Isomerization hydroisomerization

Upgrading of natural-gas liquids to motor fuels with customary technology used in the petroleum industry (isomerization, hydroisomerization, etc.) represents difficulties. One reason is that the volatility of motor fuels cannot be increased, thus limiting treatments such as hydrocracking. 

It is advantageous to pretreat butene feeds before alkylation.294-298 1,3-Butadiene is usually hydrogenated (to butenes or butane) since it causes increased acid consumption. The additional benefit of this process is that under hydrogenation conditions alkene isomerization (hydroisomerization) takes place, too. Isomerization, or the transformation of 1-butene to 2-butenes, is really attractive for HF alkylation since 2-butenes give better alkylate (higher octane number) in HF-cata-lyzed alkylation. Excessive 1,3-butadiene conversion, therefore, ensuring 70-80% isomerization, is carried out for HF alkylation. In contrast, approximately 20% isomerization is required at lower butadiene conversion for alkylation with H2SO4. 

Lanthanide-containing heterogeneous catalysts have also been widely claimed as suitable for various hydrocarbon reactions such as isomerization, hydroisomerization, hydrogenation, alkylation, disproportionation, cyclization, aromatization, ammonoxidation, and methana-tion, so that their application in reforming, hydrotreating and other industrial processes is easily predictable. 

We have explored rare earth oxide-modified amorphous silica-aluminas as "permanent" intermediate strength acids used as supports for bifunctional catalysts. The addition of well dispersed weakly basic rare earth oxides "titrates" the stronger acid sites of amorphous silica-alumina and lowers the acid strength to the level shown by halided aluminas. Physical and chemical probes, as well as model olefin and paraffin isomerization reactions show that acid strength can be adjusted close to that of chlorided and fluorided aluminas. Metal activity is inhibited relative to halided alumina catalysts, which limits the direct metal-catalyzed dehydrocyclization reactions during paraffin reforming but does not interfere with hydroisomerization reactions. 

It was assumed that C—C bond cleavage passes through an elementary step of p-alkyl transfer. The mechanism of hydroisomerization passes also by a p-alkyl transfer step, but in this case the P-H elimination-olefin reinsertion occurs rapidly and a skeletal isomerization also occurs. 

The hydroisomerization of heavy linear alkanes is of a great interest in petroleum industry. Indeed, the transformation of long chain n-alkanes into branched alkanes allows to improve the low temperature performances of diesel or lubricating oils [1-3]. On bifunctional Pt-exchanged zeolite catalysts, n-CK, transformed into monobranched isomers, multibranched isomers and cracking products [4], The HBEA zeolite based catalyst was more selective for isomerization than those containing MCM-22 or HZSM-5 zeolites [4], This was explained on one hand by a rapid diffusion of the reaction intermediates inside the large HBEA channels, and on the other hand by the very small crystallites size of this zeolite (0.02 pm). 

The development of composite micro/mesoporous materials opens new perspectives for the improvement of zeolytic catalysts. These materials combine the advantages of both zeolites and mesoporous molecular sieves, in particular, strong acidity, high thermal and hydrothermal stability and improved diffusivity of bulky molecules due to reduction of the intracrystalline diffusion path length, resulting from creation of secondary mesoporous structure. It can be expected that the creation of secondary mesoporous structure in zeolitic crystals, on the one hand, will result in the improvement of the effectiveness factor in hydroisomerization process and, on the other hand, will lead to the decrease of the residence time of products and minimization of secondary reactions, such as cracking. This will result in an increase of both the conversion and the selectivity to isomerization products. 

Of course, certain features of overall kinetics are inaccessible via a cluster model method, such as the influence of pore structure on reactivity. The cluster model method cannot integrate reaction rates with concepts such as shape selectivity, and an alternative method of probing overall kinetics is needed. This has recently been illustrated by a study of the kinetics of the hydroisomerization of hexane catalyzed by Pt-loaded acidic mordenite and ZSM-5 (211). The intrinsic acidities of the two catalysts were the same, and differences in catalyst performance were shown to be completely understood on the basis of differences in the heat of adsorption of hexene, an intermediate in the isomerization reaction. Heats of adsorption are strongly dependent on the zeolite pore diameter, as shown earlier in this review (Fig. 11). 

Although not a separate process, isomerization plays an important role in pretreatment of the alkene feed in isoalkane-alkene alkylation to improve performance and alkylate quality.269-273 The FCC C4 alkene cut (used in alkylation with isobutane) is usually hydrogenated to transform 1,3-butadiene to butylenes since it causes increased acid consumption. An additional benefit is brought about by concurrent 1-butene to 2-butene hydroisomerization. Since 2-butenes are the ideal feedstock in HF alkylation, an optimum isomerization conversion of 70-80% is recommended.273... 

