Polypropylene Plant, IOCL

Overview on Polypropylene
Production and specification

Kush Kumar Rana

Polypropylene Plant, IOCL

Content
Polypropylene fundamentals
Polypropylene properties
Polypropylene technologies
Polypropylene process
Additives used in Polypropylene
Polypropylene application

Polypropylene producers
Polypropylene market
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Polypropylene Plant, IOCL

Polypropylene
fundamentals
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Polypropylene Plant, IOCL

Polymer - ?

Polypropylene Plant, IOCL

What is PP ?

Polypropylene Plant, IOCL

Polypropylene Development
Prof Giulio Natta and Prof Karl Ziegler synthesized

polypropylene in 1954.

Karl Zieglar got Noble Prize for discovery of Ti based

catalyst in 1963.
Giulio Natta got Noble prize for using the catalyst to
prepare stereo regular polymers in 1963.
Continuous and rapid development in Polymerization
catalyst continues for getting better yield and properties.

Polypropylene Plant, IOCL

Tacticity

Isotactic Methyl Group (-CH ) on same side of polymer chain

3

Syndiotactic Methyl Group (-CH ) on alternate side of polymer chain

3

Atactic

Methyl Group (-CH3) Randomly placed

Polypropylene Plant, IOCL

Polypropylene
Properties
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Polypropylene Plant, IOCL

Characteristics of PP

Polypropylene Plant, IOCL

Types of Polypropylene
PP

PP
Homopolymer
(PPHP)

PP Impact
Copolymer
(PPICP)

PP Random
Copolymer
(PPRCP)

C3-(C3-C3-C3)n-C3

High Stiffness
High Service Temp.

C3-(C3-C3-C2-C3-C3-C3-C2-C3)nC3
C3-(C3-C3-C3)n-C3
+
C3-(C3-C3-C2-C2-C3-C3-C3-C2-C2-C2-C3-C2-C3)n-C3

High Impact Strength

Good Clarity

Polypropylene Plant, IOCL

Properties of Polypropylene
Homopolymer PP

High stiffness

High crystallinity
High melting point
Low impact strength

Random Copolymer

High Impact Copolymer

High clarity
Low melting point
Reduced crystallinity
Reduced stiffness
Better impact
Enhanced clarity

High impact strength

Higher level of toughness
Low stiffness
Low tensile strength
More opaque
Low Hardness

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Polypropylene Plant, IOCL

Comparative Properties of PP
Optical properties

RCP > HP >> ICP

Melting point

HP

Impact strength

ICP > RCP > HP

Modulus

HP

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> ICP >> RCP

> RCP > ICP

Polypropylene Plant, IOCL

Property Controlling Parameters

Average Molecular Weight

Molecular Weight Distribution
Crystallinity
Processing Conditions
Additive Recipe used

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Polypropylene Plant, IOCL

Molecular Weight

Polypropylene Plant, IOCL

Polypropylene Plant, IOCL

Molecular Weight Distribution

Polypropylene Plant, IOCL

Crystallinilty

Polypropylene Plant, IOCL

Polypropylene
Technologies
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Polypropylene Plant, IOCL

PP Polymerization Processes
- Bulk Processes
Spheripol

- Gas Phase Fluidized Bed Processes

Unipol
Novolen
Spherizone
Innovene

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Polypropylene Plant, IOCL

Gas Phase Process Novolen PP

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Polypropylene Plant, IOCL

Gas Phase Process Unipol (Dow) PP

Compressor

Reactor
1
Reactor Feed
Catalyst
Cocatalyst

Compressor

Cooler

Cooler

Reactor 2
Reactor Feed

Product
Discharge
System

Product
Discharge
System

Homopolymer Random
Copolymer

Impact Copolymer

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Gas Phase Process Borestar Process

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Polypropylene Plant, IOCL

Gas Phase Process Innovene PP

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Gas Phase Process Spherizone Process

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Polypropylene Plant, IOCL

Polypropylene
Process
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Polypropylene Plant, IOCL

Plant design highlights

No. of Lines : Two
Annual capacity: 300,000 TPA each line based on 8,0000 operating hrs.
Technology : Spheripol
Licensor: Basell Polyolefins, Italy
Capability:
Line 1: Homopolymer and Random Copolymer type PP
Line 2: Homopolymer, Random Copolymer, High Impact Copolymer
and Ter polymer Polypropylene.
Product Form: Pellets packed in 25 kg bags, palletised form.

