Isomerization operating conditions

Most of the benzene in the gasoline pool comes from the reformer unit (reformate). To reduce the reformate s benzene, one must modify the feedstock quality and/or operating conditions. Benzene s precursors in the reformer feed (C, and C ) can be prefractionated and sent to an isomerization unit. The reformer operating pressure can be reduced... 

A quantitative model requires knowledge of the diffusivity under reaction conditions and of the intrinsic activities for toluene disproportionation and xylene isomerization. While these are not easily obtained, the methodology has been worked out for the case of paraffin and olefin cracking (5). So far, we have obtained an approximate value for the diffusivity, D, of o-xylene at operation conditions from the rate of sorptive o-xylene uptake at lower temperature and extrapolation to 482°C (Table V). 

When Wa = substituted aminoacyl, that is, when Wa-Xaa is a peptide, there is a strong tendency to form an oxazolone. The 2-alkyl-5(4//)-oxazolone that is formed is chirally unstable. Isomerization of the 2-alkyl-5(4//)-oxazolone generates diaste-reomeric products. When Wa = R0C=0, there is a lesser tendency to form an oxazolone. The 2-alkoxy-5(4/7)-oxazolone that is formed is chirally stable. No isomerization occurs under normal operating conditions. Finally, when Wa = R0C=0, an additional productive intermediate, the symmetrical anhydride, can and often does form. 

Under the operating conditions, the reaction intermediates (w-hexenes and i-hexenes in n-hexane isomerization) are thermodynamically very adverse, hence appear only as traces in the products. These intermediates (which are generally olefinic) are highly reactive in acid catalysis, which explains that the rates of bifunctional catalysis transformations are relatively high. The activity, stability, and selectivity of bifunctional zeolite catalysts depend mainly on three parameters the zeolite pore structure, the balance between hydrogenating and acid functions, and their intimacy. In most of the commercial processes, the balance is in favor of the hydrogenation function, that is, the transformations are limited by the acid function. 

The operating conditions for the three processes are very similar— only temperatures are somewhat dissimilar. The Shell Development system, employing a modified Friedel-Crafts system, operates at a lower temperature—150°-210°F vs. 250°-400°F for the other two processes. However, the equilibrium effects of the temperature differences are minimized as shown by the similarity in n-C4 and n-C5 yields shown in Table VI. Unleaded octane numbers for C5/C6 isomerate, obtained from a pure C5/C6 straight-run fraction, could not be found in the literature for the Shell process. However, pilot unit operations charging laboratory blends of n-C5, n-C6, and C6 naphthenes have been reported (26, 45). In the Shell process the use of antimony trichloride and hydrogen has considerably reduced the amount of side reactions for a Friedel-Crafts system so that the yield for this process is quite close to the yield structure for the other two processes. 

This paper deals with the selective synthesis of 2-acetyl-6-methoxynaphthalene, precursor of Naproxen, over zeolite catalysts and especially over HBEA zeolites. As has been previously observed3 8, acetylation of 2-methoxynaphthalene occurs preferentially at the kinetically controlled 1-position with formation of l-acetyI-2-methoxynaphthalene (I). The desired isomer, 2-acetyl-6-methoxynaphthalene (II) and the minor isomer, l-acetyl-7-methoxynaphthalene (HI), are the other primary products. However, it will be shown that in presence of 2MN, isomerization of I can occur allowing a selective production of II, the desired product the effect of the operating conditions (solvent, temperature) and of the acidity and porosity of the zeolite catalyst will be presented. 

The typical operating conditions of xylene and EB isomerization processes are shown in Table 9.3. These conditions minimize the above side reactions. Pressure, temperature and H2/HC ratio are key parameters that define the partial pressure of C8 naphthenes intermediates for EB isomerization. Naphthene cracking and disproportionation/transalkylation are responsible for the C8 aromatics net losses that affect the overall pX yield. The C8 recycled stream from the isomerization unit to the separation unit is three times higher than the fresh feed stream (since there cannot be more than 24% of pX in the C8 aromatic cut after isomerization). This means that each percent of loss in the isomerization unit will decrease the pX yield by 3%. For example, when standard mordenite-based catalysts lead to 4% of net losses, the overall pX yield is roughly 88%. 

Tahle 9.3 Typical operating conditions of Xylene and EB isomerization processes... 

Table 9.4 Typical operating conditions for Xylene Isomerization and EB dealkylation processes...

By adjusting the amount of boron trifluoride, introduced in gaseous form in hydrofluoric add in contact with the organic phase, it is therefore possible to extract the m-xylene from an aromatic Cg cut after agitation. The HF—BFj solvent is also an isomerization catalyst whose activity is related to the operating conditions, so that the combination of extraction and isomerization (see Section 4.4.Z2) offers a number of economic advantages. 

Thus, in ammonia synthesis, mixed oxide base catalysts allowed new progress towards operating conditions (lower pressure) approaching optimal thermodynamic conditions. Catalytic systems of the same type, with high weight productivity, achieved a decrease of up to 35 per cent in the size of the reactor for the synthesis of acrylonitrile by ammoxidation. Also worth mentioning is the vast development enjoyed as catalysis by artificial zeolites (molecular sieves). Their use as a precious metal support, or as a substitute for conventional silico-aluminaies. led to catalytic systems with much higher activity and selectivity in aromatic hydrocarbon conversion processes (xylene isomerization, toluene dismutation), in benzene alkylation, and even in the oxychlorination of ethane to vinyl chloride. 

F. and the conditions mentioned, a minimum partial pressure of about 60 p.s.i. is required to prevent disproportionation. Under milder conditions, somewhat lower partial pressures will serve, but conversion is much lower. Hydrogen pressures above 100 p.s.i. tend to suppress isomerization. A total reactor pressure of 300 p.s.i. is sufficient to obtain the desired hydrogen partial pressure at operating conditions. 

The applicability of the intimacy criterion has been demonstrated 19) in a series of tests on n-heptane isomerization under conventional operating conditions, i.e., at elevated hydrogen partial pressure where catalyst deactivation is minimized. The reaction was examined over mechanically distinct but mixed particles of X (Pt-bearing particles) and Y (silica-alumina) of varying particle size R (equal for both types of particles) in 50-50 volume proportion as well as over single type catalyst in the reaction zone. The reaction conditions provided a partial pressure of n-heptane of 2.5 atm., of hydrogen of 20 atm., and a residence time of 17 sec. 

In order to study the effect of SCF operating conditions on reaction equilibrium and kinetics, an experimental facility has recently been completed and successfully tested as described in the following section. The heterogeneous catalytic isomerization of 1-hexene over Pt/ y-Al20o catalyst is chosen as the model reaction system i.e., a reaction system that undergoes simultaneous deactivation by coking. 

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