Petroleum Refining Process

Overview of petroleum refining process

Process name Action Method Purpose Feedstock(s) Product(s)
FRACTIONATION PROCESSES
Atmospheric Separation Thermal Separate fractions Desalted crude oil Gas, gas oil,
distillation distillate, residual
CONVERSION PROCESSED--DECOMPOSITION
Catalytic cracking Alteration Catalytic Upgrade gasoline Gas oil, coke Gasoline,
distillate petrochemical
feedstock
Coking Polymerize Thermal Convert vacuum Gas oil, coke Gasoline,
residuals distillate petrochemical
feedstock
Hydro-cracking Hydrogenate Catalytic Convert to lighter Gas oil, cracked oil, Lighter, higher-quality
HC's residual products
Visbreaking Decompose Thermal reduce viscosity Atmospheric tower Distillate, tar
residual
CONVERSION PROCESSES--UNIFICATION
Alkylation Combining Catalytic Unite olefins & Tower isobutane/ Iso-octane (alkylate)
isoparaffins cracker olefin
Polymerizing Polymerize Catalytic Unite 2 or more Cracker olefins High-octane naphtha,
olefins petrochemical 2stocks
 Overview of petroleum refining process
Process name Action Method Purpose Feedstock(s) Product(s)
FRACTIONATION PROCESSES
CONVERSION PROCESSES--ALTERATION OR REARRANGEMENT
Catalytic Alteration/ Catalytic Upgrade low- Coker/ hydro- High oct.
reforming dehydration octane naphtha cracker naphtha Reformate/
aromatic

Isomerization Rearrange Catalytic Convert straight Butane, pentane, Isobutane/

chain to branch hexane pentane/ hexane
TREATMENT PROCESSES
Desalting Dehydration Absorpti Remove Crude oil Desalted crude oil
on contaminants
Hydrotreating Hydrogenati Catalytic Remove impurities, Residuals, cracked Cracker feed,
on saturate HC's HC's distillate, lube

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 1. UNIFICATION (Alkylation)
• Alkylation is basically the INTRODUCTION of
one hydrocarbon group into another
hydrocarbon molecule. It is inverse of
cracking process, because it increases the
chain length
• In oil refining, ISOBUTANE is alkylated with
the low molecular weight olefins
(propene/butene,..), (means isobutane is
combined with olefin) in the presence of
strong catalyst, low temperature and high
pressure.

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• Alkylate is mixture of HIGH octane number,
branched chain paraffin hydrocarbons. It is
premium blending stock because it has
exceptionally good antiknock properties.

• Since crude oil contains only upto 40% of

the hydrocarbon constituents in the gasoline
range, refiners use FCC process to convert
high molecular weight olefins into smaller
and more volatile compounds. While
Alkylation process transforms low
molecular-weight alkenes and iso-paraffins
molecules into large iso-paraffins with high
octane number.
 Reaction Mechanism of Acid catalyzed alkylation

Step I:
• Reaction of olefin (here we use example of Propene) with an acid
to form carbo-cation named here propyl cation. In this reaction
addition of H+ ion to the double bond of alkene takes place. Means
the double bond breaks up and one of the carbon atoms picks up the
H+ ion;

•The cation of carbon atom is named as “carbo-cation”.

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Step II:
•  Ittakes place in two further steps:
(a) Reaction of carbo-cation with isobutene to form
(b) higher carbon atom carbo-cation:
• This Carbo-cation now is more reactive and has
3carbon atoms directly attached to it and known as
tertiary carbo-cation.

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• There are 3 types of carbocations depending upon
the number of carbon atoms directly attached to the
carbon atom having positive charge.
(i) Primary carbocation (p-carbocation): having single
carbon atom attached
(ii) secondary carbocation (sec-carbocation): having
two carbon atoms attached, e.g.: propyl cation
(iii) tertiay carbocation (ter-carbocation): having three
carbon atoms attached
• The order of their reactivity is:
• Ter-carbocation > sec-carbocation > p-carbocation
• Step III:
•  It takes place in two further steps:
(a) Picks up H+ ion from Acid to form ALKYLATE or
Rearranges to form a new carbocation for further
chain reaction.

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• (b) Reaction of butyl cation with propene to
form long chain cation. Means double bond
break up and cation adds to one of the
carbon atom to form a long chain cation.

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 Reaction Mechanism of Acid catalyzed alkylation

• Overall reaction:
  

• Acid sulfuric acid (H2SO4) or hydrofluoric acid (HF) is

represented as symbol “H+X-” where H+ = H+
• X- = F-/ HSO4-
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 Refinery Process for Alkylation
• Alkylation plant uses catalyst hydrofluoric
acid HF, known as HF-plant, or sulfuric acid
H2SO4: known as sulfuric plant.
• The HF is very volatile, and difficult to use,
so this plant is not commonly used while
mostly common is sulfuric plant.
• The sulfuric plant consist of 7 main parts: the
chillers, the reactor, the acid separator, the
caustic wash and three distilling plants as
shown in figure 2.

