The Chemistry of Petroleum Refining

petroleum refineryThe first step in refining petroleum is distillation; the object here is to separate the petroleum into fractions based on the volatility of its components. Complete separation into fractions containing individual compounds is economically impractical and virtually impossible technically.

More than 500 different compounds are contained in the petroleum distillates boiling below 200°C, and many have almost the same boiling points. Thus the fractions taken contain mixtures of alkanes of similar boiling points (see the table below). Mixtures of alkanes, fortunately, are perfectly suitable for uses as fuels, solvents, and lubricants, the primary uses of petroleum.

The demand for gasoline is much greater than that supplied by the gasoline fraction of petroleum. Important processes in the petroleum industry, therefore, are concerned with converting hydrocarbons from other fractions into gasoline. When a mixture of alkanes from the gas oil fraction (C12 and higher) is heated at very high temperatures (∼500°C) in the presence of a variety of catalysts, the molecules break apart and rearrange to smaller, more highly branched hydrocarbons containing 5–10 carbon atoms. This process is called catalytic cracking. Cracking can also be done in the absence of a catalyst—called thermal cracking—but in this process the products tend to have unbranched chains, and alkanes with unbranched chains have a very low “octane rating.”

The highly branched compound 2,2,4-trimethylpentane (called isooctane in the petroleum industry) burns very smoothly (without knocking) in internal combustion engines and is used as one of the standards by which the octane rating of gasolines is established.


According to this scale, 2,2,4-trimethylpentane has an octane rating of 100. Heptane, CH3(CH2)5CH3, a compound that produces much knocking when it is burned in an internal combustion engine, is given an octane rating of 0. Mixtures of 2,2,4-trimethylpentane and heptane are used as standards for octane ratings between 0 and 100. A gasoline, for example, that has the same characteristics in an engine as a mixture of 87% 2,2,4-trimethylpentane and 13% heptane would be rated as 87-octane gasoline.

Typical Fractions Obtained by Distillation of Petroleum

fractions of petroleum

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  1. Tagelsir Awad
    Tagelsir Awad at | | Reply

    Pls. Im suffering to download the books would you pls. help me to do that if possible

  2. Abdul Hafeez
    Abdul Hafeez at | | Reply

    No download link is given for petroleum refining book

  3. asep suryatna

    Good writes

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