Platinum-alumina isomerization

Proportions of Isotopically Labeled Products from Isomerization of Hexanes over 0.2% Platinum /Alumina Catalyst at 273°C ... 

Pig. 4. Effect of nCs/Hs ratio on nCt isomerization at 372°C. over platinum-alumina catalyst (S4). 

Fig. 5. Isomerization rate versus pentene partial pressure (S4). Comparison of n-pentane isomerization rate over platinum-alumina catalyst with the rate of skeletal isomerization of 1-pentene over the platinum-free catalyst 372°C.

Thus, at 372°C. and over the range of pressures and hydrogen to n-pentane ratios covered in the investigation, it appears that the proposed mechanism can account in large part for the observed kinetic data. However, Starnes and Zabor (S8) have proposed an alternative mechanism, based on their studies of n-pentane isomerization over platinum-alumina-halogen catalysts. They postulate that the paraffin is adsorbed on platinum sites with dissociation of a hydrogen atom, followed by polarization of the adsorbed species. 

Fig. 6. Effect of hydrogen pressure on rate of isomerization of n-heptane over platinum-alumina catalyst (R3). The rate n is relative to the rate of isomerization at 471 °C., ph = 5.8 atm.

Isomerization catalysts were developed along two paths—by Friedel-Crafts halide systems or by dual site heterogeneous catalysts, originating with the commercial introduction of platinum-aluminas for catalytic reforming in the 1940,s. The Friedel-Crafts systems (aluminum chloride-hydrocarbon complexes) were used exclusively during the early stages of... 

World War II when the first commercial isomerization processes were introduced to manufacture isobutane as a feedstock for aviation alkylate. The Friedel-Crafts catalysts are highly active at 100°-200°F whereas the conventional platinum-alumina reforming catalysts give reasonable reaction rates only above 850°F. 

C5- and C6- cyclizations are parallel reactions. Csicsery has shown that isomerization of tetralin to methylindan over platinum-alumina at 371°C is extremely slow (22). Davis and Venuto provided further evidence by showing that methylindan is also not converted to tetralin or naphthalene over platinum on silica-alumina (23). This behavior is similar to that observed in the cyclization of aliphatic hydrocarbons. Davis and Venuto also reported that the major aromatic products obtained from ten C8-C9 paraffins and olefins at 482°C are only formed by direct six-membered ring... 

Goble and Lawrence attributed the high isomerization activity of chlorinated platinum-alumina catalyst to the creation of a localized dual site comprising a Lewis acid site and an adjacent platinum site. However, as has since been pointed out by Asselin et al. (88), carbonium ion intermediates over low-temperature isomerization catalysts are probably created by the same process as that observed for Friedel-CrEifts catalyst abstraction of hydride ion from the paraffin by a strong Brdnsted acid according to the equation... 

As discussed in Section IV, Barron et al. (55, 61) found the cyclic mechanism of isomerization to be predominant, perhaps the sole route, on a highly dispersed platinum-alumina (0.2% w/w Pt). The cyclic mechanism was shown to be important also over platinum films and supported platinum of moderate dispersion (>100 A). Here, although the product distributions were very different from that found over the dispersed catalyst, the initial product distributions at 300°C were practically identical in the isomerization and in methylcyclopentane hydrogenolysis. At lower temperatures they were somewhat different as they also were at all temperatures on platinum films. It was suggested that, especially on platinum films, a bond-shift isomerization could accompany the cyclic... 

The cyclic mechanism (Scheme 7), which involves dehydrocyclization to an adsorbed cyclopentane intermediate C, followed by ring cleavage and desorption of the products, and is responsible for the isomerization of larger molecules on dispersed platinum-alumina catalysts (52, 55). 

The label has been located in the isomerization products obtained from 2-methylpentane-2- C, 2-methylpentane-4- C and 3-methylpentane-3- C on 10% platinum-alumina and single crystals under 20 Torr hydrogen pressure (54, 60). Under these conditions, the scrambling of the label was found to be extremely limited less than 10% of abnormal varieties are obtained. However, for these alkanes, on such catalysts and in these conditions, the selective cyclic mechanism is widely predominant and yields... 