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Figure 2 Alkylation unit flow diagram
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 Refinery Process for Alkylation
• The chillers: are used to reduce the
working temperature and to maintain
high pressure. Since acid is very
strong, highly reactive, it releases heat,
which may cause explosion. So
temperature must be controlled to be
low 10-30oC. High pressure is
maintained in order to keep the
reaction mixture in liquid form.
• The reactors: mixture is then pumped into the
reactor. The reaction time for the alkylation
process is relatively long, so the reactors
used here are very large. The residence time
for the reaction is 25-30 minutes to assure
that olefins are in good contact with isobutane
and acid, to promote the reaction.
• The acid separators: also called acid Settler.
The mixture then moves to this chamber,
where hydrocarbon mixture gets completely
separated from the acid like water and oil.
Hydrocarbons are drawn off from the top, the
acid is drawn off the bottom and then recycled
back to the feed stock (raw material Or crude
oil).
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• The caustic wash: the Hydrocarbons (HC)
from the acid separators have some traces
of acid in it, which must be removed. This
mixture is then washed with caustic soda
(NaOH), which neutralize the acid and
removes from the mixture.

• Fractionators: 3 fractionators separate the

alkylate and saturated gases. Any
unreacted isobutene is recycled back to the
feed stock.
• During the alkylation some reactions also
takesplace. Because there are lot of
molecules forming and reacting, so there
are small amount of propane, butane also
forms.
 2. Polymerization- UNIFICATION
• It is the process in which light olefins, e.g.,
ethene, propene, butene are induced to
combine/polymerize with itself to produce a
single branched molecule of two/three times
their original molecular weight having same
elements in the same proportion as the
original molecule.
• The reaction takes place in the presence of
catalyst: phosphoric acid, high pressure and
temperature in the range of 300° and 450° F.

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• The product of polymerization is known as
DIMATE.

• For example: Propene polymerizes to form

isohexene
• This process is similar to Alkylation. Here the
reaction plant is named as POLY PLANT or
DIMER plant.
 Description
• Polymerization in the petroleum industry is the
process of converting light olefin gases
including ethylene, propylene, and butylene
into hydrocarbons of higher molecular weight
and higher octane number that can be used as
gasoline blending stocks. It is similar to the
Alkylation process.
• Polymerization combines two or more identical
olefin molecules to form a single molecule with
the same elements in the same proportions as
the original molecules. Polymerization may be
accomplished thermally or in the presence of a
catalyst at lower temperatures.
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 Polymerization
• The reaction can takes place through various
types of mechanisms, such as free-radical
type (involve free-radical formation), cationic
mechanism (involve carbo-cation formation),
Anionic mechanism (involve carbo-anion
formation). And the final product in
Termination step can either have double
bond in it (by rearrangement of carbon chain)
or with the single bond (like in alkylation
process).
 Mechanism of Reaction
•  Step I(Initiation)
•  Reaction starts with the addition of acid (H+)
to the butene. The double bond breaks up
and picks up the H+ ion to form butyl cation.
•
•  

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 Mechanism of Reaction
Step II 
•Addition of propyl cation to the propene:
double bond breaks up and adds to the carbon
centre with positive charge and forms long
chain carbo-cation

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 Mechanism of Reaction
Step III (termination) 
•The unstable iso-hexyl cation picks up H+ ion
to terminate the reaction and forms stable iso-
hexane molecule.

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 Details for the Refinery process of
polymerization
• The olefin feedstock is pretreated to remove sulfur and other
undesirable compounds.
• In the catalytic process the feedstock is either passed over a
solid phosphoric acid catalyst or comes in contact with liquid
phosphoric acid, where an exothermic polymeric reaction
occurs. This reaction requires cooling water and the injection of
cold feedstock into the reactor to control temperatures
between 300° and 450° F at pressures from 200 psi to 1,200 psi.
• The reaction products leaving the reactor are sent to
stabilization and/or fractionator systems to separate saturated
and unreacted gases from the polymer gasoline product.

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Details for the Refinery process of polymerization
In the petroleum industry, polymerization is used
to indicate the production of gasoline
components, hence the term "polymer" gasoline.
Furthermore, it is not essential that only one
type of monomer be involved. If unlike olefin
molecules are combined, the process is referred
to as "copolymerization." Polymerization in the
true sense of the word is normally prevented, and
all attempts are made to terminate the reaction at
the dimer or trimer (three monomers joined
together) stage.
However, in the petrochemical section of a
refinery, polymerization, which results in the
production of, for instance, polyethylene, is
allowed to proceed until materials of the required
high molecular weight have been produced.
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