PETROLEUM

consist of complex mixture of organic hydrocarbon molecule

83-87% Carbon
11-15% Hydrogen
1-6% Sulphur

A petroleum refinery is a setup for manufacturing different types of petroleum

products from crude oil. Refining is the processing of one complex mixture of
hydrocarbons into a number of other complex mixtures of hydrocarbons. Some
refined petroleum products are Gasolines
Kerosene
Asphalt
Lubricating oil
Diesel
Refining process technology
Process operation
Coking
Thermal process
Catalytic cracking
Catalytic reforming
Hydrocracking
Hydrotreating
Alkylation
Isomerization

Technology
delayed coking ,Fluid coking
Thermal coking
Fluid cracking
Semigenerative , cycle ,continuous generation
Distillate, upgrading residual
Desulfurization, post hydro treating of FCC
Sulfuric acid, hydrofluoric acid
C4 feed, C5 feed, C5 and C6 feed

Refining process
The crude oil is charged into an atmospheric distillation tower, where it is separated
into light gas at the top of distillation tower and reduced crude at bottoms . The
reduced crude is feeded to the vacuum distillation unit and separated into vacuum
gas oil stream and vacuum reduced crude bottoms. The reduced crude bottoms from
the vacuum distillation unit is thermally cracked in a coker to produce coke. The
atmospheric and vacuum crude gas oils and coker gas oil are then feeded to fluid
catalytic cracking or hydrocracking units where heavy molecules are converted into
lower molecular weight compounds. The hydrocracked products are saturated
whereas catalytic cracker products are unsaturated and they need improvements in
quality by various methods.
FLOWCHART

IMPROVEMENT IN QUALITY

HYDRO TREATINGThe main objective of hydro treating is to eliminate or remove contaminants from
crude like sulphur , nitrogen, and some metals and to saturate olefins and aromatics
to produce further finished product.
In this process hydrogenation is done in the presence of catalyst to improve H/C
ratio of the crude.
REDUCING SULPHUR CONTENT
Sulphur and its compounds are most undesirable contaminant in the petroleum
products .combustion of fuel containing sulphur produce sulphur oxides ,which
cause acid rain and environmental pollution. Hydrodesulphurization is the process to
remove the sulphur contents from fuels.

OCTANE NUMBER

Octane number is measure of anti-knocking properties of a fuel. Higher the octane

number, more the fuel can withstand the compression before igniting. High octane
number fuel is used in gasoline engine, as it requires high compression ratio
Iso-octane and heptane is standard reference for measuring octane number of any
fuel. Iso-octane has rating of 100 whereas heptane has rating of 0. A mixture
containing 85% isooctane and 15% heptane will have octane rating 85.

.
Iso-octane

Heptane

Octane number of any fuel is equivalent to octane number of the mixture containing
iso-octane and heptane. Octane number of fuel can be increased by increasing
carbon chain branching.
In the isomerization process, straight carbon chain are converted into more branched
carbon chain and hence octane number can be increased by isomerization process.
Some isomerization may occur during the cracking process ,which results in
increased octane number.
Octane number can also be increased by adding some additive like tetraethyl lead
which act as octane booster by providing carbanion to increase the branching of
carbon chain.

ISOMERIZATION IN PETROLEUM REFINING

The need of isomerization in petroleum refining is to increase in quality by increasing

octane number.
History of isomerization
Need of Avgas (aviation gasoline) during world war II
butane isomerization was developed
use of catalyst like aluminium chloride
many of these process shutdown after the world war
use of tetra ethyl lead in 1970s
straight run gasoline (crude unit that has not been further processed) is totally
relied on tetra ethyl lead additive to raise octane number.
Isomerization for improving octane number
Isoparaffins has higher octane number.

Isomerization at various stages of refining process

Isk

Isomerization at various stages of refining process

ISOMERIZATION REACTION CONDITIONSIn isomerization reaction about 200-400 o F is preferred over high temperature
because of at low temperatures equilibrium conversion to isomer is enhanced. But at
low temperature reaction rate is slow down, so for this very active catalyst is used to
provide higher reaction rates. Catalysts used for isomerization contain platanium on
different bases.some catalyst required organic chlorides to maintain high activity.
There is possibility of formation of hydrogen chloride in reactor,
So feed to these reactor must be free of water and oxygen in order to avoid
corrosion problems in reactor and to retain activity of catalyst .

