Topic:

Polymerization Process for Gasoline

Production
ENCH4PP Petroleum and Synthetic Fuel Processing
24 April 2014

Presenter 1: Jesantha Govender

Presenter 2: Shristhi Sewpersad
Presenter 3: Waseem Amra
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Lecturer: Prof A.H. Mohammadi
 What is polymerization in the petroleum
industry?
• Polymerization in the petroleum industry is the conversion of light
olefin gases including ethylene, propylene, and butylene into
hydrocarbons of higher molecular weight and a higher octane
number (>90).

• It may be accomplished thermally or in the presence of a catalyst at

lower temperatures.

• This process combines two or more identical olefin molecules to

form a single molecule with the same elements in the same
proportions as the original molecules but two or three times their
molecular weight.

• It is a controlled process in which olefin gases are converted to

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liquid condensation products that may be suitable for gasoline or
other liquid fuels.
 Historical Development
• Polymerization, as practiced in the petroleum industry, is a process
that can claim to be the earliest to employ catalysts on a commercial
scale.

• In the early 1930’s large amounts of olefins, particularly light olefins,

became available in copious quantities from catalytic cracking plants
in refineries.

• While these olefins may be used as petrochemical feedstock, many

conventional petroleum refineries producing petroleum fuels and
lubricants are not capable of diverting these materials to
petrochemical uses.

• Processes for producing fuels from these cracking off gases are
therefore desirable and from the early days, a number of different
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process evolved.
 Historical Development

• Since the middle and late 1950s, polymerization has been

supplemented by alkylation as a method of conversion of light (C3
and C4) gases to gasoline fractions.

• The alkylation reaction also achieves a longer chain molecule by the

combination of two smaller molecules, one being an olefin and the
other an isoparaffin (usually isobutane).

• During World War II, alkylation became the main process for the
manufacture of isooctane, a primary component in the blending of
aviation gasoline.

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 Polymerization vs. Alkylation
Polymerization Alkylation
Purpose To polymerize propylenes To produce a high octane
and butylenes to form high gasoline by reacting light
octane gasoline. olefins with light iso-
paraffins.
Product Gasoline MON = 83 MON = 88-94
RON = 97 RON = 94-99
Feedstock Propylene and butylene Olefins
Isobutane
Process Variables Pressures: 3 -7.5 MPa • Lower temperatures yield
Temperatures: 175-230 °C a higher quality and avoids
polymerization.
•Strong acid strength yields
more cations and increased
activity.
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Catalyst Phosphoric acid on an inert Strong acids
support (H2SO4 and HF)
 Polymerization vs. Alkylation

• Polymerization: Produces 0.7 bbls polymer gasoline/ bbl olefin feed

Alkylation: Produces 1.5 bbls alkylate/ bbl olefin feed

• Polymerization product has a high octane sensitivity, however capital

and operating costs are much less than alkylation costs.

• Therefore Polymerization being used again due to lower costs , the

mandated phase out of leaded gasoline, and the demand for high
octane fuel.

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Location of Polymerization Process in a
Refinery Polymerization Process

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 2 Types of Polymerization
Catalytic Polymerization

• Olefins can be conveniently polymerized by means of an acid catalyst.

• These catalysts are: Sulphuric acid, Copper Pyrophosphate and Phosphoric

acid.

• Temperatures and Pressures: 150℃ to 220 ℃ and 10-81 atm

Thermal Polymerization

• Thermal polymerization is regarded not as effective as catalytic

polymerization but has the advantage that it can be used to polymerize
saturated materials that cannot be induced to react by catalysts.

• This process consists of vapour phase cracking, followed by prolonged

periods at high temperatures for the reactions to proceed near completion.
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• Temperatures are: 510℃ to 570 ℃
 Polymerization
• Hydrocarbon gases from cracking stills, particularly olefins, have
been major feedstock of polymerization.

• Polymerization processes convert by-product hydrocarbon gases

produced in cracking into liquid hydrocarbons suitable for use as
high octane motor and aviation fuels and petrochemicals.

• Products produced from polymerization process sent to gasoline

blending, petrochemical complex, and storage.

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Polymerization Process (Catalytic)

Schematic of polymerization Process 10

 Polymerization Process (Catalytic)
• The olefin feedstock is pretreated to remove sulphur compounds and other
undesirables.

• Then sent to a reactor in which it is passed over a phosphorus catalyst, usually a solid
catalyst or liquid phosphoric acid, where an exothermic polymeric reaction occurs.

• Catalyst: Normally 0.6 – 1.2 kg catalyst consumed/ m3 polymerate produced.

• This requires the use of cooling water and the injection of cold feedstock into the
reactor to control temperatures at various pressures.

• Acid in the liquids is removed by caustic wash, the liquids are fractionated, and the
acid catalyst is recycled. The vapour is fractionated to remove butanes and neutralized
to remove traces of acid.

• LPG (C3, C4) & Naphtha (C4, C5) produced

• Operating Conditions:
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 Temperature – Feed is heated to 200◦C before contacting catalyst bed Pressure –
Reactor pressure of 30 bar is maintained.
 Polymerization Reaction
• To combine olefinic gases by polymerization to form heavier
fractions, the combining fractions must be unsaturated.

• The following equation is typical of polymerization reactions:

• The reactions are highly exothermic and the temperature is controlled

through the injection of cold propane or by generating steam. 12
 Polymerization of Isobutylene

• Propylene, normal butylene and isobutylene are the olefins usually

polymerized in the vapour phase.

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 Safety and Health Considerations
Fire Prevention and Protection

• Polymerization is a closed process where the potential for a fire exists due
to leaks or releases reaching a source of ignition.

Safety

• The potential for an uncontrolled exothermic reaction exists should loss of

cooling water occur.

• Severe corrosion leading to equipment failure will occur should water

make contact with the phosphoric acid, such as during shutdowns.
Corrosion may also occur in piping manifolds, reboilers, exchangers, and
other locations where acid may settle out.

Health
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• Potential for exposure to caustic wash (sodium hydroxide), to phosphoric
acid used in the process or washed out during turnarounds, and to catalyst
dust
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Thank you

Questions

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