Polymer Manufacturing

Processes
S.Sindhu
 Polythene (PE)
• Polymer Chemistry
- The manufacture of polyethylene follows addition
polymerization kinetics involving catalysis of purified
ethylene.
- Its molecular formula is -(CH 2-CH2)n- with a molecular
weight of 1,500 to 100,000.
- Its melting point is 85 – 110 oC.
- Its density is 0.91 -0.93 , when produced by high
pressure process and 0.96, when produced by low
pressure process.
 Technology
• There are three processes by which
polyethylene is manufactured
- High pressure process
- Intermediate pressure process
- Low pressure process
 High pressure process

• This process was developed in the UK by

ICI.
• It uses peroxide catalyst at 100-300 oC
and produces low density randomly
oriented polymer which have a low
melting point.
• The process is run at pressure of 1000 –
2500 atms. This process yields Low Density
Polyethylene (LDPE).
 Intermediate pressure processs
• This process was developed in the USA by
Phillips Petroleum Co. for preparing high
density polymer with increased rigidity,
crystallinity, tensile strength and softening
point. The process uses MoO3 and Cr2O3
on alumina as catalyst and is operated at
30 – 100 atms
 Low Pressure Process
• This process was originally developed in
Germany for preparing high density
polyethylene (HDPE).
• The catalyst used in this process consists of
aluminium triethyl activated with heavy metal
derivatives such as TiCl4.
• In the process flow sheet (Figure 1), is the
description of Low Pressure Ziegler Process to
produce polyethylene
 Ziegler Process
• At the very onset, through the process of
desulphurization and removal of light ends, high purity
ethylene is prepared. The ethylene is further treated to
remove traces of oxygen and its compounds which can
possibly deactivate the catalyst. The ethylene is first
pumped into a reactor where it is mixed with catalyst
diluents stream. The optimum temperature and pressure
maintained should be 70oC and 7 atms gage. The effluent
stream then follows across a series of flash drums inorder
to remove the solvent from the catalyst. The residual
catalyst at this point is removed by adding water.
 Ziegler Process
• The flashed solvent is thereafter recycled to
the catalyst make –up unit after appropriate
drying and redistillation. The slurry which
results is then centrifuged to remove the
water, and the water is treated to remove the
catalyst before recycle. The final products of
polyethylene solids are then dried, extruded
and given the required final forms
 Ziegler Process

