MEE 410

P ETROLEUM T ECHNOLOGY

CHAPTER 3

THERMAL CRACKING
Lecture 1

 PRIMARY PROCESSING UNIT

SECONDARY PROCESSING UNIT
Secondary units are installed to:

Upgrade lower grade products

Increase value added products
Maximise production of products in demand
Production of specialty products
Minimise production of undesired products

CRACKING

THERMAL
Requires High temp
Low conversion
High coke
Short Run-length
No control on product
pattern

CATALYTIC
Low temp
High conversion
Low coke
Long Run-length
Control on product
pattern

REACTORS

FIXED BED
Low cat surface area
Coking of bed calls
for shutdown
Cat make-up &
withdrawal not on-line
Short Run-length
No control on product
pattern

FLUIDISED BED
High cat surface area
On-line regeneration
Low coke
Long Run-length
Control on product
pattern

Intro
Cracking is a petroleum refining process in which heavymolecular weight hydrocarbons are broken up into light
hydrocarbon molecules by the application of heat and
pressure, with or without the use of catalysts, to derive a
variety of fuel products.
Cracking is one of the principal ways in which crude oil is
converted into useful fuels such as motor gasoline, jet fuel,
and home heating oil.
The term cracking is used to describe any type of splitting of
molecules under the influence of heat, catalysts and solvents,
such as in processes of destructive distillation or pyrolysis.

C16H34 C5H12 + C11H22

C16H34 -> C8H18 + C8H16

Application
Cracking processes allow the production of "light" products
such as LPG and gasoline from heavier crude oil distillation
fractions such as gas oils and residues.
Thermal cracking is used to "upgrade" very heavy fractions
or to produce light fractions or distillates, burner fuel and/or
petroleum coke.
Two extremes of the thermal cracking
high-temperature process ( 750 C to 900 C or more)
- produces ethylene and other
feedstocks for the
petrochemical industry,
milder-temperature delayed coking ( 500 C)
- under the right conditions, valuable needle
coke, a highly
crystalline petroleum coke used
in the production of
electrodes for metal
industries.

Thermal Cracking
Thermal cracking is a refining process in which heat
(~800C) and pressure (~700kPa) are used to break down,
rearrange, or combine hydrocarbon molecules.
The first thermal cracking process was developed around
1913.
However, this method produced large amounts of solid,
unwanted coke.
Distillate fuels and heavy oils were heated under pressure in
large drums until they cracked into smaller molecules with
better antiknock characteristics.

What is Knocking?
The sound of abnormal combustion.
Light Knocking wont harm an engine.
Heavy or prolonged can result in engine damage.

Thermal Cracking
Heat sensitive high molecular weight paraffins fragment when
temperature exceeds 400 degree C.
A molecule of Cn H2n+2 where n ranges from and above 25 easily splits in
to two, almost at the middle, resulting in one saturated molecule and
other unsaturated molecule.
All cracking reactions ultimately give rise to coke and hydrogen.
Cn H2n+2 Cn/2 Hn+ 2 + Cn/2 Hn
The above rcn is foremost and conclusive at moderate temperatures
around 400 deg C. , But fragmentation continues with increasing
temperature, giving rise to often simple products and occasionally
complex molecules.
A paraffin of lesser molecular order, cracking can be illustrated as
C12 C6 + C6
C6 C4 + C 2 / C 3 + C 3

Thermal cracking operations

Cracking
Temperature
(degree C)

Nature of Operation

Products

425-460

Visbreaking

Fuel oil

460- 520

Thermal Cracking

Gas, Gasoline. Tar oils,

Circulating oils

520-600

Low Temperature
Coking

Gas, Gasoline soft coke.

600-800

Gas Production

Gas and unsaturated

800-1000

High Temperature
Coking

Gas, Heavy aromatics

pitch or coke

Above 1000

Decomposition

H2, Gas, Carbon-black