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Plant Areas
The different areas of PP plant area

PP Line 1
PP line 2
Common Area

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Polypropylene Plant, IOCL

The major section of PP line 1 are1

1100

Catalyst Preparation

1200

Precontacting, Pre-polymerization, Bulk Polymerization

1300

Polymer degassing, Propylene recovery

1500

Polymer steaming, drying

1600

Blow down area

1800

Polymer Powder extrusion and Additivation

1900

Product Homogenization, storage

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Polypropylene Plant, IOCL

The major section of Common Area are1

1100

Donor Metering

2100

Teal storage & Metering, Atmer metering

1600

Common Process Utilities

1700

Monomer Purification

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Polypropylene Plant, IOCL

Bagging /warehouse
Homogenization
Extrusion

Common Area

Battery
Limit

Main Substation
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Mineral Oil
storage

TEAL SYSTEM

Polypropylene Plant, IOCL

Extrusion Building
Loop Reactors

Recovery/Steaming
& Drying

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Polypropylene Plant, IOCL

Area 1100/2100
Catalyst, Co-catalyst & Donor
storage and metering

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Polypropylene Plant, IOCL

The catalyst system consists of three components:

i. Ziegler

Natta

catalyst-

Titanium

supported on MgCl2 (solid)

ii. Triethyl aluminum (TEAL) (liquid)
iii. External Donor (liquid)

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catalyst

Polypropylene Plant, IOCL

Catalyst:
Ticl4 catalyst supported on MgCl2 base.
A crystalline solid having a controlled particle size, is
dispersed in a mixture of mineral oil and grease.
The oil/grease mixture ratio is 70/30 by weight, and is
mixed with catalyst.
Catalyst concentration ranges from 200 to 260 grams of
catalyst per liter of mixture.

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Polypropylene Plant, IOCL

Catalyst Generation for PP

1st Generation - Crystalline -TiCl3+AlCl3+AlEt2Cl

2nd Generation - Crystalline -TiCl3+AlCl3+AlEt2Cl
3rd Generation - Crystalline -TiCl4+MgCl2+TEAL+Di(Ethyl Benzoate)+De(MPT)
4th Generation - Crystalline -TiCl4+MgCl2+TEAL+Di (Alkylphalate)+De (Alkoxy
Silane)

5th Generation - Crystalline -TiCl4+MgCl2+TEAL+Di (1,3-diether)

6th Generation - Metallocene of Zr or Hf + Methylaluminoxane (MAO)

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Polypropylene Plant, IOCL

Catalyst technology :
TiCl4 ,Mgcl2 ( Carrier ) and internal Donor.
Polymer morphology and PSD are highly dependant on size and
structure of the catalyst.
Stereo regularity is controlled by internal donor.

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Polypropylene Plant, IOCL

TEAL (Triethyl Aluminium):

Acts as co-catalyst. It converts the inactive Ticl4 present in the

catalyst to the active form Ticl3.

Used in the process in pure form.

Colourless liquid, highly pyrophoric in nature.

Burst into flame if it comes in contact with air or explodes in

contact with water.

Safety devices are provided as flame detectors connected to

interlocks that shuts-off the discharge in case of TEAL leaks &
fires.

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Polypropylene Plant, IOCL

Donor:

Donor is used in conjunction with the high mileage catalyst

as stereoregulating agent (Controls the arrangement of
chains within the polymer).

Donor Regulates Tacticity in the polymer. Adjusting the

Donor addition quantity controls the atactic content of the
final product.

