On average, crude oils are made

of the following elements or

compounds:

• Carbon - 84%
• Hydrogen - 14%
Crude Oil • Sulfur - 1 to 3%
(hydrogen sulfide,
sulfides, disulfides,
Crude oil is the term for "unprocessed" oil, the stuff that elemental sulfur)
comes out of the ground. It is also known as petroleum. • Nitrogen - less than 1%
(basic compounds with
Crude oil is a fossil fuel, meaning that it was made amine groups)
naturally from decaying plants and animals living in • Oxygen - less than 1%
ancient seas millions of years ago -- anywhere you find (found in organic
crude oil was once a sea bed. Crude oils vary in color, compounds such as
from clear to tar-black, and in viscosity, from water to carbon dioxide, phenols,
almost solid. ketones, carboxylic
acids)
• Metals - less than 1%
Crude oils are such a useful starting point for so many (nickel, iron, vanadium,
different substances because they contain hydrocarbons. copper, arsenic)
Hydrocarbons are molecules that contain hydrogen and
carbon and come in various lengths and structures, from • Salts - less than 1%
straight chains to branching chains to rings. (sodium chloride,
magnesium chloride,
calcium chloride)
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

From Crude Oil

The problem with crude oil is that it contains hundreds of different types of hydrocarbons
all mixed together. You have to separate the different types of hydrocarbons to have
anything useful. Fortunately there is an easy way to separate things, and this is what oil
refining is all about.

The oil refining process starts with a fractional distillation column.

Different hydrocarbon chain lengths all have progressively higher boiling points, so they
can all be separated by distillation. This is what happens in an oil refinery - in one part of
the process, crude oil is heated and the different chains are pulled out by their
vaporization temperatures. Each different chain length has a different property that makes
it useful in a different way.

To understand the diversity contained in crude oil, and to understand why refining crude
oil is so important in our society, look through the following list of products that come
from crude oil:

• Petroleum gas - used for heating, cooking, making plastics

 small alkanes (1 to 4 carbon atoms)
 commonly known by the names methane, ethane, propane, butane
 boiling range = less than 104 degrees Fahrenheit / 40 degrees Celsius
 often liquified under pressure to create LPG (liquified petroleum gas)
• Naphtha or Ligroin - intermediate that will be further processed to make
gasoline
 mix of 5 to 9 carbon atom alkanes
 boiling range = 140 to 212 degrees Fahrenheit / 60 to 100 degrees Celsius
• Gasoline - motor fuel
 liquid
 mix of alkanes and cycloalkanes (5 to 12 carbon atoms)
 boiling range = 104 to 401 degrees Fahrenheit / 40 to 205 degrees Celsius
• Kerosene - fuel for jet engines and tractors; starting material for making other
products
 liquid
 mix of alkanes (10 to 18 carbons) and aromatics
 boiling range = 350 to 617 degrees Fahrenheit / 175 to 325 degrees
Celsius
• Gas oil or Diesel distillate - used for diesel fuel and heating oil; starting material
for making other products
 liquid
 alkanes containing 12 or more carbon atoms
 boiling range = 482 to 662 degrees Fahrenheit / 250 to 350 degrees
Celsius
• Lubricating oil - used for motor oil, grease, other lubricants
 liquid
 long chain (20 to 50 carbon atoms) alkanes, cycloalkanes, aromatics
 boiling range = 572 to 700 degrees Fahrenheit / 300 to 370 degrees
Celsius
• Heavy gas or Fuel oil - used for industrial fuel; starting material for making other
products
 liquid
 long chain (20 to 70 carbon atoms) alkanes, cycloalkanes, aromatics
 boiling range = 700 to 1112 degrees Fahrenheit / 370 to 600 degrees
Celsius
 • Residuals - coke, asphalt, tar, waxes; starting material for making other products
 solid
 multiple-ringed compounds with 70 or more carbon atoms
 boiling range = greater than 1112 degrees Fahrenheit / 600 degrees Celsius

You may have noticed that all of these products have different sizes and boiling ranges.
Chemists take advantage of these properties when refining oil. Look at the next section to
find out the details of this fascinating process.

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:

1. 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.
2. 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.
3. Refineries must treat the fractions to remove impurities.
4. 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.

