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Sustainable Mobility

Technical and environmental challenges for the automotive sector

Week 2 Session 4 Crude oil refining: petroleum cuts


and crude distillation
Olivier Bernaert

IFPEN / IFP School 2014

Crude composition

The raw material of a refinery is the crude oil.


A barrel of crude contains:
- Approximately 85 % of carbon element.
- 10 % of hydrogen.
A barrel of crude is composed mainly (up to 95 %) of hydrocarbons composed of carbon and
hydrogen, the other 5 % are called impurities:
- Approximately 2 % of sulfur compounds. The sulfur level in the crude-oil is a key parameter
for crude selection and crude prices. The higher the sulfur level in the crude, the more
difficult it will be to treat the crude to produce diesel and gasoline with a low sulfur
specification. In general, the higher the sulfur content of a crude the lower the price. In all
cases, these sulfur compounds must be removed in order to respect the sulfur specification
of the final product, for instance less than 10 ppm wt in Europe.
- Typically around 2 % of nitrogen.
- Water, salts and sediments which could be present in the crude oil. Water and salts must be
removed from the crude at the inlet of the refinery to avoid corrosion problems and fouling
by salt depositions in the units of the refinery.

Hydrocarbon types
In crude-oil you can find naturally four types of hydrocarbon.
First we have paraffins. Paraffins are linear hydrocarbons made up of carbon and hydrogen atoms.
Long linear paraffins are also called waxes.
Secondly, Iso-paraffins, which are non-linear paraffins with one or multiple small groups of carbon
and hydrogen attached to them.
The third type of hydrocarbon is the naphtene family.
These hydrocarbons are composed of carbon and hydrogen linked together in a ring shape.

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The last family is Aromatic compounds.


Aromatics are also hydrocarbons composed of rings of carbon and hydrogen, but with double
bonds between the carbon elements.
Compared to naphtenes, aromatics have, for a same number of carbons, less hydrogen.
The first aromatic is called benzene with six atoms of carbon.
In conclusion, a crude-oil is characterized by its paraffin, iso-paraffin, naphtene and aromatic
content.

It is important to know the type of hydrocarbon you have in a crude because these molecules will
directly influence the quality of the gasoline or diesel you will obtain from this crude-oil.
For instance, the Research Octane Number (or RON) of paraffin is very low. These compounds are
not ideal for gasoline fuel.
On the contrary, iso-paraffins and aromatics have a high RON suitable for the gasoline fuel
specifications.
To consider the cetane number, we find that paraffins have a high cetane number compared to isoparaffins and aromatics.
Remember, if the RON is low, the cetane number is high and, on the contrary when the RON is high,
the cetane number is low.

Petroleum cuts

In a crude, we typically have more than 200 000 different compounds.


This very high number of compounds means that it is simply impossible to perform precise analysis
of all the different compounds of the crude-oil.
In practice, we divide the crude-oil into different smaller petroleum cuts.
We do not need to analyze the real compounds in each cut, but just characterize the cuts using
simple analysis, like for instance: density, sulfur content, boiling temperature and carbon numbers.
The crude-oil is divided into these different smaller petroleum cuts in the first unit of the refinery
called: the Crude Oil Distillation Unit or CDU

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At the top of the column, we have the lighter compounds with the lowest carbon number, and the
lowest boiling temperature.
First we have the gas with carbon numbers between C1 and C4 and with a boiling temperature
range < 0C. That means that under atmospheric pressure, and at ambient temperature, these
compounds are in the form of a gas. We find in this cut gas such as methane, ethane, propane and
butane.
Then, we have the naphta cut. This cut is the raw material used in the petrochemical industry to
produce different types of plastics with different properties.
The naphta cut has a carbon number-range between C5 and C6 and a boiling temperature range
between 0C and 80Celsius. The boiling temperature range, mentioned here, is directly linked to
the volatility and distillation curve.
Next, the gasoline cut, is composed of hydrocarbons with C7 to C11 carbon numbers, and with a
boiling temperature range from 80 to 180C.
This cut is the base of the gasoline fuels used for spark ignition engines.
The Kerosene cut is the main base to produce jet fuel delivered to all international airports.
Typically, the carbon number of this cut is between C11 and C13.
The next cut is the Diesel cut which is the base of the diesel fuel for diesel engines cars and trucks.
The hydrocarbon chains contain between C13 and C25.
Finally, at the bottom of the crude distillation column, we have the atmospheric residue. This cut is
in fact all the heavy hydrocarbons with carbon numbers higher than C25, and with a boiling
temperature higher than 360C.
Petroleum cuts uses
The main uses of the different cuts obtained
at the outlet of the crude distillation column
are:
Gas for production of commercial
propane and butane
Naptha as the raw material for the
petrochemical industry
Gasoline, diesel and kerosene as
fuels for cars, trucks and planes

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And, atmospheric residue as heavy fuels used, for example, for boats or power plants.

Crude Distillation Unit (CDU)


In practice, the Crude distillation unit (or CDU) is the first unit of a refinery.
As we have just seen, the target of this unit is to cut the crude into different cuts.
First the crude is stored in a big oil tank.

Then the crude is de-salted in a desalter. A desalter is in fact a big horizontal vessel.
We can compare this equipment with a washing machine.
Fresh water is mixed with the crude to really wash the crude and eliminate all the salt and
sediments with the water.
Because of the density difference between water and crude oil, we recover the water (including the
salts) at the bottom of the desalter, and the crude at the top of the desalter.
At the outlet of the desalter, the crude is heated to a higher temperature, first in a second series of
heat exchangers and finally in a furnace.
At the outlet of the furnace, the temperature reaches 360Celsius.
At this level of temperature, all the cuts (from gas to Diesel) are in a gas form. Only the atmospheric
residue remains liquid.
This mixture of gas and liquid enters the crude distillation column.
By operating the distillation column, we will recover at the top (at around 120C) the gas, then
below, the other liquid cuts: naphta, gasoline, kerosene and diesel.
At the bottom of the column, we recover the atmospheric residue at a temperature around 360C.

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By playing with the operating parameters of the crude unit, the refiner can regulate the boiling
range temperature of each cut, and change the initial and final boiling point of the ASTM D86
distillation curve.
Finally, by changing the shape of this curve, the refiner can play on different specifications, such as,
density of the cut, volatility or cold flow properties.

For instance, if the density of a cut is too high compared to the specification, the final boiling point
of the cut can be decreased to limit the quantity of heavy products and in this way, decrease the
density.
It is important to notice that some specifications cannot be regulated by distillation column
operation, such as sulfur content which needs additional treatment.
Summary
To finish and summarize, we have seen that, at the outlet of the Crude Distillation Unit (CDU), we
obtain six main cuts, with different boiling temperatures, and carbon number ranges. These cuts
are the basis of the commercial products, such as, gasoline and diesel fuels.
In general, the specifications of the cuts, obtained just at the outlet of the distillation column, are
really far from the targeted specifications of the final products.
In conclusion, these cuts will need further refinery treatment in specific units to improve the quality
of the petroleum cuts, and to meet the final products specifications.

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