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Polypropylene Plant, IOCL

Liquid additive- Atmer 163:

Suppresses the residual high reactivity of polymer fines coming from the
loop reactors.
Protects reciprocating compressor by removing any traces of Teal.
Fed to the outlet of the second loop reactor and to the suction of recycle
gas compressor for the gas phase reactor.
Fed into waste oil treatment drum to neutralize Teal contained into the
recovered exhausted oil.
Used as antistatic additive in extrusion section according to additivation
recipe.

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Polypropylene Plant, IOCL

Catalyst, Teal & Donor Feeding Criteria

Catalyst paste flow rate sets the throughput of the plant.
Teal flow is fed in ratio against the total monomer feed to the first
loop reactor.
As an alternative, Teal can be fed in ratio rationed versus the
catalyst feed to the precontacting pot.
Donor is flow ratio controlled against TEAL flow.
Setting of the flow ratios maintains the TEAL/Titanium and
Donor/Titanium mass ratios within the required ranges, at normal
plant operating conditions.

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Polypropylene Plant, IOCL

Area 1200/2200
Pre-contacting, Pre-polymerization
&
Bulk Polymerization

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Polypropylene Plant, IOCL

Preontacting, prepoly & bulk polymerization
Prepoly reactor

Catalyst
TEAL

1st loop reactor

Donor

Precontacting
pot

Propylene

Hydrogen

Jacket cooling pumps

Jacket water circulation pump

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2nd loop
reactor

Polypropylene Plant, IOCL

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Polypropylene Plant, IOCL

Pre-contacting:
Pre-contacting pot is a constantly stirred vessel of about 3 litres
volume & coupled with magnetic agitator.
Chilled water is circulated in the jacket to maintain a constant
temperature of about 10C.
The Catalyst paste, Donor, and TEAL are fed to pre-contacting pot.
Here the Catalyst activation takes place.
The overflow feeds the pre-polymerization reactor R2200.
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Polypropylene Plant, IOCL

Pre-polymerization:
Catalyst mixture leaving the precontacting pot is injected into a stream of cold
propylene, which feeds the pre-polymerizer reactor (R 2200); capacity- 1.1 m3
The slurry is fed to a pre-polymerizer reactor (R 2200) where reaction takes
place at low kinetics.
A small amount of propylene is polymerized under controlled conditions of
temperature (20C), pressure (34-35 bar) and residence time in the prepolymer
reactor.
Temperature control is by controlling chilled water temp in the prepolmer
reactor jacket.

Contd..
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Polypropylene Plant, IOCL

Bulk Polymerization:
The main polymerization reaction for homopolymer, random copolymer and
terpolymer (future) production takes place in two loop reactors in series.
The polymerization conditions are the same on both reactors,
Reaction Conditions.
Reaction temperature
:
70-73 C
.
Pressure
:
34 45 barg.
.
Slurry concentration
:
50% by weight
.
Propane concentration
:
not more than 40% by weight

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Polypropylene Plant, IOCL

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Polypropylene Plant, IOCL

Bulk Polymerization:
Each loop Reactor has its own circulating pump, which continuously recirculates
the contents of the loop.
The pressure is controlled by the reactors surge drum (V2202), which is a vessel
connected to the 2nd loop reactor R 2202. Surge drum is equipped with a steam
heated propylene vaporizer (E 2203).
The slurry is transferred from R2201 to R 2202.
The slurry is discharged from R 2202 through the valve LV 2301 (installed in
the bottom) to the flash line.

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Polypropylene Plant, IOCL

Bulk Polymerization:
Important Process variables/ Controls
Pressure control- Indirectly by controlling the Reactor surge drum pressure,
as reactors are floating with surge drum.
Temperature control- By controlling the jacket water temperature in the loop
reactor jacket.
Density Control- Ensures the amount of reactant and product balance and
thereby controls the flowability of the slurry. Density control is with the fresh
monomer feed into the reactors.
Discharge control- Is based on the level of the reactor surge drum.