Photo courtesy Phillips Petroleum Company

An oil refinery

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:
Photo courtesy Phillips Petroleum
Distillation columns in an oil refinery
1. 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.
2. The mixture boils, forming vapor (gases); most substances go into the vapor phase.
3. 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).
4. The vapor rises in the column.
5. As the vapor rises through the trays in the column, it cools.
6. 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.).
7. The trays collect the various liquid fractions.
8. 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.
 The oil refining process starts with a fractional distillation column. On the right, you can see several chemical
processors that are described in the next section.

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
Cracking takes large hydrocarbons and breaks them into smaller ones.
 Cracking breaks large chains into smaller chains.

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.
 • 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. Photo courtesy Phillips Petroleum Company
Catalysts used in catalytic cracking or
 hydrocracking - similar to fluid catalytic reforming
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.
 A reformer combines chains.

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 (see "What does octane mean?" for details).

Rearranging chains.

Now that we have seen how various fractions are changed, we will discuss the how the
fractions are treated and blended to make commercial products.
 An oil refinery is a combination of all of these units.
Next Page >>

Treating and Blending the Fractions

Distillated and chemically processed fractions are treated to remove impurities, such as
organic compounds containing sulfur, nitrogen, oxygen, water, dissolved metals and
inorganic salts. Treating is usually done by passing the fractions through the following:

• a column of sulfuric acid - removes unsaturated

hydrocarbons (those with carbon-carbon double-
bonds), nitrogen compounds, oxygen compounds
and residual solids (tars, asphalt)
• an absorption column filled with drying agents to
remove water
• sulfur treatment and hydrogen-sulfide scrubbers to
remove sulfur and sulfur compounds

After the fractions have been treated, they are cooled and
then blended together to make various products, such as:

• gasoline of various grades, with or without additives

Photo courtesy Phillips Petroleum
• lubricating oils of various weights and grades (e.g. Plastics produced from refined oil
10W-40, 5W-30) fractions
• kerosene of various various grades
• jet fuel
• diesel fuel
• heating oil
• chemicals of various grades for making plastics and other polymers

The "crude oil" pumped out of the ground is a black liquid called petroleum. This liquid
contains aliphatic hydrocarbons, or hydrocarbons composed of nothing but hydrogen and
carbon. The carbon atoms link together in chains of different lengths.
It turns out that hydrocarbon molecules of different lengths have different properties and
behaviors. For example, a chain with just one carbon atom in it (CH4) is the lightest chain,
known as methane. Methane is a gas so light that it floats like helium. As the chains get
longer, they get heavier.

The first four chains -- CH4 (methane), C2H6 (ethane), C3H8 (propane) and C4H10 (butane) -- are
all gases, and they boil at -161, -88, -46 and -1 degrees F, respectively (-107, -67, -43 and
-18 degrees C). The chains up through C18H32 or so are all liquids at room temperature, and
the chains above C19 are all solids at room temperature.

The different chain lengths have progressively higher boiling points, so they can be
separated out by distillation. This is what happens in an oil refinery -- crude oil is heated
and the different chains are pulled out by their vaporization temperatures. (See How Oil
Refining Works for details.)

The chains in the C5, C6 and C7 range are all very light, easily vaporized, clear liquids called
naphthas. They are used as solvents -- dry cleaning fluids can be made from these liquids,
as well as paint solvents and other quick-drying products.

The chains from C7H16 through C11H24 are blended together and used for gasoline. All of them
vaporize at temperatures below the boiling point of water. That's why if you spill gasoline on
the ground it evaporates very quickly.

Next is kerosene, in the C12 to C15 range, followed by diesel fuel and heavier fuel oils (like
heating oil for houses).

Next come the lubricating oils. These oils no longer vaporize in any way at normal
temperatures. For example, engine oil can run all day at 250 degrees F (121 degrees C)
without vaporizing at all. Oils go from very light (like 3-in-1 oil) through various thicknesses of
motor oil through very thick gear oils and then semi-solid greases. Vasoline falls in there as
well.

Chains above the C20 range form solids, starting with paraffin wax, then tar and finally
asphaltic bitumen, which used to make asphalt roads.

All of these different substances come from crude oil. The only difference is the length of the
carbon chains!

