Lecture 11 2018 - 2019 Fakhri H.

Ibraheem

Polymerization to produce polymer gasoline

Polymerization:
Propene and butenes can be polymerized to form a high octane product.
1. Definition: Polymerization 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. Polymerization may be accomplished
thermally or in the presence of a catalyst at lower temperatures.

2. Catalyst: 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.
Conventional (Solid Phosphoric Acid) SPA catalyst consists of silicon phosphate, which is
phosphoric acid chemically bonded to silica. On the other hand, the developed catalyst consists
of only phosphoric acid monomer supported on silica.

Propene and butenes can be polymerized to form a high octane product.

3. Chemistry:
Lecture 11 2018 - 2019 Fakhri H. Ibraheem

4. Process:

PFD to produce polymer gasoline using water as quenching media

PFD to produce polymer gasoline using HC gases as quenching media

4. Polymerization Operating Conditions:

Temperature: 175 – 235 C
Pressure: 200 – 1500 psi
Lecture 11 2018 - 2019 Fakhri H. Ibraheem

Normal catalyst consumption rates are in the range of one pound of catalyst per 100 - 200
gallons of polymer produced (830 – 1660) l/kg. The reaction is highly exothermic and
temperature is controlled either by injection of cold propane quench or by generating steam.
For solid phosphoric acid (SPA) reactor, the water content of the feed needs to be controlled
carefully because if the water content is too high, the catalyst softens and the reactor may plug.
Conversely, if the feed is too dry, coke tends to deposit on the catalyst, reducing its activity and
increasing the pressure drop across the reactor.
The distribution of water between the catalyst and the reactants is a function of temperature and
pressure which vary from unit to unit, and for this reason different water concentrations are
required in the feeds to different units.
There are two general types of units used for the SPA process:
1. Chamber reactor.
2. Tubular reactor.

SPA with chamber reactor:

The chamber reactor contains a series of catalyst beds with bed volume increasing from the inlet to the
outlet of the reactor operate with high recycle rates, the most common commercial design having five
beds. The catalyst load distribution is designed to control the heat of conversion. The operating
conditions are:
1. Pressure about 500-800 psig.
2. Temperature between 180 – 200 ̊C.

SPA with tubular reactor:

The tubular reactor is basically a shell-and-tube heat exchanger in which the polymerization reactions
take place in a number of parallel tubes immersed in a cooling medium and filled with the SPA
catalyst. Reactor temperature is controlled with the cooling medium which is water, The heat released
from the reactions taking place inside the tubes evaporates the water on the shell side.
Temperature controlled by:
1. Water temp.
2. Feed temp.
Tubular reactors usually operate at :
1. Pressure between 800-1100 psig.
2. Temperature around 200 ̊C.

With the SPA process, propylene and butylene are satisfactory feed-stocks and ethylene may also
be included, to produce a copolymer gasoline.
Lecture 11 2018 - 2019 Fakhri H. Ibraheem

Reaction mechanism: