Crude Oil Refining Process
Syed Amjad Ahmad
Crude oil
• Crude oil is the term for "unprocessed" oil, the stuff that comes
out of the ground. It is also known as petroleum. Crude oil is a
fossil fuel, meaning that it was made naturally from decaying
plants and animals living in ancient seas millions of years ago --
most places you can find crude oil were once sea beds. Crude
oils vary in color, from clear to tar-black, and in viscosity, from
water to almost solid.
• Crude oils are such a useful starting point for so many different
substances because they contain hydrocarbons. Hydrocarbons
are molecules that contain hydrogen and carbon and come in
various lengths and structures, from straight chains to
branching chains to rings.
Hydrocarbons
There are two things that make hydrocarbons exciting to
chemists:
Hydrocarbons contain a lot of energy. Many of the things
derived from crude oil like gasoline, diesel fuel, paraffin wax
and so on take advantage of this energy.
Hydrocarbons can take on many different forms. The
smallest hydrocarbon is methane (CH4), which is a gas that
is a lighter than air. Longer chains with 5 or more carbons
are liquids. Very long chains are solids like wax or tar. By
chemically cross-linking hydrocarbon chains you can get
everything from synthetic rubber to nylon to the plastic in
tupperware. Hydrocarbon chains are very versatile!
• The major classes of hydrocarbons in crude oils
include:
• Paraffins
– general formula: CnH2n+2 (n is a whole number, usually from 1 to 20)
– straight- or branched-chain molecules
– can be gasses or liquids at room temperature depending upon the
molecule
– examples: methane, ethane, propane, butane, isobutane, pentane,
hexane
• Aromatics
– general formula: C6H5 - Y (Y is a longer, straight molecule that connects
to the benzene ring)
– ringed structures with one or more rings
– rings contain six carbon atoms, with alternating double and single
bonds between the carbons
– typically liquids
– examples: benzene, napthalene
• Napthenes or Cycloalkanes
– general formula: CnH2n (n is a whole number usually from 1 to 20)
– ringed structures with one or more rings
– rings contain only single bonds between the carbon atoms
– typically liquids at room temperature
– examples: cyclohexane, methyl cyclopentane
• Other hydrocarbons
– Alkenes
• general formula: CnH2n (n is a whole number, usually from 1 to 20)
• linear or branched chain molecules containing one carbon-carbon double-bond
• can be liquid or gas
• examples: ethylene, butene, isobutene
– Dienes and Alkynes
• general formula: CnH2n-2 (n is a whole number, usually from 1 to 20)
• linear or branched chain molecules containing two carbon-carbon double-bonds
• can be liquid or gas
• examples: acetylene, butadienes
Crude Oil Components
• On average, crude oils are made of the following elements or
compounds:
• Carbon - 84%
• Hydrogen - 14%
• Sulfur - 1 to 3% (hydrogen sulfide, sulfides, disulfides,
elemental sulfur)
• Nitrogen - less than 1% (basic compounds with amine groups)
• Oxygen - less than 1% (found in organic compounds such as
carbon dioxide, phenols, ketones, carboxylic acids)
• Metals - less than 1% (nickel, iron, vanadium, copper, arsenic)
• Salts - less than 1% (sodium chloride, magnesium chloride,
calcium chloride)
The Refining Process
As mentioned previously, a barrel of crude oil has a mixture of all sorts of
hydrocarbons in it. Oil refining separates everything into useful substances.
Chemists use the following steps:
• The oldest and most common way to separate things into various components
(called fractions), is to do it using the differences in boiling temperature. This
process is called fractional distillation. You basically heat crude oil up, let it
vaporize and then condense the vapor.
• Newer techniques use Chemical processing on some of the fractions to make
others, in a process called conversion. Chemical processing, for example, can
break longer chains into shorter ones. This allows a refinery to turn diesel fuel into
gasoline depending on the demand for gasoline.
• Refineries must treat the fractions to remove impurities.
• Refineries combine the various fractions (processed, unprocessed) into mixtures
to make desired products. For example, different mixtures of chains can create
gasolines with different octane ratings.
• The products are stored on-site until they can be delivered to various markets
such as gas stations, airports and chemical plants. In addition to making the oil-
based products, refineries must also treat the wastes involved in the processes to
minimize air and water pollution.
