time. Furthermore, these data are in full agreement with the model advanced above, which describes para-selectivity in terms of a classical diffusion-reaction interplay. 

It has also been shown that the selectivity features of para-selective catalysts can be readily understood from an interplay of catalytic reaction with mass transfer. This interaction is described by classical diffusion-reaction equations. Two catalyst properties, diffusion time and intrinsic activity, are sufficient to characterize the shape selectivity of a catalyst, both its primary product distribution and products at higher degrees of conversion. In the correlative model, the diffusion time used is that for o-xylene adsorption at... 

To reveal factors which influence activities of acid-base catalysts in alkylation and isomerization is the challenge to activity in this field. Q he greatest amount of work has been done in connection with the effect of para-selectivity, which is observed in alkylation of aromatic hydrocarbons on ZSM-5 type zeolites [1]. This effect has been explained by a number of authors either by the influence of diffusion factors [2,3] or by the isomerizing activity of the external surface of zeolite crystals [4]. In refs. [5,6] and especially in ref.[7] the para-selective effect of ZSM-5 type zeolites is shown to be due to decreasing their isomerizing activity becaiase of the decrease in the concentration of strong protic centres as a result of modifiers introduced. Para-selective effect is related to the action of chemical factors. However, in... 

In 2003, Kulkarni and coworkers presented a method for the -selective oxybromi-nation of a variety of substituted phenols employing a novel heterogeneous catalytic system, the CrZSM-5 as catalyst, H2O2 as oxidant and KBr as bromine source ". Next to CrZSM-5 also other zeolites have been tested as catalysts, but although MoZSM-5 showed the highest conversion after 5 hours (89%), para-selectivity was lower (para 36% ortho 31% dibromination 22%) than observed with the CrZSM-5 material (83%... 

Alkylation of toluene with methanol, a process of practical importance, was investigated over several acidic clay catalysts.98 Cation-exchanged synthetic saponites201 and fluor-terasilicic mica modified by La3+ ions202 were found to exhibit increased para selectivity compared with H-ZSM-5. 

The zeolite can easily be regenerated by heating. Similar high para selectivity can be achieved in the case of toluene by use of tert-butyl hypobromite as reagent with zeolite HX in a solvent mixture (CCI4 and ether). ZnBr2 supported on mesoporous silica or acid-activated montmorillonite is a fast, effective, reusable catalyst for the para-bromination of alkylbenzenes.257... 

Exclusive ring-nitration occurs with alkylbenzenes. The nitration of toluene in the presence of H-ZSM-5 and molecular oxygen shows a remarkable enhancement of para selectivity (ortho para ratio = 0.08).268 A review is available for the nitration of aromatics by nitrogen oxides on zeolite catalysts.269... 

If we examine the formation of hydroxyacetophenones more closely, we can see (Fig. 4a) that on HY, at least part of ortho-hydroxyacetophenone could be formed directly from phenylacetate (i.e, intramolecularly) whereas the para-isomer is clearly a secondary product. On HZSM5 both compounds are secondary products (Fig. 4b). Moreover, one can see that the ortho-/para-hydroxyace-tophenone molar ratio changes with conversion especially over HZSM5 where it decreases from 6 to 1 as conversion decreases. Two explanations can be considered i) a consecutive transformation of para-hydroxyacetophenone which would not occur in the case of the ortho-isomer ii) a change in the ortho-/para-selectivity of the zeolite in the course of deactivation. The points at high conversion being obtained on the fresh catalyst, a preferential deactivation of the sites located outside of the particles will decrease the ortho-/para-hydroxyacetophenone molar ratio if one supposes that these sites which are easily accessible favour the formation of the ortho-... 

Some zeolitic and non-zeolitic molecular sieve catalysts are claimed to be capable for ortho- and para-selective alkylation using olefin as alkylating agent (refs. 1,2). Zeolite catalysts are less active and selective in the methylation of aniline by methanol (refs. 3,4). Reaction is usually carried out with a large excess of methanol since a large fraction of the alcohol decomposes without participating in the alkylation. Numerous N- and C-alkylated aniline derivatives appear in the reaction product. It was found that N-alkylation requires basic sites while C-alkylation occurs mainly on acidic sites (refs. 5-7). 

Nitration of monosubstituted aromatics, toluene in particular, has been extensively studied using zeolites in order to direct the reaction towards the formation of the desired para-isomer. Toluene has been nitrated para-selectively with benzoyl nitrate over zeolite catalysts.[14,15] For example, when mordenite is used as a catalyst, MNTs are formed in almost quantitative yields, giving 67 % of the para-isomer in 10 min, but tetrachloromethane is required as solvent. However, the main problems associated with the use of benzoyl nitrate are handling difficulties due to its sensitivity toward decomposition, and the tendency toward detonation upon contact with rough surfaces. Nagy et a/.[19 21] reported the nitration of benzene, chlorobenzene, toluene and o-xylene with benzoyl nitrate in the presence of an amorphous aluminosilicate, as well as with zeolites HY and ZSM-11, in hexane as a... 

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