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Polypropylene Plant, IOCL

Area 1300/2300
Polymer Degassing & Propylene
Recovery

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Polypropylene Plant, IOCL

Polymer degassing & Propylene Recovery

LP C3 Scrubber

Flash Drum
Polymer slurry
from reactor

Recycle gas
compressor
Recycle gas filter

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Polypropylene Plant, IOCL

Polymer degassing & Propylene Recovery

From recycle gas compressor

From flash drum

Recycle C3 Scrubber

To steamer scrubber
C3 Feed tank

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Polypropylene Plant, IOCL

Polymer Degassing and propylene Recovery

The slurry discharged from the second reactor is heated in the flash pipe to
vaporize the un-reacted liquid propylene.

The gas and polymer mixture is discharged into flash drum where the operating
pressure is 18kg/cm2g.

The propylene gas is sent to HP recovery where the propylene is recovered,

scrubbed and recycled.

The polymer from the flash drum bottom can be sent to

1. Bag Filter (in case of Homo-polymer/ Random Copolymer / Ter-

polymer polymer Production).

2.

Gas phase reactor (in case of High Impact Copolymer production),

where copolymer reaction takes place. The Gas phase reactor
discharges to Bag filter.

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Polypropylene Plant, IOCL

Polymer Degassing and propylene Recovery

In Bag filter, the pressure is further reduced to 0.6 kg/cm2g thereby

recovering propylene through LP recovery.
Propylene recovered in LP recovery is scrubbed with oil-atmer mixture,
compressed and sent to HP recovery.

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Polypropylene Plant, IOCL

Area 2400
Gas Phase Polymerization
&
Ethylene Striper

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Polypropylene Plant, IOCL

GAS PHASE REACTOR
Recirculation compressor

Gas phase reactor

From Flash drum

JW Circulation pump

Hydrogen

Ethylene

Propylene
From recycle C3 Scrubber

To Recycle gas filter

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Polypropylene Plant, IOCL

GAS PHASE CO-POLYMERIZATION

In this section a rubbery ethylene-propylene phase is added to the homopolymer

matrix (coming from bulk polymerisation) to produce a high-impact heterophasic
copolymer
- System consists of GPR (Gas Phase Reactor), compressor & cooler
- GPR is vertical cylindrical fluidised bed reactor fed with homopolymer matrix from V2301.
- Polymer is fluidized by means of reaction gas circulated by the centrifugal
compressor 21PK2401 and distributed under polymer bed.Gas passes through the
polymer bed ensures fluidisation & removes heat of reaction.
- The polymer from the gas phase reactor bottom is discharged to the bag filter.

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Polypropylene Plant, IOCL

Area 1500/2500
Polymer steaming and drying

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Polypropylene Plant, IOCL

Polymer Steaming

Steam/ Propylene to
steamer scrubber

In the steamer the polymer is

fluidized with live steam. The
steaming is done to
1.
2.

3.

M
Polymer In

Deactivate the residual catalyst

activity.
Deactivate the Residual Teal in
the polymer.
Recover the residual propylene
in the polymer

LP STEAM

Polymer Out

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Polypropylene Plant, IOCL

Polymer Drying

Wet Nitrogen to
Scrubber

In the dryer the polymer which is

moist because of the steaming is
dried by fluidizing with hot nitrogen.
The Dryer discharges the dry
polymer to the conveying system
for transfer to the intermediate
powder silos.

Wet Nitrogen
Wet Polymer

Polymer Fines to
Conveying system
Fluidised Bed of
Polymer

Hot Nitrogen

Dried Polymer To conveying

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Polypropylene Plant, IOCL

Area 1700/2700

Raw Materials Purification.

