Petroleum Refining

The higher the API

gravity, the lighter the
crude

In the reforming reaction, naphthenes

are targeted to generate aromatics which
have higher octane numbers

Octane Number
% volume of
Iso-octane (2,2,4-tri-methyl
pentane) in a mixture of Iso-octane and nheptane that
gives same knocking (untimely
burning of fuel in SI engine) characteristic as
the fuel under consideration.

Iso-paraffins and aromatics have high octane

number while n-paraffins/cycloparaffins have
very low value, unsaturates do have high octane
values
but
not
preferred due
to gum
contribution.

Specification of Petrol

REFINERY PROCESSES
Refining of crude oils: primary separation processes and
secondary conversion processes.
Separation processes
Atmospheric and vacuum distillation of crude oils is the
main primary separation processes producing various
straight run products, e.g., gasoline to lube oils/vacuum
gas oils (VGO). These products, particularly the light and
middle distillates, i.e., gasoline, kerosene and diesel are
more in demand all over the world.

VDU operates at 25-40 mm Hg

Residual Fluidized Catalytic Cracking (RFCC)

naphtha
Light naphtha is the fraction boiling
between 30 C and 90 C and consists of
molecules with 56 carbon atoms.
Heavy naphtha boils between 90 C and
200 C and consists of molecules with 6
12 carbons.

CONVERSION PROCESSES
Upgrade lower-value materials such as heavy residues
to more valuable products such as naphtha and LPG.
Naphtha is mainly used to supplement the gasoline pool,
while LPG is used as a fuel or as a petrochemical
feedstock.

Improve the characteristics of a fuel. For example, a

lower octane naphtha fraction is reformed to a higher
octane reformate product. The reformate is mainly
blended with naphtha for gasoline formulation or
extracted for obtaining aromatics needed for

 Reduce harmful impurities in petroleum fractions and

residues to control pollution and to avoid poisoning
certain processing catalysts.
For example, hydrotreatment of naphtha feeds to catalytic
reformers is essential because sulfur and nitrogen
impurities poison the catalyst.

THERMAL CONVERSION PROCESSES

Steam cracking

Coking

Vis-breaking

STEAM CRACKING OF HYDROCARBONS

(Production of Olefins)
Producing light olefins, especially ethylene.
The feedstocks for steam cracking units
range from light paraffinic hydrocarbon
gases to various petroleum fractions and
residues.

Coking
Coking is a severe thermal cracking process
designed to handle heavy residues with high
asphaltene and metal contents, which if fed to
catalytic cracker may poison the catalysts.
Products are hydrocarbon gases, cracked naphtha,
middle distillates, and coke.
Hydrotreatment is usually required to saturate olefinic
compounds and to desulfurize products from coking
units.

Viscosity Breaking (Vis-breaking)

Viscosity breaking aims to thermally crack longchain feed molecules to shorter ones, thus reducing
the viscosity and the pour point of the product.
Feed is usually a high viscosity, high pour point fuel
oil that cannot be used or transported, especially in
cold climates, due to the presence of waxy
materials.
Vis-breaking is a mild cracking process that
operates at approximately 450C using short
residence times.

Cracking

Chemistry of cracking

Reforming
To improve the octane number of a
naphtha feedstock by changing its chemical
composition.

Catalytic reforming is considered the key

process for obtaining benzene, toluene, and
xylenes (BTX).

Reforming

Isomerization
Converting straight chain alkanes to side
chain paraffins, which have high octane
number.

n-pentane = 61.7
iso-pentane = 92.3

 isomerisation
of
butane
methylpropane (isobutane):

(from

LPG)

to

2-

Butane vapour is passed over a solid catalyst,

aluminium chloride, on an inert solid at ca 300 K. The
two alkanes are then separated either by distillation or
by passing them through a molecular sieve, an
aluminosilicate. The branched chain alkane is trapped
and the straight chain passes through and is
recirculated into the reactor. The 2-methylpropane is
subsequently released and used to make a branched
alkane,
2,2,4-trimethylpentane
(iso-octane),
for
petrol.

Alkylation
Produces larger hydrocarbon molecules in the
gasoline range from smaller molecules. The
products are saturated branched hydrocarbons
having high octane ratings. (butane alkylate = ON
92-97)
Acid catalyzed reaction between isobutane and
various light olefins, and the product is known as the
alkylate.
concentrated sulfuric acid or anhydrous hydrofluoric
acid is used as a catalyst

Polymerization
Combining of two or more olefinic
molecules to yield larger molecules.
Typical feedstocks for polymerization
process are C3 and C4 olefins that are
obtained from catalytic cracking.
The end product from polymerization
reactor is a dimer or a trimer of the
olefins.

Animation links for refining operations

http://www.nesteoil.com/oilrefininginaction/
http://sciencenetlinks.com/interactives/ener
gy/interactive/api_treat_012810.swf