The Plan

• Section 9.5 Crude Oil Refining

• Section 9.6 (very brief) on Combustion
• Review (if time)
 9.5 Crude Oil Refining

Crude oil is the

petroleum that is
pumped directly from
the ground.

It is a complex mixture
of hydrocarbons with
one or two carbon
atoms up to a limit of
~50 carbon atoms.
 Hydrocarbons & Crude Oil
Crude oil is a mixture of HYDROCARBONS
(compounds made up of carbon and
hydrogen). Some examples:

H H

Increasing length
Longer chains
H C C H
H H mean…
Ethane
1. Less ability to
H H H H flow
H C C C C H
H H H H 2. Less flammable
Butane
3. Less volatile
 Physical Processes in
Refining
– This is usually not useful, so it must be
separated by distillation.

– Classified on the basis of viscosity,

hydrocarbon content & sulfur content.
• The less viscous, the less refining it needs.
• Can be separated using chemical & physical
means.
• Petroleum
products and
the ranges of
hydrocarbons
in each
product.
 Crude Oil Refining
Physical Chemical
• Fractional distillation • Cracking
(fractionation) – larger molecules broken
– diff. bp of components down with heat/catalysts
allow for separation – A) thermal 1900’s
– as separation occurs • T & P, C
the fractions are (carbon/coke)
collected – B) catalytic 1930’s
• these are • uses catalyst, C
component steams – C) hydrocracking 1960’s
– lower bp = smaller • combines catalytic &
molecule hydrogenation (+H2)
– higher bp = larger • C produced
molecule
 Crude Oil Refining

Physical Chemical
• Solvent extractions • Catalytic reforming
– solvent is added to – changing naptha (aliphatic) to
aromatic (cyclic) gasoline
dissolve specific
– aromatics burn better
components
• impurities, products
• Alkylation (isomerization)
• Dewaxing – increasing the # of branches
– cooling to solidify a (alkyl’s)
specific fraction – more branches = better
burning
CH3 – octane number in gas

CH3CH2CH2CH3 + 2H2 CH3

CH3CH2CH2CH3 CH3CHCH3
• Some types of crude oil are better for
gasoline production, whereas others may
be better suited for motor oil products.

• The raw resource is sent to be refined

into different components of
hydrocarbons, called a fraction.

This separation can

involves both
physical and
chemical processes.
Physical Processes in Oil Refining
• Crude oil is a complex
mixture of thousands of
compounds with various
boiling points.

• Chemical engineers take

advantage of the
differences in boiling
points to separate the
components.

• This technological
process is called
fractional distillation
or fractionation.
Fractional Distillation Set-up
 Fractional Distillation of Petroleu
m
• Petroleum can be separated into different
fractions by fractional distillation.

• This separation can take place because

petroleum is a mixture of substances with
different boiling points.
 Fractional Distillation
Crude oil can be separated by fractional distillation. The
oil is evaporated and the hydrocarbon chains of different
lengths condense at different temperatures:
Fractions with
low boiling
points
condense at
the top

Fractions with
high boiling
points
condense at
the bottom
(Petroleum Gas)

Petrol
Naphtha Temperature
Kerosene increases down
the column
Diesel

Lubricants

Bitumen
 Separating Mixtures of Hydrocarbons

• Since different
hydrocarbons have
different boiling
points they can be
Decreasing separated by
temperature
distillation.

• Crude oil is heated

to about 500oC in
the absence of air.

• The vapors rise and

cool changing to
liquids at different
Crude Oil Mixture
Crude Oil Mixture
Crude Oil Mixture
Crude Oil Mixture
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Crude Oil Mixture
Crude Oil Mixture
Crude Oil Mixture
Crude Oil Mixture
Crude Oil Mixture
Crude Oil Mixture
Crude Oil Mixture
Crude Oil Mixture
Crude Oil Mixture
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Crude Oil Mixture
Crude Oil Mixture
 Decreasing
melting point
Crude Oil Mixture
 Fractionation
• When crude oil is heated to 500°C with no air,
most constituent compounds vaporize.

• The compounds with a higher boiling point

remain as a mixture of asphalts and tars.

• The vaporized components of the mixture

gradually cool in a metal tower.

• To get from one layer to

the next the gas must pass
through the liquid in the next
tray.
 Fractionation
• Those with higher boiling points condense in
lower trays and those with lower boiling points
condense in higher trays.

• Side streams are withdrawn at various locations

along the column. These streams are called
fractions.

• The explanation for this is based on bonding

theory.