A. Isomerization and Hydrogenolysis of Hexanes AND Pentanes on Platinum-Alumina... 

The relative rate of isomerization of the butenes is small over platinum-alumina between 0 and 100° 31). Cis-2-butene undergoes cis-trans isomerization some fifteen times faster than the frans-isomer, while double-bond migration of 1-butene proceeds at an intermediate... 

Platinum-alumina catalysts have been of profound importance in petroleum naphtha reforming and paraffin isomerization processes. Much information has been established concerning platinum crystallite size and interaction with the acidic support in terms of... 

Platinum on alumina-reforming catalysts, whether modified by additional components or not, are referred to as bifunctional. Separate and distinct reactions occur on the platinum site and on the alumina. The platinum typically performs dehydrogenation and hydrogenolysis, whereas the acidic alumina isomerizes, cy-clizes, and cracks. 

The introduction of dual-function catalysts for naphtha lefomiing and the demand for high-octane gasoline led to further interest in isomerization. The platinum/alumina (cUorided) catalysts were a success despite the resulting lower conversion to high-octane products from the need to operate at higher temperatures. The Shell Hysomer process, which used a 5A-zeolite to separate low-octane paraffins from the product allowed operators to recycle unconverted feed and achieve almost 100% conversion. ... 

Isomerization. Isomerization is a catalytic process which converts normal paraffins to isoparaffins. The feed is usually light virgin naphtha and the catalyst platinum on an alumina or zeoflte base. Octanes may be increased by over 30 numbers when normal pentane and normal hexane are isomerized. Another beneficial reaction that occurs is that any benzene in the feed is converted to cyclohexane. Although isomerization produces high quahty blendstocks, it is also used to produce feeds for alkylation and etherification processes. Normal butane, which is generally in excess in the refinery slate because of RVP concerns, can be isomerized and then converted to alkylate or to methyl tert-huty ether (MTBE) with a small increase in octane and a large decrease in RVP. 

They represent an improvement over earlier platinum on alumina catalysts in their abiHty to resist coke fouling when operated at low pressures. Dehydrogenation and hydrogenation occur on the active metal sites isomerization takes place on the acidic alumina surface. 

Catalytic processes frequently require more than a single chemical function, and these bifunctional or polyfunctional materials innst be prepared in away to assure effective communication among the various constitnents. For example, naphtha reforming requires both an acidic function for isomerization and alkylation and a hydrogenation function for aromati-zation and saturation. The acidic function is often a promoted porous metal oxide (e.g., alumina) with a noble metal (e.g., platinum) deposited on its surface to provide the hydrogenation sites. To avoid separation problems, it is not unusual to attach homogeneous catalysts and even enzymes to solid surfaces for use in flow reactors. Although this technique works well in some environmental catalytic systems, such attachment sometimes modifies the catalytic specifici-... 

The catalysts generally used in catalytic reforming are dual functional to provide two types of catalytic sites, hydrogenation-dehydrogenation sites and acid sites. The former sites are provided by platinum, which is the best known hydrogenation-dehydrogenation catalyst and the latter (acid sites) promote carbonium ion formation and are provided by an alumina carrier. The two types of sites are necessary for aromatization and isomerization reactions. 

Isomerization of alkylcyclopentanes may also occur on the platinum catalyst surface or on the silica/alumina. For example, methylcyclopen-tane isomerizes to cyclohexane ... 

Purely parallel reactions are e.g. competitive reactions which are frequently carried out purposefully, with the aim of estimating relative reactivities of reactants these will be discussed elsewhere (Section IV.E). Several kinetic studies have been made of noncompetitive parallel reactions. The examples may be parallel formation of benzene and methylcyclo-pentane by simultaneous dehydrogenation and isomerization of cyclohexane on rhenium-paladium or on platinum catalysts on suitable supports (88, 89), parallel formation of mesityl oxide, acetone, and phorone from diacetone alcohol on an acidic ion exchanger (41), disproportionation of amines on alumina, accompanied by olefin-forming elimination (20), dehydrogenation of butane coupled with hydrogenation of ethylene or propylene on a chromia-alumina catalyst (24), or parallel formation of ethyl-, methylethyl-, and vinylethylbenzene from diethylbenzene on faujasite (89a). 

Aris A process for the hydrocatalytic isomerization of C8 fractions. Developed by Leuna-Werk and Petrolchemische Kombinate Schwedt in 1976. The catalyst is platinum deposited in a mixture of alumina and natural mordenite. 

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