IOCL's Polypropylene Plant Overview and Production Process

Polypropylene Plant, IOCL
Overview on Polypropylene
Production and specification
Kush Kumar Rana
Content
Polypropylene fundamentals
Polypropylene properties
Polypropylene technologies
Polypropylene process
Additives used in Polypropylene
Polypropylene application
Polypropylene producers
Polypropylene market
2
Polypropylene
fundamentals
3
Polymer - ?
What is PP ?
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.
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
Properties
8

Characteristics of PP
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
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
11
Comparative Properties of PP
Optical properties
RCP > HP >> ICP
Melting point
HP
Impact strength
ICP > RCP > HP
Modulus
HP
12
> ICP >> RCP
> RCP > ICP
Property Controlling Parameters
Average Molecular Weight

Molecular Weight Distribution
Crystallinity
Processing Conditions
Additive Recipe used
13
Molecular Weight
Molecular Weight Distribution
Crystallinilty
Polypropylene
Technologies
18
PP Polymerization Processes
- Bulk Processes
Spheripol
- Gas Phase Fluidized Bed Processes

Unipol
Novolen
Spherizone
Innovene
19
20
Gas Phase Process Novolen PP
21
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
22
Gas Phase Process Borestar Process
23
Gas Phase Process Innovene PP
24
Gas Phase Process Spherizone Process
25
Polypropylene
Process
26
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.
27
Plant Areas
The different areas of PP plant area
PP Line 1
PP line 2
Common Area
28
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
29
The major section of Common Area are1
1100
Donor Metering
2100
Teal storage & Metering, Atmer metering
1600
Common Process Utilities
1700
Monomer Purification
30
Bagging /warehouse
Homogenization
Extrusion
Common Area
Battery
Limit
Main Substation
31
Mineral Oil
storage
TEAL SYSTEM
Extrusion Building
Loop Reactors
Recovery/Steaming
& Drying
32
Area 1100/2100
Catalyst, Co-catalyst & Donor
storage and metering
33
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)
34
catalyst
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.
35
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)
36
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.
37
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.
38
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.
39
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.
44
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.
45
Area 1200/2200
Pre-contacting, Pre-polymerization
&
Bulk Polymerization
46

Preontacting, prepoly & bulk polymerization
Prepoly reactor
Catalyst
TEAL
1st loop reactor
Donor
Precontacting
pot
Propylene
Hydrogen
Jacket cooling pumps
Jacket water circulation pump

47
2nd loop
reactor
48
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.
49
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..
50
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
51
52
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.
53
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.
54
Area 1300/2300
Polymer Degassing & Propylene
Recovery
55

Polymer degassing & Propylene Recovery
LP C3 Scrubber
Flash Drum
Polymer slurry
from reactor
Recycle gas
compressor
Recycle gas filter
56

Polymer degassing & Propylene Recovery
From recycle gas compressor
From flash drum
Recycle C3 Scrubber
To steamer scrubber
C3 Feed tank
57

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.
58
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.
59
Area 2400
Gas Phase Polymerization
&
Ethylene Striper
60

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

61

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.
62
Area 1500/2500
Polymer steaming and drying
63

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
64

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
65
Area 1700/2700
Raw Materials Purification.
66

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
67
Propylene Drying Unit

21PK 1703
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.
68

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
69
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.
70

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
71
21P 2701
Butene Feed Pump
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.
72

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.
73
Area 1800/2800
Extrusion and Additivation.
74
Extruder:
Pellet water system

Powder feed
Extruder
PP Pellets
75
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.
76
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.
77
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.
78
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.
79
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
80
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
81
Polypropylene
Additives used
82

Additives used for PP
83
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 )
84
eg

85

86
Polypropylene
Application
87
Applications - Film
PP is used extensively in the Film applications primarily because of its
high strength
High clarity
88
Applications Molding (Household applications)

PP is used extensively in the Molding applications primarily because of its
high strength
Good flowability
Low density
89
Applications Molding (other applications)

PP is used in specialized Molding applications because of its
high strength
Good Chemical resistance
Good Flexural Strength
90
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
91
Applications Consumer Durables

Polypropylene is fast replacing Polystyrene and ABS for use in consumer
durables sector.
92
Applications - Fibres
PP is used extensively in the Fibre applications primarily because PP fibres are
Light weight
Rot Proof
Resistant to Fading
93
Applications Fabrics
PP is used in both woven and non woven fabric applications
94
Applications - Packaging
PP is used extensively in the Packaging applications both
Flexible packaging- metallized PP film
Containers- Food Grade
Rigid packaging
95
Applications Industrial Use

PP is used extensively in the industrial applications because of
high strength
High chemical resistance
96
Polypropylene
Producers
97
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
98
Polypropylene
Market
99
Polypropylene-Domestic Market Outlook
100
Annual Per Capita Polymer Consumption
22.6
25
24
20
15
10
5
0
India
China
101
World
102

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Polypropylene Plant, IOCL

Kush Kumar Rana

Polypropylene Plant, IOCL

Polypropylene Plant, IOCL

Polypropylene Plant, IOCL

Polypropylene Plant, IOCL

Polypropylene Plant, IOCL

Karl Zieglar got Noble Prize for discovery of Ti based

Polypropylene Plant, IOCL

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

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

Methyl Group (-CH3) Randomly placed

Polypropylene Plant, IOCL

Polypropylene Plant, IOCL

Polypropylene Plant, IOCL

High Impact Strength

Polypropylene Plant, IOCL

High Impact Copolymer

High impact strength

Polypropylene Plant, IOCL

RCP > HP >> ICP

ICP > RCP > HP

> ICP >> RCP

> RCP > ICP

Polypropylene Plant, IOCL

Property Controlling Parameters

Average Molecular Weight

Polypropylene Plant, IOCL

Polypropylene Plant, IOCL

Polypropylene Plant, IOCL

Molecular Weight Distribution

Polypropylene Plant, IOCL

Polypropylene Plant, IOCL

Polypropylene Plant, IOCL

- Gas Phase Fluidized Bed Processes

Polypropylene Plant, IOCL

Polypropylene Plant, IOCL

Gas Phase Process Novolen PP

Polypropylene Plant, IOCL

Gas Phase Process Unipol (Dow) PP

Polypropylene Plant, IOCL

Gas Phase Process Borestar Process

Polypropylene Plant, IOCL

Gas Phase Process Innovene PP

Polypropylene Plant, IOCL

Gas Phase Process Spherizone Process

Polypropylene Plant, IOCL

Polypropylene Plant, IOCL

Plant design highlights

Polypropylene Plant, IOCL

Polypropylene Plant, IOCL

The major section of PP line 1 are1

Precontacting, Pre-polymerization, Bulk Polymerization

Polymer degassing, Propylene recovery

Polymer steaming, drying

Blow down area

Polymer Powder extrusion and Additivation

Product Homogenization, storage

Polypropylene Plant, IOCL

The major section of Common Area are1

Teal storage & Metering, Atmer metering

Common Process Utilities