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Unipol PE

Process
Gas Phase
Unipol PE Process
Description

• Purification

• Polymerization

• Degassing and Recovery

• Extrusion/Pelletizing
Purification:

• The gas fluidized bed process is very sensitive to


poisons.

• Acetylene, carbon monoxide and carbon dioxide


are by-products of the pyrolysis process to make
ethylene.

• These by-products in minute levels are able to


reduce the polymerization rate significantly.

• Both ethylene and comonomer require purification.


Purification Steps:

• A typical ethylene purification train will have the following:

• palladium bed to remove acetylene

• a copper oxide bed to remove carbon monoxide

• a copper bed to remove oxygen

• molecular sieves to remove moisture.

• Comonomers are usually

• degassed using a stripper column and

• dried using molecular sieve


Polymerization

• Reactor

• Consists of a reaction zone and disengagement zone

• On startup, the reaction zone is charged with a base of polymer


particles before gas flow is initiated.

• Monomer (ethylene gas) is fed to the compressor inlet, whereas


the α-olefin comonomer (1- butene or 1-hexene) is added to the
reactor inlet.

• The catalyst is stored in a catalyst feeder under a nitrogen blanket.

• If co-catalyst (e.g., trialkyl aluminum) is required, it is fed


separately to the reactor inlet.
Polymerization

• Reactor

• Particle entrainment is further reduced by a cyclone and a


filter to avoid deposition of polymer on heat-transfer
surfaces and compressor blades.

• Polymerization heat is removed by a heat exchanger before


the recycle gas is compressed and returned to the reactor.

• The distribution plate at the bottom of a reactor plays an


important role in the operation of the reactor. As the
polymer particles are hot and possibly active, they must be
prevented from settling to avoid agglomeration.
Polymerization

• Reactor

• The polymer particles are withdrawn close to the


distributor through sequential operation of a pair of
timed valves, defining a segregation zone.

• The reactor is operated at a temperature below the


melting point of the polymer particles. For HDPE
production, the operating temperature is 90-110oC.

• An operating temperature of about 90oC or lower is


preferred for production of LLDPE, which contains
about 15 mol % of one or more of the C3 to C6 α-olefins
Polymerization

• Reactor

• There are now four types of catalysts for ethylene


polymerization: Ziegler-Natta, Phillips, metallocenes and late
transition metal catalysts. Only the first three types are in use
commercially, whereas the last is still in research and
development stage.

• Ziegler-Natta catalysts have many variations but are generally


TiCl4 supported on MgCl2, combined with a variety of
electron donors and cocatalysts. Ziegler-Natta catalysts
account for most of the polyethylene produced industrially. In
operations, a trialkyl aluminum co-catalyst (typically triethyl
aluminum) is added separately to the reactor feed.
Spheripol PP
Technology
Bulk Polymerization
• The catalyst, liquid propylene and hydrogen for
molecular weight control are continuously fed into
the loop reactor.

• The bulk polymerization typically occurs in two


tubular loop reactors filled with liquid propylene
and optional gas-phase copolymerization reactors.

• Reduced reactor residence time and economically


optimized equipment sizing can be achieved
relative to other technologies, due to the high
monomer density and increased catalyst activity.
• The finishing section consists of highly efficient
liquid propylene vaporization operations at very
high polypropylene concentrations, separation
of the unconverted monomers, and complete
recycling of the monomers back to the reactor.
HDPE
HDPE Slurry Process
PVC Suspension Polymerization
PVC Suspension Polymerization
PVC Suspension Polymerization
Process Description
• PVC is produced by polymerization of vinyl
chloride monomer (VCM).

• The main polymerization methods include


suspension, emulsion, and bulk (mass) methods.
About 80% of production involves suspension
polymerization.

• Emulsion polymerization produces finer resin


grades having much smaller particles, which are
required by certain applications.
PVC Suspension Polymerization
Process Description
• First, the raw material VCM is pressurized and liquefied,
and then fed into the polymerization reactor, which
contains water and suspending agents (polyvinyl alcohol)
in advance.

• Next, the initiator is fed into the reactor, and PVC is


produced under a few bars at 40 – 60°C.and suspending
agents such as poly(vinyl alcohol).

• The mass is reacted at 50-65°C. PVC forms as tiny


particles which grow until they reach a desired size or
about 85-90% of the contained monomer is converted to
resin.
PVC Suspension Polymerization
Process Description
• The resin-water mixture is heated, sometimes under vacuum,
until the unconverted monomer is substantially removed. The
resin is then removed from the water and dried in rotary,
flash or fluid bed dryers by exposure to heated air.

• If only vinyl chloride monomer is reacted, the product is PVC


homopolymer. If a monomer such as vinyl acetate is mixed
with the vinyl chloride then a PVC copolymer is produced.
bed dryers by exposure to heated air.

• The role of water is to remove and control the heat given off
in the polymerization process.
PET Melt Phase Condensation
Polymerization Process
Solid Phase Condensation Polymerization Process
Solid State Polymerization
• Solid State Polymerization (SSP)

• A process in which the polymer chain lengths are increased by


heat in the absence of oxygen and water, by means of either
vacuum or purging with an inert gas to drive off the by-products of
reactions.

• The reaction is driven by temperature, pressure, and the diffusion of


by-products from the interior of the pellet to the surface.

• SSP is an important step frequently used after melt-polymerization


for the purpose of enhancing the mechanical and rheological
properties of polymers before injection blow molding or extruding.
The SSP technique is widely applied in industrial manufacture of
bottle-grade PET, films, and superior industrial fibers.

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