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Polypropylene Plant, IOCL

Propylene Purification

Feed tank PP line 1

Coalescer
21V-1701

Feed tank PP line 2

C3 from BL
26 kg/cm2(g)
35-45 deg C

Moisture

Light End Stripper

21C-1701

Phosphine/
Sulphur/ Arsine
Removal Column
21C-1702

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Propylene Drying Unit

21PK 1703

Polypropylene Plant, IOCL

Propylene Purification:

Propylene coming from Battery Limit passes through a

water/ propylene separator (coalescer) to remove any free
water.
Propylene is sent to light ends stripper to remove any
lighter impurities that may be there in propylene.
From light end stripper, propylene is then sent to Sulphur,
Arsine and Phosphine removal unit.
Propylene is then sent to drying unit. From Drying Unit
propylene goes to the Feed tanks of the respective lines.

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Polypropylene Plant, IOCL

Ethylene Purification

PP line 1

PP line 2

Ethylene
from BL
50kg/cm2g
30-45 deg C

CO & O2 Removal Tower

21C 2704A/B

Ethylene Dryingand
Unit
CO2 removal unit
21PK 2702

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Polypropylene Plant, IOCL

2. Ethylene Purification:
Since ethylene pressure is 50 kg/cm2 g, ethylene doesnt need to be
compressed .
Ethylene from Battery Limit is sent to CO and O2 removal towers.
After CO removal, ethylene is sent to drying and CO2 removal unit.

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Polypropylene Plant, IOCL

Butene Purification

21V
2710
Butene
Feed
Tank

Coalescer
21V-2703
C4 from BL
8 kg/cm2(g)
35-45 deg C

Moisture

PP Line 2

Light End Stripper

21C-2731

Butene Drying Unit

21PK 2731

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21P 2701
Butene Feed Pump

Polypropylene Plant, IOCL

Butene Purification:

Butene coming from Battery Limit passes through a water/

propylene separator (coalescer) to remove any free water.
Butene is sent to light ends stripper to remove any lighter
impurities that may be there in the feed.
From light end stripper, butene is sent to drying unit.
After drying butane goes to the Butene Feed tank.

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Polypropylene Plant, IOCL

Hydrogen Purification and compression

Line 1
Hydrogen From BL
17 kg/cm2g

hydrogen filter
21PK2705A/B

Line 2

Hydrogen compressor package

Hydrogen from the battery limit which is at 17 kg/cm2g is filtered

and compressed to 50kg/cm2g and sent to the two polymerization
lines.

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Polypropylene Plant, IOCL

Area 1800/2800
Extrusion and Additivation.

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Polypropylene Plant, IOCL

Extruder:

Pellet water system

Powder feed

Extruder
PP Pellets
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Polypropylene Plant, IOCL

Polymer Extrusion and Additivation.

PP polymer powder from the dryer is sent to the intermediate
silos, installed on the top of the extruder building, by means of
nitrogen closed loop pneumatic haulage .
From the silos the polymer powder is fed to the extruder.
Liquid additives are added based on the application of the
particular grade of polymer.
PP polymer powder and additives are homogenized, extruded and
granulated by an under-water pelletizer in the extruder.
Pellets are then quenched and transported by the water stream to
the dryer.

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Polypropylene Plant, IOCL

Polymer Extrusion and Additivation.

Water is separated from the pellets first by gravity and then by
centrifugal force.
Final drying is accomplished by dry air flow through the pellets.
Agglomerates are continuously and automatically removed.
Dried pellets are separated from fines and coarse pellets by a
vibrating screen.
From Hopper the pellets are fed to pneumatic haulage for the
conveying to the homogenizing silos.

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Polypropylene Plant, IOCL

Product blending, storage and bagging.

There are SIX Homogenization silos.
Extruded PP pellets are conveyed to the blending silos.
Product lot is blended for homogenization in the blenders.
Product from homogenization silos is fed to the bagging silos
by pneumatic conveying package.

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Polypropylene Plant, IOCL

Product bagging and warehouse facility.

There are 7 bagging and palletizing machines for PP.
3 Machines are for PP line 1.
4 Machines are for PP line 2.
The product is bagged in 25 kg bags and stored in palletized form.
Capacity of each bagging and palletizing machine is 1200 bags/hr
Warehouse is designed for storage capacity equivalent to 21 days
full production.