Fractional Distillation of Crude Oil

BOILING POINTS AND STRUCTURES OF HYDROCARBONS

The boiling points of organic compounds can give important clues to other physical
properties. A liquid boils when its vapor pressure is equal to the atmospheric pressure.
Vapor pressure is determined by the kinetic energy of molecules. Kinetic energy is
related to temperature and the mass and velocity of the molecules. When the temperature
reaches the boiling point, the average kinetic energy of the liquid particles is sufficient to
overcome the forces of attraction that hold molecules in the liquid state. Then these
molecules break away from the liquid forming the gas state.
Vapor pressure is caused by an equilibrium between molecules in the gaseous state and
molecules in the liquid state. When molecules in the liquid state have sufficient kinetic
energy, they may escape from the surface and turn into a gas. Molecules with the most
independence in individual motions achieve sufficient kinetic energy (velocities) to
escape at lower temperatures. The vapor pressure will be higher and therefore the
compound will boil at a lower temperature.

BOILING POINT PRINCIPLE:

Molecules which strongly interact or bond with each other through a variety of
intermolecular forces can not move easily or rapidly and therefore, do not achieve the
kinetic energy necessary to escape the liquid state. Therefore, molecules with strong
intermolecular forces will have higher boiling points. This is a consequence of the
increased kinetic energy needed to break the intermolecular bonds so that individual
molecules may escape the liquid as gases.

THE BOILING POINT CAN BE A ROUGH MEASURE OF THE AMOUNT OF

ENERGY NECESSARY TO SEPARATE A LIQUID MOLECULE FROM ITS
NEAREST NEIGHBORS.

MOLECULAR WEIGHT AND CHAIN LENGTH TRENDS IN BOILING POINTS

A series of alkanes demonstrates the general principle that boiling points increase as
molecular weight or chain length increases (table 1.).

Table 1. BOILING POINTS OF ALKANES

Normal State at
Formula Name Boiling Point C
Room Temp. +20 C
CH4 Methane -161 gas
CH3CH3 Ethane - 89
CH3CH2CH3 Propane - 42
CH3CH2CH2CH3 Butane -0.5
CH3CH2CH2CH2CH3 Pentane + 36 liquid
CH3(CH2)6CH3 Octane +125

QUES. State whether the compounds above will be a gas or liquid state at room
temperature (20 C). Hint: If the boiling point is below 20 C, then the liquid has already
boiled andthe compound is a gas.

The reason that longer chain molecules have higher boiling points is that longer chain
molecules become wrapped around and enmeshed in each other much like the strands of
spaghetti. More energy is needed to separate them than short molecules which have only
weak forces of attraction for each other.

FOCUS ON FOSSIL FUELS

Petroleum refining is the process of separating the many compounds present in crude
petroleum. The principle which is used is that the longer the carbon chain, the higher the
temperature at which the compounds will boil. The crude petroleum is heated and
changed into a gas. The gases are passed through a distillation column which becomes
cooler as the height increases. When a compound in the gaseous state cools below its
boiling point, it condenses into a liquid. The liquids may be drawn off the distilling
column at various heights.

Although all fractions of petroleum find uses, the greatest demand is for gasoline. One
barrel of crude petroleum contains only 30-40% gasoline. Transportation demands
require that over 50% of the crude oil be converted into gasoline. To meet this demand
some petroleum fractions must be converted to gasoline. This may be done by "cracking"
- breaking down large molecules of heavy heating oil; "reforming" - changing molecular
structures of low quality gasoline molecules; or "polymerization" - forming longer
molecules from smaller ones.

For example if pentane is heated to about 500 C the covalent carbon-carbon bonds begin
to break during the cracking process. Many kinds of compounds including alkenes are
made during the cracking process. Alkenes are formed because there are not enough
hydrogens to saturate all bonding positions after the carbon-carbon bonds are broken.
Simple Distillation

The core refining process is

simple distillation, illustrated
in a stylized fashion at the
right. Because crude oil is
made up of a mixture of
hydrocarbons, this first and
basic refining process is
aimed at separating the
crude oil into its "fractions,"
the broad categories of its
component hydrocarbons.
Crude oil is heated and put
into a still -- a distillation
column -- and different
products boil off and can be
recovered at different
temperatures. The lighter
products -- liquid petroleum
gases (LPG), naphtha, and so-called "straight run" gasoline -- are recovered at the lowest
temperatures. Middle distillates -- jet fuel, kerosene, distillates (such as home heating oil and
diesel fuel) -- come next. Finally, the heaviest products (residuum or residual fuel oil) are
recovered, sometimes at temperatures over 1000 degrees F. The simplest refineries stop at
this point. Most in the United States, however, reprocess the heavier fractions into lighter
products to maximize the output of the most desirable products, as shown schematically in the
illustration, and as discussed below.

Downstream Processing
Additional processing follows crude distillation, "downstream" (or closer to the refinery gate
and the consumer) of the distillation process. Downstream processing is grouped together in
this discussion, but encompasses a variety of highly complex units designed for very different
upgrading processes. Some change the molecular structure of the input with chemical
reactions, some in the presence of a catalyst, some with thermal reactions.

In general, these processes are designed to take heavy, low-valued feedstock -- often itself the
output from an earlier process -- and change it into lighter, higher-valued output. A catalytic
cracker, for instance, uses the gasoil (heavy distillate) output from crude distillation as its
feedstock and produces additional finished distillates (heating oil and diesel) and gasoline.
Sulfur removal is accomplished in a hydrotreater. A reforming unit produces higher octane
components for gasoline from lower octane feedstock that was recovered in the distillation
process. A coker uses the heaviest output of distillation, the residue or residuum, to produce
a lighter feedstock for further processing, as well as petroleum coke.

As noted above and in the section on demand, U.S. demand is centered on light products, such
as gasoline. As shown in the graph, refiners in the United States more closly match the mix of
products demand by using downstream processing to move from the natural yield of products
from simple distillation, illustrated earlier, to the U.S. demand slate, illustrated here. After
simple distillation alone, the output from a crude oil like Arab Light would be about 20 percent
of lightest, gasoline-like products, and about 50 percent of the heaviest, the residuum. After
further processing in the most sophisticated refinery, however, the finished product output is
about 60 percent gasoline, and 5 percent residuum.

Crude Oil Quality

The physical characteristics of crude oils differ. Crude oil with a similar mix of physical and
chemical characteristics, usually produced from a given reservoir, field or sometimes even a
region, constitutes a crude oil "stream." Most simply, crude oils are classified by their density
and sulfur content. Less dense (or "lighter") crudes generally have a higher share of light
hydrocarbons -- higher value products -- that can be recovered with simple distillation. The
denser ("heavier") crude oils produce a greater share of lower-valued products with simple
distillation and require additional processing to produce the desired range of products. Some
crude oils also have a higher sulfur content, an undesirable characteristic with respect to both
processing and product quality. For pricing purposes, crude oils of similar quality are often
compared to a single representative crude oil, a "benchmark," of the quality class.

The quality of the crude oil dictates the level of processing and re-processing necessary to
achieve the optimal mix of product output. Hence, price and price differentials between
crude oils also reflect the relative ease of refining. A premium crude oil like West Texas
Intermediate, the U.S. benchmark, has a relatively high natural yield of desirable naphtha and
straight-run gasoline (see graph). Another premium crude oil, Nigeria's Bonny Light, has a high
natural yield of middle distillates. By contrast, almost half of the simple distillation yield from
Saudi Arabia's Arabian Light, the historical benchmark crude, is a heavy residue ("residuum")
that must be reprocessed or sold at a discount to crude oil. Even West Texas Intermediate and
Bonny Light have a yield of about one-third residuum after the simple distillation process.

In addition to gravity and sulfur content, the type of hydrocarbon molecules and other natural
characteristics may affect the cost of processing or restrict a crude oil's suitability for specific
uses. The presence of heavy metals, contaminants for the processing and for the finished
product, is one example. The molecular structure of a crude oil also dictates whether a crude
stream can be used for the manufacture of specialty products, such as lubricating oils or of
petrochemical feedstocks.
Refiners therefore strive to run the optimal mix (or "slate") of crudes through their refineries,
depending on the refinery's equipment, the desired output mix, and the relative price of
available crudes. In recent years, refiners have confronted two opposite forces -- consumers'
and government mandates that increasingly required light products of higher quality (the most
difficult to produce) and crude oil supply that was increasingly heavier, with higher sulfur
content (the most difficult to refine).