According to the Horiuti-Polanyi mechanism, isomerization requires the participation of hydrogen. The first addition step, formation of the half-hydrogenated state [Eq. (11.3)], cannot take place without hydrogen. Numerous investigations have supported the role of hydrogen in these so-called hydroisomerizations. 

The hydroisomerization of light paraffins (C5-C6-C7) to produce their branched isomers is an important industrial process aimed at improving the octane number of the light straight mm stream (LSR). Reformulated gasolines with their impact on olefins and aromatics reduction [26, 27] have increased the number of LSR isomerization units. Table 5.1 gives the octane number of the different C5-C7 linear and branched paraffins. 

Dorbon M, Chodorge JA, Cosyns JA, Viltard JC, Didillon B. Method for producing high-purity isobutene through hydroisomerization reactive distillation and skeletal isomerization ofc4 alkenes. FR 2757506, Institut Frangais du Petrole, 1998. 

Another example of secondary shape selectivity is shown by John and co-workers (77,73). They found that the hydroisomerization/hydroeracking of n-hexane over Pt/H-mordenite is significantly inhibited by the presence of benzene. They also found a correlation between the aromatic size relative to zeolite pore size on the inhibition of the hexane reaction and the changes in isomer selectivities. Figure 4 illustrates the relation between the various aromatics co-fed and the n-hexane isomerization rates on H-mordenite. From Figure 4, it is shown that as the kinetic diameter of the aromatics is increased, the isomer formation rate appears to pass through a minimum. This result can be explained by considering the size of the zeolite pore and the kinetic... 

Kuba et al. (2003) monitored a WC>3/Zr02 catalysts with and without platinum during n-pentane isomerization and hydroisomerization at 523 K their equipment consisted of a reactor placed next to an integrating... 

The increase of 1 unit of the RON corresponds to about 900.000 US per year for a 300.000 tpa hydroisomerization unit (1). In Figure 7.1, several major refinery processes to improve RON are shown these include isomerization, reforming, addition of FCC-Naphtha, alkylation, addition of oxygenates or polygas or butanes. The effect of these options with respect to the new specifications is different for each particular process. Keeping in mind the Californian ban on MTBE and also the fact... 

The noble metal component may be either palladium or platinum the effect of the concentration of both metals on methylpentane as well as on dimethylbutane selectivity in C6 hydroisomerization on lanthanum and ammonium Y-zeolite with Si/Al of 2.5 has been studied by M.A. Lanewala et al. (5). They found an optimum of metal content for that reaction between 0.1 and 0.4 wt.-%. The noble metal has several functions (i) to increase the isomerization activity of the zeolite (ii) to support the saturation of the coke precursors and hence prevent deactivation, as was shown by H.W. Kouvenhoven et al. (6) for platinum on hydrogen mordenite (iii) to support the hydrodesulfurization activity of the catalysts in sulfur containing feedstocks. 

Commercial zeolite based hydroisomerization catalysts comprise alumina bound and platinum impregnated dealuminated mordenite. The activity and selectivity of the hydroisomerization of n-paraffins is strongly influenced by acid leaching. The influence of silica to alumina ratio has been studied for pentane isomerization over platinum mordenite many times since one of the first papers published (6). 

Laboratory studies have shown that omega (MAZ structure type) based paraffin hydroisomerization catalyst shows higher activity than mordenite based catalyst and better selectivity, i.e. higher octane due to higher yield of di-branched paraffins compared to mordenite performance (17). The isomerization of a C5/C6 cut at 15 bar results in a final calculated RON of 80.4 for the alumina bound dealuminated PtH-MOR catalyst supplied by IFP with undisclosed (most likely similar) Si/Al ratio, measured at 265 °C compared to a RON value of 80.9 for an alumina bound dealuminated PtH-MAZ catalyst with bulk Si/Al = 16, measured at 250 °C. Both measurements were performed in a bench-scale tubular reactor with a volume of 50 cm3 of 2 mm diameter extrudates with WHSV of 1.5 h and H2/HC of 4. This... 

Hydroisomerization is one of the few major refinery processes that allow refineries to cope with the future fuel regulations on the one side and the necessity to supply premium fuel with the necessary octane on the other side. Due to the limited volume the chemical industry can cope with in addition to the present level, future reduction of the aromatics in fuels will force the refineries to convert as much of the aromatics as possible to fuel components. One possible option is to feed the one-ring aromatics such as benzene to an isomerization unit. A state of the art hydroisomerization catalyst such as HYSOPAR is very active for benzene hydrogenation at temperatures as low as 100°C, where 100% hydrogenation is achieved, and can cope with up to 15 wt.-% of benzene in the feed. When sulfur in the range of 50 ppm is present in the feed, a partial inhibition of... 

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