• Low boiling points are due to small molecules,

which have fewer electrons and therefore weaker
London forces compared to large molecules.
 Solvent Extraction
• Another physical refining process, in
which a solvent is added to selectively
dissolve and remove an impurity or to
separate some useful products from the
mixture.
 Chemical Processes in Oil
Refining
• The two necessary chemical processes
are cracking and reforming.

• These processes are used because

there are not enough of the
hydrocarbons that are in demand being
produced from fractional distillation
(like gasoline & diesel).
 Cracking
• In the absence of oxygen, alkanes can be
“cracked” (broken into smaller fragments)
at high temperatures and in the presence of
catalysts.

• This reduces high molecular weight

hydrocarbons, C15 - C18 such as those found
in oil, to low molecular weight hydrocarbons,
like C5 - C12 such as those found in gasoline.

• This is the basis of the oil refining process.

• Eg. C17H36(l)  C9H20(l) + C7H16(l) + C(s)
 Cracking
• The story with oil refining is there are always
improvements in technology.

• Thermal Cracking used extensively until the 1930’s

produced a lot of waste solid coke.

• Catalytic Cracking uses catalysts and produces a lot

less undesirable byproducts.

• Hydrocracking, yet another improvement in the

1960’s, is a combination of catalytic cracking and
hydrogenation.

• During hydrogenation no coke is produced.

C17H36(l) + H2(g)  C9H20(l) + C8H18(l)
 Catalytic Cracking

alkane + 400-600oC  smaller alkanes + alkenes + H2

 Catalytic Reforming
• Essentially this is the opposite of cracking.

• Larger molecules are formed from smaller ones

(naptha fraction into aromatic gasoline molecules).

• E.g., C5H12(l) + C5H12(l)  C10H22(l) + H2(g)

• Reforming is used to:

1. Convert low grade gasoline to higher grades.
2. Make larger hydrocarbons for synthetic
lubricants.
 Alkylation (Isomerization)
• Another way to improve the quality of
gasoline is to increase the branching
molecules in a process called
alkylation.

• Also called isomerization, because it

converts a molecule into a branched
isomer.
 Summary
Catalytic Cracking:
Larger molecules  smaller molecules + carbon

Hydrocracking:
Larger molecule + hydrogen  smaller molecules

Catalytic Reforming:
Aliphatic molecule  aromatic molecule + hydrogen

Alkylation (Isomerization):
Alphatic molecule  more branched isomer
• The octane number
is a description of
how rapidly
gasoline burns

• It is based on (A) n-
heptane, with a
number of 0, and
(B) 2,2,4-
trimethylpentane,
with an assigned
number of 100.

• Higher the #
= the better the
burn.
 Case Study-Octane Number

• Discuss in a group.
 Sulfur in Gasoline
• This is a huge pollution problem, because sulfur
emission reduce air quality and can also lower pH
of rain.

• Sulfur also has negative effects on the cars

catalytic converter.

• The reduced effectiveness increases other

pollutants in the air like carbon monoxide.

• The technology to reduce sulfur in gasoline is a

process called hydrogenation or hydrotreating.
 9.6 Combustion Reactions
• Complete Combustion

• Incomplete Combustion
 Complete Combustion
• Alkanes are relatively unreactive but they
burn (react with oxygen) at high
temperatures to form carbon dioxide and
water and to release energy (the reaction is
exothermic). In this way they can be used
as fuels.

Example:
2 C8H18(l) + 25 O2(g)  16 CO2(g) + 18 H2O(g) + energy

• This is octane, the chief component of

gasoline. We burn this as a fuel in our cars.
• Combustion of alkanes as fuels is
essentially the same as the oxidation of
carbohydrate during cellular respiration in
living systems.

• Both have the same outcomes, the release

of energy to do work and the production of
carbon dioxide and water.

i.e., C6H12O6(l) + 6 O2(g)  6 CO2(g) + 6 H2O(l) + energy

 Incomplete Combustion
• These reaction may produce carbon
monoxide, and soot or any combination of
carbon dioxide, carbon monoxide, and
carbon (soot), in addition to water and
energy.

• 2 C8H18(l) + 17 O2(g)  16 CO(g) + 18 H2O(g)

• 2 C8H18(l) + 9 O2(g)  16 C(s) + 18 H2O(g)

• Alcohols can be added to gasoline to reduce

the carbon monoxide emissions.

• Alcohol is considered an oxygenator & makes

combustion more complete.
Study for the Quiz tomorrow so
this is Not True for You.