Fractional distillation, petroleum

Source Daubert, T. E., Petroleum Fraction Distillation Interconversions, Hydrocarbon Processing, September 1994, pp. 75-78. 

Many azeotropic combinations exist among hydrocarbons themselves. Aromatic hydrocarbons, for example, are almost always found in petroleum fractions distilling below the true boiling point of the aromatics. Marschner and Cropper (41) accurately delineated the limits of azeotropy for benzene and toluene with saturated hydrocarbons, and Denyer et al. (11) did the same for the thiols. Consideration of such data is desirable in the design and operation of equipment for the distillation of gasoline fractions to produce specialized products. 

TABLE 13.3. Economic Optimum Reflux Ratio for Typical Petroleum Fraction Distillation near 1 atms... 

Petroleum fractions distilling from 95°C to 115°C containing 55-60% of toluene, were used. The remainder constituted aliphatic hydrocarbons which would not nitrate under the conditions of the process. The MNT thus obtained, containing some petroleum components, was purified by distilling off the petroleum fraction. 

The most comrson use for these cycles is the separation of normal and isoparaffins in a variety of petroleum fractions. Distillation is not practical for these separations because the boiling ranges of the two products overlap. The feedstock most often contains several caibon numbers and can range from about C3 to CIS The adsorbent used is 5A molecular sieve, whose 0.5 nm pones ndmit normal paraffins and exclude isoparaffins. 

C. How is the trend in alkane boiling points used in petroleum fractional distillation ... 

Benzene was first isolated by Faraday in 1825 from the liquid condensed by compressing oil gas. It is the lightest fraction obtained from the distillation of the coal-tar hydrocarbons, but most benzene is now manufactured from suitable petroleum fractions by dehydrogenation (54%) and dealkylation processes. Its principal industrial use is as a starting point for other chemicals, particularly ethylbenzene, cumene, cyclohexane, styrene (45%), phenol (20%), and Nylon (17%) precursors. U.S. production 1979 2-6 B gals. 

D 2887, applies to products and petroleum fractions whose final boiling points are equal to or below 538°C (1000°F), and have boiling points above 38°C (100°F). The results obtained are equivalent to those obtained from the TBP distillation, ASTM D 2892. 

To extend the applicability of the characterization factor to the complex mixtures of hydrocarbons found in petroleum fractions, it was necessary to introduce the concept of a mean average boiling point temperature to a petroleum cut. This is calculated from the distillation curves, either ASTM or TBP. The volume average boiling point (VABP) is derived from the cut point temperatures for 10, 20, 50, 80 or 90% for the sample in question. In the above formula, VABP replaces the boiling point for the pure component. 

The stocks used for jet fuel production come almost essentially from direct distillation of crude oil. They correspond to the fraction distilled between 145 and 240°C, more or less expanded or contracted according to the circumstances. The yield of such a cut depends largely on the nature of the crude but is always larger than the demand for jet fuel which reaches about 6% of the petroleum market in Europe. For the refiner, the tightest specifications are ... 

Naphthenic acids occur ia a wide boiling range of cmde oil fractions, with acid content increa sing with boiling point to a maximum ia the gas oil fraction (ca 325°C). Jet fuel, kerosene, and diesel fractions are the source of most commercial naphthenic acid. The acid number of the naphthenic acids decreases as heavier petroleum fractions are isolated, ranging from 255 mg KOH/g for acids recovered from kerosene and 170 from diesel, to 108 from heavy fuel oil (19). The amount of unsaturation as indicated by iodine number also increases in the high molecular weight acids recovered from heavier distillation cuts. 

Alkali Treatment. Caustic washing is the treatment of materials, usually products from petroleum refining, with solutions of caustic soda. The process consists of mixing a water solution of lye (sodium hydroxide or caustic soda) with a petroleum fraction. The treatment is carried out as soon as possible after the petroleum fraction is distilled, since contact with air forms free sulfur, which is corrosive and difficult to remove. The lye reacts either with any hydrogen sulfide present to form sodium sulfide, which is soluble in water, or with mercaptans, foUowed by oxidation, to form the less nocuous disulfides. 

Methylphenol. y -Cresol is produced synthetically from toluene. Toluene is chlorinated and the resulting chlorotoluene is hydrolyzed to a mixture of methylphenols. Purification by distillation gives a mixture of 3-methylphenol and 4-methylphenol since they have nearly identical boiling points. Reaction of this mixture with isobutylene under acid catalysis forms 2,6-di-/ f2 -butyl-4-methylphenol and 2,4-di-/ f2 -butyl-5-methylphenol, which can then be separated by fractional distillation and debutylated to give the corresponding 3- and 4-methylphenols. A mixture of 3- and 4-methylphenols is also derived from petroleum cmde and coal tars. 

Benzene is a natural component of petroleum, but the amount of benzene present ia most cmde oils is small, often less than 1.0% by weight (34). Therefore the recovery of benzene from cmde oil is uneconomical and was not attempted on a commercial scale until 1941. To add further compHcations, benzene cannot be separated from cmde oil by simple distillation because of azeotrope formation with various other hydrocarbons. Recovery is more economical if the petroleum fraction is subjected to a thermal or catalytic process that iacreases the concentration of benzene. 

The equihbrium shown in equation 3 normally ties far to the left. Usually the water formed is removed by azeotropic distillation with excess alcohol or a suitable azeotroping solvent such as benzene, toluene, or various petroleum distillate fractions. The procedure used depends on the specific ester desired. Preparation of methyl borate and ethyl borate is compHcated by the formation of low boiling azeotropes (Table 1) which are the lowest boiling constituents in these systems. Consequently, the ester—alcohol azeotrope must be prepared and then separated in another step. Some of the methods that have been used to separate methyl borate from the azeotrope are extraction with sulfuric acid and distillation of the enriched phase (18), treatment with calcium chloride or lithium chloride (19,20), washing with a hydrocarbon and distillation (21), fractional distillation at 709 kPa (7 atmospheres) (22), and addition of a third component that will form a low boiling methanol azeotrope (23). 

In addition to straight run naphthas, 70—190°C cuts obtained by distillation from streams produced by cracking high boiling petroleum fractions can also be used as feed to reformers. Naphthas produced by hydrocracking are particularly suitable. 

Irreversible processes are mainly appHed for the separation of heavy stable isotopes, where the separation factors of the more reversible methods, eg, distillation, absorption, or chemical exchange, are so low that the diffusion separation methods become economically more attractive. Although appHcation of these processes is presented in terms of isotope separation, the results are equally vaUd for the description of separation processes for any ideal mixture of very similar constituents such as close-cut petroleum fractions, members of a homologous series of organic compounds, isomeric chemical compounds, or biological materials. 

Distillation (qv) is the most widely used separation technique in the chemical and petroleum industries. Not aU. Hquid mixtures are amenable to ordinary fractional distillation, however. Close-boiling and low relative volatihty mixtures are difficult and often uneconomical to distill, and azeotropic mixtures are impossible to separate by ordinary distillation. Yet such mixtures are quite common (1) and many industrial processes depend on efficient methods for their separation (see also Separation systems synthesis). This article describes special distillation techniques for economically separating low relative volatihty and azeotropic mixtures. 

ASTM (atmospheric) ASTM D 86 Petroleum fractions or products, including gasolines, turbine fuels, naphthas, kerosines, gas oils, distillate fuel oils, and solvents that do not tend to decompose when vaporized at 760 mmHg... 

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