VAPOUR PHASE PROCESS

In the vapor phase isomerization of normal butane ,a feed of normal butane vapor
mixed with a some amount of dry hydrogen chloride vapor(for high activity ) upon a
fixed bed of aluminum chloride at a temperature of 220- 400. A fraction of the normal
butane is converted into its isoparaffin , isobutane. Normal butane and hydrogen
chloride are recovered for recycling While isobutane is withdrawn from the reactor .

BUTAMER PROCESS

The Butamer process is a fixed-bed, vapour-phase process in presence of small

amount of organic chloride. The reaction is conducted in the presence of a small
amount of hydrogen, to suppress the polymerization due to formation of intermediate
in the isomerization reaction and dehydrogenation because of hydrogen chloride
reaction is carried out in dry environment. This process uses a high activity, selective
catalyst which converts n-butane to iso -butane.

MECHANISM OF BUTAMER PROCESS

The formation of intermediate is catalysed by platanium catalyst

pt

CH3 -CH2 - CH2 -CH3 CH3 - CH2 - CH = CH2 + H2

the above reaction is reversible under butamer process conditions and equilibrium is
to the left side.

CH3 -CH2 - CH = CH2 + H+A- CH3 - CH2 C+H - CH3

+ ACarbocation
The above carbocation is not stable ,which immediately do methyl shift

Second carbocation is more stable than first because of inductive effect of three
methyl group

Finally by hydrogenation

Iso-butane

PROCESS VARIABLES:-

Reactor temperature:- increase in temperature increases iso-butane

content.
Hydrogen-to-Hydrocarbon Ratio (H2/HC):- conversion increases by
reducing ratio.
Pressure:-no significant effect.
Liquid Hourly Space Velocity :- increase in LHSV ,decreases the
conversion.

Flow diagram of butamer process

BENSAT PROCESS:
The BenSat process is used to

treat C5-C6 feedstocks with high benzene

contents. All the benzene is converted to cyclohexane upon a fixed bed of catalyst
Process conditions are moderate, and only a slight excess of hydrogen is needed.
Heat of reaction associated with benzene conversion is high ,which is managed
carefully to control temperature rise in the reactor. But this result in decrease of
octane number. Octane number of benzene is greater than cyclohexane. So BenSat
product need further processing in a isomerization unit in process like UOP penex
process.

UOP PENEX PROCESS

This process is specially used catalytic isomerization of pentanes,heaxanes,and

mixtures of it.in this process reaction take place in the presence of hydrogen ,over a
fixed bed of catalyst .Low temperature ,moderate pressure and low hydrogen partial
pressure is desired.

Light naphtha is feeded in any of the two dryer. These dryer are installed with
molecular sieves, to remove water to avoid deactivation of catalyst. After mixing with
small amount of hydrogen the feed enters a charge heater before entering the
reactors.in this two reactors are there which operate in series. The rector effluent is
cooled before entering the product stabilizer. The scrubber is used to remove HCL
formed from organic chloride which is added to enhance catalyst activity. The
stabilized isomerized liquid product from the bottom of the stabilizer then passes to
gasoline blending.
An efficient recycle process is obtained by combining the Penex process with UOPs
Molex process, Which have molecular sieves to separate the stabilized product from
bottom into high octane isoparaffin and low octane normal paraffin stream. The low
octane normal paraffin is again charged into penex unit.

feed

penex

MECHANISM OF PENEX PROCESS

molex

This reaction is believed to go through an olefin intermediate in acidic medium

Which is formed by dehyogenation of the paraffin.

The equilibrium conversion of paraffin is low at isomerization conditions.But to

Proceed the reaction sufficient olefin must be there to form a ccarbonium ion.

Hence by formation of the carbonium ion the olefin is removed and equilibrium is
mantained. The above carbocation goes skeletal isomerization via cycloalkyl
intermidiate:

The strong acidity of isomerization catalyst provide sufficient driving force