Figure 1. Manufacture of Polythene

 Description
• As part of the chemical reaction, a second compound, called a
“comonomer” is added.
• This might be a chemical like hexene, butene-1 or propylene.
Depending how much of which type is added, these chemicals
affect the polymer’s final properties such as stiffness.
• Hydrogen is added to the reaction mixture to terminate the
polymer chain length to control the polymer’s melting
point. The reaction components are continuously fed into a
reactor that is constantly being stirred.
• To keep everything as a slurry, an inert diluent compound
such as hexane or butane is also added to the reactor. The
diluent also helps absorb the heat that is generated in the
reaction
POLYVINYL CHLORIDE (PVC)
• Polymer Chemistry
- The manufacture of Polyvinyl Chloride (PVC)
follows addition type kinetics and produces
linear polymers.
The vinyl chloride monomer (VCM) has a boiling
point of 13.4oC and is a gas at room temperature
and pressure. The vapor pressure of VCM over
the typical polymerization temperature range of
50oC to 70oC is 800 – 1250 KPa.
 Technology
• The two most commercially use methods for the manufacture
of PVC are Emulsion Polymerization and Suspension
Polymerization.
• The Suspension Polymerization process provides 80 % of the
world production.
• The Suspension Polymerization process is actually a bulk
polymerization process which is carried out in millions of
droplets .
• Each of these droplets act as small reactors. The liquid vinyl
chloride is dispersed in water by vigorous stirring in a reactor.
• The reactor is fitted with baffles for optimum agitation and
also has a condenser for heat removal. In the reactor , small
droplets of size 30 - 40μm diameter are formed.
 Technology
• A monomer soluble free radical initiator is charged into the
reactors. After charging , the reactor temperature is increased
to 45 – 75 o C .
• The heat decomposes some of the initiators to free radicals ,
and the monomers in these droplets begin to polymerize., the
reaction is highly exothermic and the heat is removed via
cooling jackets or by boil – off to the condenser.
• Thereafter, the condensed monomer is returned to the reactor.
Although the PVC is insoluble in its monomer, it is swollen by
VCM to form a coherent gel.
• Even in the gel phase , the polymerization continues. The
polymerization is rapid at first, but slowly, as the conversion
reaches 80 – 85 %, the rate is reduced due to monomer
starvation
 Technology
• At a predetermined pressure , the reaction is ended by
adding a chain terminator or by venting the unreacted
monomer to a recovery plant.
• Even after venting, the aqueous slurry contains 2 – 3 %
unreacted monomer, which is then removed by stripping
in a Stripping Column.
• The unreacted monomer is recovered and stored for later
polymerization stages. The slurry is then passed through
a heat exchanger and is passed through a continuous
centrifuge to give a wet cake with 20 – 30 % moisture
Figure 2. Manufacture of Poly(Vinyl Chloride). a)Reactor; b)Blowdown
Vessel; c)VCM Recovery Plant; d)Stripping Column; e)Heat Exchanger;
f)Centrifuge; g)Driers
 Manufacture of formaldehyde
• Formaldehyde (methanal, melting point: –92°C, boiling
point: –21°C) is produced solely from methanol by using a
silver catalyst.
• The process can be air oxidation or simple
dehydrogenation.
2CH3OH + O2 → 2HCH=O + 2H2O
CH3OH → HCH=O + H2
• These two reactions occur simultaneously in commercial
units in a balanced autothermal reaction because the
oxidative reaction furnishes the heat to cause the
dehydrogenation to take place.
 Manufacture of formaldehyde – cont’d
• In the process fresh and recycled methanol are vaporized, superheated, and
passed into the methanol-air mixer.
• Atmospheric air is purified, compressed, and preheated to 54°C in a finned heat
exchanger.
• The products leave the converter (a water-jacketed vessel containing the catalyst)
at 620°C and at 34 to 69 kPa absolute.
• About 65 percent of the methanol is converted per pass. Temperatures are on the
order of 450 to 900°C and there is a short contact time of 0.01 seconds.
• The reactor effluent contains about 25% formaldehyde, which is absorbed with
the excess methanol and piped to the make tank.
• The latter feeds the methanol column for separation of recycle methanol
overhead, the bottom stream containing the formaldehyde and a few percent
methanol.
• The water intake adjusts the formaldehyde to 37% strength (marketed as
formalin).
• The catalyst is easily poisoned so stainless-steel equipment must be used to
protect the catalyst from metal contamination.
Manufacturing process - formaldehyde
 Manufacture of vinyl esters
• The addition of acids to acetylene furnishes the respective
esters by addition across the double bond.
CH≡CH + CH3COOH → CH3COOCH=CH2 Vinyl acetate
CH≡CH + HCl → CH2=CHCI Vinyl chloride
• If two molecules of acid react, a compound such as 1,1-
ethane diacetate is formed:
CH≡CH + 2CH3COOH → (CH3COO)2CHCH3
• Vinyl chloride is usually prepared by the oxychlorination
(dehydrochlorination) of ethylene.
CH2=CH2 + Cl2 → CH2ClCH2Cl dichloroethane CHLORINATION
CH2=CH2 + 0.5O2 + 2HCl → CH2ClCH2Cl + H2O OXYCHLORINATION
CH2ClCH2Cl → CH2=CHCI + HCl DEHYDROCHLORINATION
 Manufacture of vinyl chloride – cont’d
• The cupric chloride (CuCl2) catalyst (on an inert fixed carrier) may react as
follows:
CH2=CH2 + 2CuCl2 → CH2ClCH2Cl + Cu2Cl2
2Cu2Cl2 + O2 → CuO.CuCl2
CuO.CuCl2 + 2HCl → 2CuCl2 + H2O
Direct chlorination
• EDC (Ethylene dichloride) is prepared by reacting
ethylene and chlorine in the presence of iron(III) chloride
as a catalyst, these compounds react exothermically:
• CH2=CH2 + Cl2 → ClCH2CH2Cl
• This process results in high purity EDC and high yields.
Dissolved catalyst and moisture must be removed before
EDC enters the vinyl chloride production process.
 Oxychlorination

