Operating temperature, isomerization process

Mobil s Low Pressure Isomerization Process (MLPI) was developed in the late 1970s (123,124). Two unique features of this process are that it is Operated at low pressures and no hydrogen is used. In this process, EB is converted to benzene and diethylbenzene via disproportionation. The patent beheved to be the basis for the MLPI process (123) discusses the use of H-ZSM-5 zeoHte with an alumina binder. The reaction conditions described are start-of-mn temperatures of 290—380°C, a pressure of 273 kPa and WHSV of 5—8.5/h. The EB conversion is about 25—40% depending on reaction conditions, with xylene losses of 2.5—4%. The PX approach to equiHbrium is about 99 ndash 101%. The first commercial unit was Hcensed in 1978. A total of four commercial plants have been built. 

In the Institut Fransais du Petrc le process (62), ethylene is dimerized into polymer-grade 1-butene (99.5% purity) suitable for the manufacture of linear low density polyethylene. It uses a homogeneous catalyst system that eliminates some of the drawbacks of heterogeneous catalysts. It also inhibits the isomerization of 1-butene to 2-butene, thus eliminating the need for superfractionation of the product (63,64). The process also uses low operating temperatures, 50—60°C, and pressures (65). 

The other commercialized pentane isomerization process is that of the Standard Oil Co. (Indiana) (20). This process differs from the Indiana-Texas butane process in that the aluminum chloride is introduced as a slurry directly to the reactor and that about 0.5% by volume of benzene is added continuously in the feed to suppress side reactions. Temperature, catalyst composition, space velocity, and hydrogen chloride concentration are generally similar to those in the corresponding butane process, but the reactor pressure is about 100 pounds lower. The Pan American Refining Co. operated the Indiana pentane isomerization process commercially during the last nine months of the war and produced about 400 barrels of isopentane per calendar day. 

Numerous other technologies, mainly gas-phase hydrogenations, were developed over the years (Sinclair-Engelhard,333,334 Hytoray,335,336 Arco,337 DSM,338 UOP339). The Arco and DSM processes operate at 400°C and under 25-30 atm. Despite the high temperature, isomerization is negligible because of the very short contact time. 

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%. 

Mobil Chemical has devdoped a xylene isomerization process called LTI (Low Temperature Isomerization) whick in the liquid phase, uses qsedal zeolites as catalysts (ZSM5), commercialized by the designation AP (Aromatics Processing These systems are more active than those the REX type, which are generally proposed for vapor phase operation. 

The effect of the temperature. The operating temperature affects the isomerization process in two important ways. 

Initially, aluminum chloride was the catalyst used to isomerize butane, pentane, and hexane. Siace then, supported metal catalysts have been developed for use ia high temperature processes that operate at 370—480°C and 2070—5170 kPa (300—750 psi), whereas aluminum chloride and hydrogen chloride are universally used for the low temperature processes. 

The Alphabutol process (Figure 7-8) operates at low temperatures (50-55°C) and relatively low pressures (22-27 atm). The reaction occurs in the liquid phase without a solvent. The process scheme includes four sections the reactor, the co-catalyst injection, catalyst removal, and distillation. The continuous co-catalyst injection of an organo-hasic compound deactivates the catalyst downstream of the reactor withdrawal valve to limit isomerization of 1-hutene to 2-hutene. Table 7-2 shows the feed and product quality from the dimerization process. 

MHTI [Mobil high temperature isomerization] A process for converting mixed xylene streams to />-xylene. The catalyst is the zeolite ZSM-5. Developed by Mobil Research Development Corporation and first commercialized in 1981. Eleven units were operating as of 1991. See also MLPI and MVPI. 

Like in any catalytic process, process variables crucially impact reaction kinetics, conversion efficiency and catalyst stability. Increasing temperature favors cracking, thus decreasing the isomerate yield. It is preferred to have a high-activity catalyst and operate at the lowest possible temperature to achieve the highest RONC. Hydrogen shifts the equihbrium concentrations of olefins and carbenium ions. 

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. 

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