Oligomerization

PGS.TS. Trương Hữu Trì

 CONTENTS

1 Background information

2 Industrial Processes

2
 Background information
 Oligomerization units have two main areas:
• upgrading C2 and C3 cuts from catalytic cracking, whose ethylene
and propylene are converted into olefinic gasoline;
• producing high-quality middle distillates from light olefins.
 Olefin oligomerization reactions are exothermic and endotroplc
(reduction in the number of molecules). As a result, conversion is
promoted by low ternperature and high pressure

Exothermicity of oligomerization reactions.

 Background information
A number of catalytic systems can activate the olefin oligomerization
reaction:
• phosphoric acid deposited on a solid support (quartz, kieselguhr);
• amorphous or crystallized (zeolites) silico-amines;
• transition metals (nickel and titanium) which act in the
homogeneous phase.

Main
characteristics
of different
catalytic routes
 Background information
 Acid Catalysis
The reaction takes place via a carbocation formed by the reaction of the
olefin with the catalytic acid
 Background information
 Catalysis by Transitien Metals
 Olefin oligomerization can be accomplished in the homogeneous phase by
complex catalysts containing titanium and nickel or cobalt salts.
 This method is widely used in petrochemistry to produce alpha-olefins from
ethylene or butenes (Alphabutol, Dimersol X processes).
 In refining, this type of process has found an application in order to reduce the
C3 cut propylene content and produce of a high-octane olefin C6 gasoline,
mainly in the United States.
 It is also implemented in converting ethylene from catalytic cracking C2 cuts
into gasoline (Dirnersol E process).
 In this type of reaction, olefin reactivity decreases with molecular weight. It will
therefore be easy to get good dimer selectivity (C6- for propylene).
 The reaction intermediate is the result of the monomer coupling on the metal or
being inserted on the metal hydride. Belowis a simplified diagram for propylene
 Background information
 Catalysis by Transitien Metals
 Industrial Processes
 Catpoly Process (UOP)
 This process can
transform
propylene, butene or
a mixture of both.
 It uses a phosphoric
acid catalyst laid
down on a solid
support of the
kieselguhr type.
 Industrial Processes
 Catpoly Process (UOP)
 The process involves a reactor where the catalyst is divided up into
several beds.
 Cold propane is introduced between them to adjust the temperature
 which rises because of the reaction exothermicity.
 After elimination of the entrained acid, the product is sent to a
stabilization column which removes the excess C3/C4.
 The process works under the following conditions:
• Space velocity: 0.5 to 1 m3/h per m3 of catalyst
• Temperature: 180-200°C
• Pressure: 30-40 bar
 Industrial Processes
 Catpoly Process (UOP)
 Properties of the resulting essentially olefmic gasoline.

Characteristics of oligomerization gasoline (Catpoly process)

 Industrial Processes
 Polynaphta Process (IFP)
 This process is designed to convert C3, C4 and C5 oletins into a gasoline
cut. It uses a silico-alurnina catalyst in a fixed bed reactor. After
preheating, the feed is sent to two in-series reactors separated by a heat
exchanger that eliminates the heat of reaction.
 The product under goes separation: stabilization of the gasoline and
gasoline/gas oil separation.
 The process works under the following conditions:
• Temperature: 150-200°C
• Pressure: 30-50 bar
• Space velocity: 0.3 to 0.5 m3/h per m3 of catalyst
 Under these conditions conversion reaches 95-98%.

Product characteristics
(Polynaphta process).
 Industrial Processes
 Polynaphta Process (IFP)
 Industrial Processes
 Dimersol Process (IFP)
 This process implements a soluble catalyst consisting of an organic
nickel salt.
 It involves a liquid phase reactor whose temperature is adjusted by
external circulation of the liquid phase cooled in a heat exchanger.
The catalyst is injected continuously in the reactor.
 The catalyst is eliminated from the product by ammonia injection
and caustic washing, and the product is then fractionated.
 The process works under the following conditions:
• Temperature: 40-50°C
• Pressure: 10-30 bar
• Residence time: 1-5 h
 Under these conditions, conversion of 80 to 89% is achieved
 Industrial Processes
 Dimersol Process (IFP)

Dimersol process
flow diagram
(IFP)
 Industrial Processes
 MOGD Process (Mobil Olefin to Gasoline and Distillate)
 This process uses a zeolitic catalyst to oligomerize light olefins to iso-
olefins with a higher molecular weight.
 The catalyst, ZSM-5, is a crystallized silico-alumina whose pores have a
diameter of 5.5 A.
 This fact gives it particular selectivity to produce olefins with a low
methyl and ethyl group substitution ratio.
 The process generally involves four fixed bed adiabatic reactors, three in
the reaction phase and the fourth being regenerated, The three reactors
are placed in series with intermediate heat exchangers designed to
absorb the heat of reaction.
 The reactor effluent is fractionated to ·produce a distillate cut and a
gasoline cut which is recycled when maximum distillate production is
desired.
 The distillate cut is generally sent to hydrotreating to saturate its olefinic
bonds, thereby providing a high Quality product (kerosene or diesel oil).
 Industrial Processes
 MOGD Process (Mobil Olefin to Gasoline and Distillate)
 The process works under the following conditions:
• Temperature: 150-200oC
• Pressure: 7-12 bar
• Space velocity: 1 to 2 m3/h per m3 of catalyst
 It can use light olefins as feed. from ethylene to butenes, but also olefinic
 cuts with an end point of 200oC
 The products are essentially olefinic. The heavy cut must be
hydrogenated in order to enter the diesel oil pool.

Typical product
properties are given
in table below