• Vinyl chloride plants use recycled HCl to produce more EDC via
oxychlorination, which entails the reaction of ethylene, oxygen, and
hydrogen chloride over a copper(II) chloride catalyst to produce EDC:
• CH2=CH2 + 2 HCl + ½ O2 → ClCH2CH2Cl + H2O. The reaction is highly
exothermic.
• Due to the relatively low cost of ethylene, compared to acetylene,
most vinyl chloride has been produced via this technique since the late
1950s. This is despite the lower yields, lower product purity and higher
costs for waste treatment.
• By-products of the oxychlorination reaction, may be recovered, as
feedstocks for chlorinated solvents production. One useful byproduct
of the oxychlorination is ethyl chloride, a topical anesthetic.
 Thermal cracking
• When heated to 500 °C at 15–30 atm (1.5 to 3 MPa) pressure, EDC
vapor decomposes to produce vinyl chloride and anhydrous HCl.
• ClCH2CH2Cl → CH2=CHCl + HCL
• The thermal cracking reaction is highly endothermic, and is generally
carried out in a fired heater.
• Even though residence time and temperature are carefully controlled, it
produces significant quantities of chlorinated hydrocarbon side
products.
• In practice, EDC conversion is relatively low (50 to 60 percent). The
furnace effluent is immediately quenched with cold EDC to stop
undesirable side reactions.
• The resulting vapor-liquid mixture then goes to a purification system.
Some processes use an absorber-stripper system to separate HCl from
the chlorinated hydrocarbons, while other processes use a refrigerated
continuous distillation system.
 Hazards of VCM
• In 1950’s VCM was trialled as a potential anaesthetic gas for medical
applications. However, it is also now known, from studies on workers in PVC
polymerisation plants during the 1970’s that VCM can be a carcinogen, with the
potential to cause a rare form of cancer (cancer of the blood vessels of the liver
known as angiosarcoma), if there is significant exposure over a prolonged period.
• Exposure to vinyl chloride vapors, even in very small concentrations, causes
some workers to develop liver cancer. The government requires that worker
exposure to vinyl chloride monomer be no more than 1 ppm over an 8-hour
period, and no more than 5 ppm for any 15-minute period. To achieve this
requires extensive and expensive pollution-abatement systems.
• Vinyl acetate is also made from ethylene in a vapor-phase process. The feed
mixture is ethylene, acetic acid, and oxygen, and is circulated through a fixed-bed
tubular reactor. The catalyst is a noble metal, probably palladium, and has a life
of several years.
 Manufacture of Phthalic anhydride
• Phthalic anhydride (melting point: 131.6°C, boiling point: 295°C
with sublimation) can be made from the reaction of o-xylene with air
and also from naphthalene, which is isolated from coal tar and from
petroleum.
CH3C6H4CH3 + [O] → HOOCC6H4COOH
HOOCC6H4COOH → OCC6H4COO + H2O
• The use of naphthalene as the source of phthalic anhydride
diminished but has become popular once again.
• Phthalic anhydride is used for the manufacture of plasticizers, such
as dioctyl phthalate, unsaturated polyester resins, and alkyl resins.
• Phthalic anhydride reacts with alcohols such as 2-ethylhexanol, and
the products are often liquids that, when added to plastics, impart
flexibility without adversely affecting the strength of the plastic.
Most of these plasticizers are used for poly(vinyl chloride)
flexibility. Dioctyl phthalate is a common plasticizer.
Phthalic anhydride – flow chart