PROCESS FUNDAMENTALS H AND BOOK

3. CRUDE OIL REFINING

We have seen images of thick, black crude oil gushing out of the ground or a
drilling platform in TV or News. But when you pump the gasoline for your car,
you've probably noticed that it is clear. And there are so many other products that
come from oil, including crayons, plastics, heating oil, jet fuel, kerosene, synthetic
fibers and tires. How is it possible to start with crude oil and end up with gasoline
and all of these other products?

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 -- anywhere you find crude oil was once a sea bed. 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.
There are two things that make hydrocarbons exciting to chemists:
z 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.
z Hydrocarbons can take on many different forms. The smallest
hydrocarbon is methane (CH 4), 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!
On average, crude oils are made of the following elements or compounds:
z Carbon - 84%
z Hydrogen - 14%
z Sulfur - 1 to 3% (hydrogen sulfide, sulfides, disulfides, elemental
sulfur)
z Nitrogen - less than 1% (basic compounds with amine groups)

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z Oxygen - less than 1% (found in organic compounds such as carbon

dioxide, phenols, ketones, carboxylic acids)
z Metals - less than 1% (nickel, iron, vanadium, copper, arsenic)
z Salts - less than 1% (sodium chloride, magnesium chloride,
calcium chloride
The major classes of hydrocarbons in crude oils include:
Paraffins
z general formula: C nH 2n+2 (n is a whole number, usually from 1 to
20)
z straight- or branched-chain molecules
z can be gasses or liquids at room temperature depending upon the
molecule
z examples: methane, ethane, propane, butane, isobutane, pentane,
hexane
Aromatics
z general formula: C 6H 5 - Y (Y is a longer, straight molecule that
connects to the benzene ring)
z ringed structures with one or more rings
z rings contain six carbon atoms, with alternating double and single
bonds between the carbons
z typically liquids
z examples: benzene, napthalene
Napthenes or Cycloalkanes
z general formula: CnH2n (n is a whole number usually from 1 to 20)
z ringed structures with one or more rings
z rings contain only single bonds between the carbon atoms
z typically liquids at room temperature
z examples: cyclohexane, methyl cyclopentane

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Other Hydrocarbons
Alkenes
z general formula: C nH 2n (n is a whole number, usually from 1 to 20)
z linear or branched chain molecules containing one carbon-carbon
double-bond
z can be liquid or gas
z examples: ethylene, butene, isobutene
Dienes and Alkynes
z general formula: C nH 2n-2 (n is a whole number, usually from 1 to
20)
z linear or branched chain molecules containing two carbon-carbon
double-bonds
z can be liquid or gas
z examples: acetylene, butadienes
Now that we know what's in crude oil, let's see what we can make from it.

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.

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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
z small alkanes (1 to 4 carbon atoms)
z commonly known by the names methane, ethane, propane, butane
z boiling range = less than 104 degrees Fahrenheit / 40 degrees
Celsius
z often liquified under pressure to create LPG (liquified petroleum
gas)
Naphtha - intermediate that will be further processed to make gasoline
z mix of 5 to 9 carbon atom alkanes
z boiling range = 140 to 212 degrees Fahrenheit / 60 to 100 degrees
Celsius
Gasoline - motor fuel
z liquid
z mix of alkanes and cycloalkanes (5 to 12 carbon atoms)
z boiling range = 104 to 401 degrees Fahrenheit / 40 to 205 degrees
Celsius
Kerosene or ATF - fuel for jet engines and tractors; starting material for making
other products
z liquid
z mix of alkanes (10 to 18 carbons) and aromatics
z 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
z liquid
z alkanes containing 12 or more carbon atoms
z boiling range = 482 to 662 degrees Fahrenheit / 250 to 350 degrees
Celsius

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Lubricating oil - used for motor oil, grease, other lubricants

z liquid
z long chain (20 to 50 carbon atoms) alkanes, cycloalkanes,
aromatics
z 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
z liquid
z long chain (20 to 70 carbon atoms) alkanes, cycloalkanes,
aromatics
z boiling range = 700 to 1112 degrees Fahrenheit / 370 to 600
degrees Celsius
Residuals - coke, asphalt, tar, waxes; starting material for making other products
z solid
z multiple-ringed compounds with 70 or more carbon atoms
z 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.

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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.
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.
In the next section, we will look at how we separate crude oil into its components.

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:
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.
z 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.
z The trays increase the contact time between the vapor and the
liquids in the column.
z The trays help to collect liquids that form at various heights in the
column.
z 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

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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:
z pass to condensers, which cool them further, and then go to storage
tanks
z 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.
In the next section, we'll look at how we chemically process one fraction into
another.

Chemical Processing
You can change one fraction into another by one of three methods:
z breaking large hydrocarbons into smaller pieces (cracking)
z combining smaller pieces to make larger ones (unification)
z rearranging various pieces to make desired hydrocarbons
(alteration)

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.
z 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.
z visbreaking - residual from the distillation tower is heated (900
degrees Fahrenheit / 482 degrees Celsius), cooled with gas oil

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and rapidly burned (flashed) in a distillation tower. This process

reduces the viscosity of heavy weight oils and produces tar.
z 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.
z fluid catalytic cracking - a hot, fluid catalyst (1000 degrees
Fahrenheit / 538 degrees Celsius) cracks heavy gas oil into diesel
oils and gasoline.
z 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.
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.
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:

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z a column of sulfuric acid - removes unsaturated hydrocarbons

(those with carbon-carbon double-bonds), nitrogen compounds,
oxygen compounds and residual solids (tars, asphalt)
z an absorption column filled with drying agents to remove water

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