Fractional Distillation
• The various components of crude oil have different sizes, weights and boiling temperatures; so, the first step is to
separate these components. Because they have different boiling temperatures, they can be separated easily by a process
called fractional distillation. The steps of fractional distillation are as follows:
• You heat the mixture of two or more substances (liquids) with different boiling points to a high temperature. Heating is
usually done with high pressure steam to temperatures of about 1112 degrees Fahrenheit / 600 degrees Celsius.
• The mixture boils, forming vapor (gases); most substances go into the vapor phase.
• The vapor enters the bottom of a long column (fractional distillation column) that is filled with trays or plates.
–The trays have many holes or bubble caps (like a loosened cap on a soda bottle) in them to allow the vapor to pass through.
–The trays increase the contact time between the vapor and the liquids in the column.
–The trays help to collect liquids that form at various heights in the column.
–There is a temperature difference across the column (hot at the bottom, cool at the top).
• The vapor rises in the column.
• As the vapor rises through the trays in the column, it cools.
• When a substance in the vapor reaches a height where the temperature of the column is equal to that substance's
boiling point, it will condense to form a liquid. (The substance with the lowest boiling point will condense at the highest
point in the column; substances with higher boiling points will condense lower in the column.).
• The trays collect the various liquid fractions.
• The collected liquid fractions may:
–pass to condensers, which cool them further, and then go to storage tanks
–go to other areas for further chemical processing
• Fractional distillation is useful for separating a mixture of substances with narrow differences in boiling points, and is the
most important step in the refining process.
• Very few of the components come out of the fractional distillation column ready for market. Many of them must be
chemically processed to make other fractions. For example, only 40% of distilled crude oil is gasoline; however, gasoline
is one of the major products made by oil companies. Rather than continually distilling large quantities of crude oil, oil
companies chemically process some other fractions from the distillation column to make gasoline; this processing
increases the yield of gasoline from each barrel of crude oil.
Chemical Processing
• You can change one fraction into another by one of three methods:
• breaking large hydrocarbons into smaller pieces (cracking)
• combining smaller pieces to make larger ones (unification)
• rearranging various pieces to make desired hydrocarbons (alteration)
Cracking breaks large chains into smaller chains.
• Cracking
Cracking takes large hydrocarbons and breaks them into smaller ones.
• There are several types of cracking:
• Thermal - you heat large hydrocarbons at high temperatures (sometimes high pressures as well) until they break apart.
– steam - high temperature steam (1500 degrees Fahrenheit / 816 degrees Celsius) is used to break ethane, butane and naptha into ethylene and benzene,
which are used to manufacture chemicals.
– visbreaking - residual from the distillation tower is heated (900 degrees Fahrenheit / 482 degrees Celsius), cooled with gas oil and rapidly burned (flashed) in
a distillation tower. This process reduces the viscosity of heavy weight oils and produces tar.
– coking - residual from the distillation tower is heated to temperatures above 900 degrees Fahrenheit / 482 degrees Celsius until it cracks into heavy oil,
gasoline and naphtha. When the process is done, a heavy, almost pure carbon residue is left (coke); the coke is cleaned from the cokers and sold.
Catalysts used in catalytic cracking or reforming
• Catalytic - uses a catalyst to speed up the cracking reaction. Catalysts include zeolite, aluminum hydrosilicate, bauxite and silica-alumina.
– fluid catalytic cracking - a hot, fluid catalyst (1000 degrees Fahrenheit / 538 degrees Celsius) cracks heavy gas oil into diesel oils and gasoline.
– hydrocracking - similar to fluid catalytic cracking, but uses a different catalyst, lower temperatures, higher pressure, and hydrogen gas. It takes heavy oil and
cracks it into gasoline and kerosene (jet fuel).
• After various hydrocarbons are cracked into smaller hydrocarbons, the products go through another fractional distillation column to separate
them.
• Unification
Sometimes, you need to combine smaller hydrocarbons to make larger ones -- this process is called unification. The major unification process is
called catalytic reforming and uses a catalyst (platinum, platinum-rhenium mix) to combine low weight naphtha into aromatics, which are used in
making chemicals and in blending gasoline. A significant by-product of this reaction is hydrogen gas, which is then either used for hydrocracking or
sold.
• Alteration
Sometimes, the structures of molecules in one fraction are rearranged to produce another. Commonly, this is done using a process called
alkylation. In alkylation, low molecular weight compounds, such as propylene and butylene, are mixed in the presence of a catalyst such as
hydrofluoric acid or sulfuric acid (a by-product from removing impurities from many oil products). The products of alkylation are high octane
hydrocarbons, which are used in gasoline blends to reduce knocking.