Oil Refineries

A refinery is a factory. A refinery takes a raw

material (crude oil) and transforms it into petrol
and hundreds of other useful products. A typical
large refinery costs billions of pounds to build
and millions more to run and upgrade. It runs
around the clock 365 days a year, employs
hundreds of people and occupies as much land as
several hundred football pitches.

A REFINERY breaks crude oil down into its

various components, which then are selectively
changed into new products. This process takes
place inside a maze of pipes and vessels. The
refinery is operated from a highly automated
control room.

All refineries perform three basic steps:

• Separation (fractional distillation)

• Conversion (cracking and rearranging the
molecules)

• Treatment
Modern separation involves piping crude oil through hot furnaces. The resulting liquids
and vapours are passed into distillation towers:-

B Pt Number of
FRACTION o Uses
C carbons

»Refinery
1-4 Bottled gas, fuels
gas

40 ~8 Fuel for cars

»Petrol
Raw material for chemicals and
110 ~10
plastics.
»Naptha

180 ~15 Fuel for Aeroplanes

»Kerosine

250 ~20 Fuel for cars and lorries

»Diesel
Fuel for Power Stations,
340 ~35
Lubricants and grease
»Oils
Hot
crude » 400+ 40+ Road surfacing.
»Bitumen

• It is important to realise that the column is hot at the bottom and cool at the top.
• The crude oil separates into fractions according to weight and boiling point.
• The lightest fractions, including petrol and liquid petroleum gas (LPG), vapourise and
rise to the top of the tower.
• Kerosine (aviation fuel) and diesel oil, stay in the middle of the tower
• Heavier liquids separate lower down.
• The heaviest fractions with the highest boiling points settle at the very bottom.

TRENDS AS WE UP AND DOWN THE COLUMN

The following table shows how the behaviour of the hydrocarbon molecules alter:

AT THE TOP OF THE COLUMN AT THE BOTTOM OF THE COLUMN

• Short carbon chains • Long carbon chains

• Light molecules • Heavy molecules
• Low boiling points • High boiling points
• Gases & very runny liquids • Thick, viscous liquids
• Very volatile • Low volatility
• Highly flammable • Not very flammable
• Light colour • Dark colour

Petrol comes off near the top of the column. Fuel oil comes off near the bottom of the
Does the list above describe petrol? column. Does the list above describe fuel oil?

The fractions are now ready for piping to the next areas within the refinery. Some
fractions require very little additional processing. However, most molecules require much
more processing to become high-value products.

Conversion: cracking and rearranging

molecules

Some fractions from the distillation towers need to be

transformed into new components . This is where a refinery
makes money, because the low-value fractions that aren't in great
demand can be converted to petrol and other useful chemicals.

The most widely used conversion method is called

cracking because it uses heat and pressure to "crack"
heavy hydrocarbon molecules into lighter ones. A
cracking unit consists of one or more tall, thick-walled,
reactors and a network of furnaces, heat exchangers and
other vessels. Catalytic cracking, or "cat cracking," is the
basic petrol-making process. Using intense heat (about
600°C), low pressure and a powdered catalyst (a
substance that speeds up a chemical reaction), the cat
cracker can convert most of the heavy fractions into
smaller more useful molecules.

Some refineries also have cokers, which use heat and

moderate pressure to turn the really heavy fractions into
lighter products and a hard, coal like substance that is
used as an industrial fuel.

Cracking and coking are not the only forms of

conversion. Other refinery processes, instead of splitting
molecules, rearrange them to add value. Alkylation
makes petrol components by combining some of the
gaseous byproducts of cracking. The process, which
essentially is cracking in reverse, takes place in a series of
large, horizontal vessels.

Reforming uses heat, moderate pressure and catalysts to turn naphtha into high-octane
petrol.

Treatment: the finishing touch

Today, a major portion of refining involves blending, purifying, fine-tuning and
improving products to meet specific requirements. To make petrol, refinery workers
carefully blend together a variety of hydrocarbons. Technicians also add performance
additives and dyes that distinguish the various grades of fuel. By the time the petrol is
pumped into a car it contains more than 200 hydrocarbons and additives.

Example: Petrol companies produce different blends of fuels to suit the weather. In
winter, they put in more volatile hydrocarbons (with short carbon chains) and in summer
they add less volatile hydrocarbons to compensate for the higher temperatures.