Isomerization of light naphtha

Isomerization of light naphtha—mainly pentanes and hexanes—was practiced to only a limited extent. 

Napththa Isomerization. The only commercial isomerization of light naphtha was carried out in two plants employing the isomate process developed by the Standard Oil Co. (Indiana) (20). In this process, a feed containing normal pentane and low octane number hexanes is converted to isopentane and to hexanes of higher octane number. Pentanes and hexanes in any ratio may be processed. By recycle of selected fractions of the product, concentrates of isopentane or of neohexane and diisopropyl can be obtained as the ultimate products. 

Table VII. Reproducibility of Catalyst Testing in Microflow Reactors for Isomerization of Light Naphtha...

Fig. 6. Isomerization of light naphtha. Conditions temperature, 330°F. contact time, 0.1 to 1.0 hours Aids, 11.5 wt.% and HCl, 3.2 wt.% based on light naphtha.

Sulfated zirconias, nowadays a well established class of acid solids first reported by Holm and Bailey [2], and systematically studied by Arata [3] and Tanabe et aL [4], are considered as potential alternative catalysts for the skeletal isomerization of n-butane. These catalysts have recently found a commercial application (Par-Isom Process of UOP) for the isomerization of light naphtha (Cs-Ce), but since they are less active than Pt-chlorinated aluminas, there is a real interest for improving their catalytic performance [5]. 

Light naphtha is a mixture produced by distillation of crude oil. Light naphtha primarily contains alkane compounds (paraffins), and it can be blended into gasoline. The octane value of methyl-substituted alkanes (iso-paraffins) is higher than that of straight-chain compounds (normal paraffins), so it is often advantageous to isomerize the light naphtha to increase the proportion of branched compounds. 

In the HTFT oil refinery the light oil and <345°C fraction of the decanted oil (obtained by passing the decanted oil through a vacuum flash drum) were clay treated. Clay treatment is similar to Bauxite treatment and is used to increase the octane number of the naphtha by acidic isomerization and to reduce the oxygenate content of the oil. Processing the LTFT and HTFT in separate (and different)... 

Jao, R.-M., Leu, L.-J., and Chang, J.-R. (1996) Effects of catalyst preparation and pretreatment on light naphtha isomerization over mordenite-supported Pt catalysts. Appl Catal A., 135, 301-315. 

Catalytic Reforming A catalytic reaction of heavy naphtha(1) used to produce high-octane gasoline. The byproducts are hydrogen and light hydrocarbons the primary reaction is dehydrogenation of naphthenes to produce aromatics. Some reshaping of paraffins to produce aromatics and some isomerization of paraffins to produce isoparaffins also occur. 

The feed to an aromatics complex is normally a C6+ aromatic naphtha from a catalytic reformer. The feed is split into Cg+ for xylene recovery and C7 for solvent extraction. The extraction unit recovers pure benzene as a product and C7+ aromatics for recycling. A by-product of extraction is a non-aromatic C6+ raffinate stream. The complex contains a catalytic process for disproportionation and transalkylation of toluene and C9+ aromatics, and a catalytic process for isomerization of C8 aromatics. Zeolitic catalysts are used in these processes, and catalyst selectivity is a major performance factor for minimizing ring loss and formation of light and heavy ends. The choice of isomerization catalyst is dependent on whether it is desired to isomerize ethylbenzene plus xylenes to equilibrium or to dealkylate ethylbenzene to benzene while isomerizing the xylenes. Para-selectivity may also be a desired... 

Isomerization increases the octane value of light straight run naphtha by rearranging the low octane straight chain C5-C6 paraffins into their higher octane branched isomers as shown in Table 7.2. 

In the area of oil refining, a general lecture sets the scene for present and future challenges. It is followed by in-depth case studies involving FCC, hydrocracking and light naphtha isomerization. Also, an entire chapter is devoted to the often-overlooked subject of base oils. 

The latter conclusion is supported by the data of Table VI, which demonstrate that testing in a bench-scale and microflow reactor gives almost identical results for light naphtha isomerization over undiluted catalyst of actual size. The absence of a noticable effect of bed length and gas velocity is in line with the assumption that in this case extraparticle mass transfer effects are relatively unimportant, as discussed earlier. 

With properly designed equipment and careful execution of the tests, the accuracy of small-scale testing can be quite high. Table VII shows some data on the reproducibility of microflow tests on light naphtha isomerization carried out in several reactor units during a period of about half a year. The agreement between results of individual tests is sufficiently good for practical purposes of catalyst evaluation and optimization of process conditions. 

Table VI. Comparison of Test Results on Light Naphtha Isomerization in Bench-scale and Microflow Reactors...

Table VIII. Comparison of Microflow Test Results with Data from Commercial Plants on Light Naphtha Isomerization over Pt/H-Mordenite Catalysts...

The maximum production of isohexanes is considered the practical parameter of choice upon which refiners base their selection of operating conditions in light naphtha isomerization. 

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. 

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