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Polypropylene Plant, IOCL

The first numeric digit of the grade name denotes the family of the PP
resin.
1 - Homopolymer PP
2 - Random Copolymer
3 - Impact Copolymer
4 - Super High Impact Copolymer

The second, third and fourth numeric digit indicate the MFI of the
product (MFI X 10).
The fifth alphabetical digit indicates the Application of the grade.
o M: Molding
o E: Extrusion
o Y: Fiber and filaments
o R: Raffia
o F : Film
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Polypropylene Plant, IOCL

The Sixth alphabetical grade indicates the additivation package for the grade.
o S : Slip and antiblock
o G : General
o N: Nucleating Agent
o U : UV stabilizer
o C : High Clarity

Seventh alphabetical digit is optional and indicates the special properties of

the grade.
o P : Easy processability

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Polypropylene Plant, IOCL

Polypropylene
Additives used
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Polypropylene Plant, IOCL

Additives used for PP

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Polypropylene Plant, IOCL

Additives used for PP

Additives

Modifier

Processing Aids

Primary Antioxidant

Property Extender

(Increases service life) eg 1010

Secondary Antioxidant (Encounter Thermal Degradation)

PEPQ / 168

Thermal Stabilizer (Enhance Thermal Stability)

eg DSTDP
UV Stabilizer (Encounter UV Degradation )

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eg

Polypropylene Plant, IOCL

Additives used for PP

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Polypropylene Plant, IOCL

Additives used for PP

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Polypropylene Plant, IOCL

Polypropylene
Application
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Applications - Film
PP is used extensively in the Film applications primarily because of its
high strength
High clarity

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Applications Molding (Household applications)

PP is used extensively in the Molding applications primarily because of its

high strength
Good flowability

Low density

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Applications Molding (other applications)

PP is used in specialized Molding applications because of its

high strength
Good Chemical resistance

Good Flexural Strength

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Applications Molding (Automotive applications)

PP (Impact Copolymer Grades) are used extensively in the Automotive
Molding applications primarily because of its
High strength
Better Impact Flexural Balance
Good UV resistance

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Polypropylene Plant, IOCL

Applications Consumer Durables

Polypropylene is fast replacing Polystyrene and ABS for use in consumer
durables sector.

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Applications - Fibres
PP is used extensively in the Fibre applications primarily because PP fibres are
Light weight
Rot Proof
Resistant to Fading

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Polypropylene Plant, IOCL

Applications Fabrics
PP is used in both woven and non woven fabric applications

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Applications - Packaging
PP is used extensively in the Packaging applications both
Flexible packaging- metallized PP film
Containers- Food Grade

Rigid packaging

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Applications Industrial Use

PP is used extensively in the industrial applications because of
high strength
High chemical resistance

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Polypropylene Plant, IOCL

Polypropylene
Producers
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Polypropylene Plant, IOCL

Polypropylene Capacities in India

Company
Reliance, Hazira

Polymer
Homo &
Copolymers

Technology
Unipol, Dow (2 Lines)

Capacity, KT/Year
450

Reliance,
Jamnagar
IPCL, Nagothane
IPCL, Baroda
IPCL, Baroda

Homo PP

Unipol, Dow (6 Lines)

2130

Homo PP & RCP

ICP
Homo &
Copolymer

Spheripol I, Basell
Montell
Adipol, Basell

140
40
100

Spheripol II, Basell

300

Spheripol II, Basell

600

Haldia Petrochem, Homo &

Calcutta
Copolymers
IOCL, Panipat
Homo &
Copolymers

Total PP Capacity in India (incl. IOCL) : 3760 KT

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Polypropylene Plant, IOCL

Polypropylene
Market
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Polypropylene Plant, IOCL

Polypropylene-Domestic Market Outlook

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Polypropylene Plant, IOCL

Annual Per Capita Polymer Consumption

22.6

25

24

20
15
10

5
0
India

China

101

World

Polypropylene Plant, IOCL

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