Petrochemical &

Petroleum Refining Technology

The Refining Process
(Conversion : Unification)
 THE REFINING PROCESS
Change the size and/or structure of hydrocarbon
molecules

1. Decomposition (dividing)
- thermal & catalytic cracking

2. Unification (combining)
- alkylation & polymerization

3. Alteration (rearranging)
- isomerization & catalytic reforming
 THE REFINING PROCESS
UNIFICATION

Processes to make gasoline components from

materials that are too light to otherwise be in
gasoline
• Alkylation
• Polymerization
Cracking + Polymerization + Alkylation = Gasoline yield representing 70
percent of the starting crude oil.
Polymerization

Convert light olefin gases including ethylene,

for example, propylene and butylene into
hydrocarbons of higher molecular weight and
higher octane number that can be used as
gasoline blending stocks.
 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.

Product : Polymer gasoline

 Introduction
• 1930s & 1940s, polymerization was widely used
produced leaded gasoline

• Replaced by alkylation process. Why?

market demand for unleaded gasoline

• Low cost processes still required to produce high

octane gasoline blending components
 polymerization still added to some refineries
Chemist Thomas
Midgley insisted
that tetraethyl lead
was safe
Important facts of Polymerization
• Propene & butene can be polymerized to form a
high octane product boiling in the gasoline boiling
range.

• The product is an olefin having unleaded octane

numbers of RON 97 and MON 83.

• This process produces ~0.7 barrels of polymer

gasoline per barrel of olefin feed as compared with
~1.5 barrels of alkylate by alkylation

• But the product has high octane sensitivity, low

capital & operating cost compared to alkylation –
polymerization are being added to some refineries
 Polymerization
Catalyst:
• Phosphoric Acid on an inert support

Example :
• Phosphoric acid + natural clay @
• Film of liquid phosphoric acid on crushed quartz

• Normal catalyst consumption rates are in the range of 1 lb

catalyst per 100-200 gallons of polymer produced (830-
1660L/kg)
 Polymerization

* Sulfur in the feed poisons the catalyst and basic

compounds neutralize the acid  increase acid
consumption

* Oxygen dissolved in the feed strongly affects the

reactions and must be removed

Temperature - 300-425˚F
Pressure - 400-1500 psi
Space Velocity - 0.3 gal/lb
 Polymerization

Schematic Diagram of Polymerization Unit

 Process description
• The feed, consisting of propane and butane as well as
propene & butene is contacted with amine solution to
remove hydrogen sulfide & caustic washed remove
mercaptans

• It is then scrubbed with H2O to remove any caustic @

amines & then dried by passing through a silica gel @
molecular sieve bed

• Finally a small amount of H2O (350-400 ppm) is added to

promote ionization of the acid before the olefin feed steam
is heated to 204oC & passed over catalyst bed. Reactor
pressures are about 3450 kPa (500 psi or 34 atm).
• The polymerization reaction is highly exothermic, and
temperature is controlled either by injecting a cold
propane quench or by generating steam.
• The propane and butane in the feed act as diluents and
a heat sink to help control the rate of reaction and the
rate of heat release. Propane is also recycled to help
control the temperature
• After leaving the reactor, the product is fractionated to
separate the butane & lighter material from the
polymer gasoline
• Gasoline boiling range polymer production is normally
90-97 wt% on olefin feed @ about 0.7 barrel of
polymer per barrel of olefin feed.
Cont…

• Polymerization reaction is highly exothermic

• Temperature controlled by:

- Injecting cold propane quench
- Generating steam
- Propane being recycled
Pre-polymerization Kettle
Thank You