Overview On Polypropylene Production and Specification: Kush Kumar Rana

Polypropylene Plant, IOCL
1
Overview on Polypropylene
Production and specification

Kush Kumar Rana

2
Content
Polypropylene fundamentals
Polypropylene properties
Polypropylene technologies
Polypropylene process
Additives used in Polypropylene
Polypropylene application
Polypropylene producers
Polypropylene market
3
Polypropylene
fundamentals
Polymer - ?
5
What is PP ?
6
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.
7

Atactic
Syndiotactic
Isotactic
Methyl Group (-CH
3
) on same side of polymer chain
Methyl Group (-CH
3
) Randomly placed
Methyl Group (-CH
3
) on alternate side of polymer chain
Tacticity
8
Polypropylene
Properties
9
Characteristics of PP
10
Types of Polypropylene
PP
PP
Homopolymer
(PPHP)
PP Random
Copolymer
(PPRCP)
PP Impact
Copolymer
(PPICP)
C
3
-(C
3
-C
3
-C
3
)
n
-C
3
C
3
-(C
3
-C
3
-C
2
-C
3
-C
3
-C
3
-C
2
-C
3
)
n
-
C
3

C
3
-(C
3
-C
3
-C
3
)
n
-C
3

+
C
3
-(C
3
-C
3
-C
2
-C
2
-C
3
-C
3
-C
3
-C
2
-C
2
-C
2
-C
3
-C
2
-C
3
)
n
-C
3

High Stiffness
High Service Temp.
High Impact Strength
Good Clarity
11
High stiffness
High crystallinity
High melting point
Low impact strength

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
Homopolymer PP Random Copolymer High Impact Copolymer
Properties of Polypropylene
12
Optical properties RCP > HP >> ICP
Melting point HP > ICP >> RCP
Impact strength ICP > RCP > HP
Modulus HP > RCP > ICP

Comparative Properties of PP
13
Average Molecular Weight
Molecular Weight Distribution
Crystallinity
Processing Conditions
Additive Recipe used

Property Controlling Parameters
Molecular Weight

Molecular Weight Distribution
Crystallinilty
18
Polypropylene
Technologies
19
- Bulk Processes
Spheripol

- Gas Phase Fluidized Bed Processes

Unipol
Novolen
Spherizone
Innovene
PP Polymerization Processes
20
21
Gas Phase Process Novolen PP
22
Reactor
1
Reactor 2
Product
Discharge
System
Compressor Compressor
Cooler
Cooler
Product
Discharge
System
Reactor Feed
Catalyst
Cocatalyst
Reactor Feed
Homopolymer Random
Copolymer
Impact Copolymer
Gas Phase Process Unipol (Dow) PP
23
Gas Phase Process Borestar Process
24
Gas Phase Process Innovene PP
25
Gas Phase Process Spherizone Process
26
Polypropylene
Process
27
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.

28
Plant Areas
The different areas of PP plant area
PP Line 1
PP line 2
Common Area
29
The major section of PP line 1 are-
1 1100 Catalyst Preparation
2 1200 Precontacting, Pre-polymerization, Bulk Polymerization
3 1300 Polymer degassing, Propylene recovery
4 1500 Polymer steaming, drying
5 1600 Blow down area
6 1800 Polymer Powder extrusion and Additivation
7 1900 Product Homogenization, storage
30
The major section of Common Area are-
1 1100 Donor Metering
2 2100 Teal storage & Metering, Atmer metering
3 1600 Common Process Utilities
4 1700 Monomer Purification

31

Extrusion
Bagging /warehouse
TEAL SYSTEM
Homogenization
Main Substation
Common Area
Mineral Oil
storage
Battery
Limit
32

Loop Reactors
Recovery/Steaming
& Drying
Extrusion Building
33
Area 1100/2100

Catalyst, Co-catalyst & Donor

storage and metering
34

The catalyst system consists of three components:

i. Ziegler Natta catalyst- Titanium catalyst
supported on MgCl2 (solid)
ii. Triethyl aluminum (TEAL) (liquid)
iii. External Donor (liquid)

35
Catalyst:

Ticl
4
catalyst supported on MgCl
2
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.

36
1
st
Generation - Crystalline -TiCl
3
+AlCl
3
+AlEt
2
Cl
2
nd
3
+AlCl
3
+AlEt
2
Cl
3
rd
4
+MgCl
2
+TEAL+Di(Ethyl Benzoate)+De(MPT)
4
th
4
+MgCl2+TEAL+Di (Alkylphalate)+De (Alkoxy
Silane)
5
th
Generation - Crystalline -TiCl4+MgCl2+TEAL+Di (1,3-diether)
6
th
Generation - Metallocene of Zr or Hf + Methylaluminoxane (MAO)

Catalyst Generation for PP
37
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.

38
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.

39
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.
44
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.

45
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.
46
Area 1200/2200

Pre-contacting, Pre-polymerization
&
Bulk Polymerization
47
Preontacting, prepoly & bulk polymerization
Jacket cooling pumps
Precontacting
pot
Prepoly reactor
1
st
loop reactor
2
nd
loop
reactor
Jacket water circulation pump
Propylene
Hydrogen
Donor
TEAL
Catalyst
48

49
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.
50

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 m
3

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..
51
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

52
53

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.
54

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.
55
Area 1300/2300

Polymer Degassing & Propylene
Recovery

56
Polymer slurry
from reactor
Flash Drum
Recycle gas filter
LP C3 Scrubber
Recycle gas
compressor
Polymer degassing & Propylene Recovery
57
Recycle C3 Scrubber
C3 Feed tank
From flash drum
From recycle gas compressor
To steamer scrubber
Polymer degassing & Propylene Recovery
58
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/cm
2
g.
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.
59
Polymer Degassing and propylene Recovery
In Bag filter, the pressure is further reduced to 0.6 kg/cm
2
g thereby
recovering propylene through LP recovery.
Propylene recovered in LP recovery is scrubbed with oil-atmer mixture,
compressed and sent to HP recovery.
60
Area 2400

Gas Phase Polymerization
&
Ethylene Striper
61
Recirculation compressor
Gas phase reactor
JW Circulation pump
Hydrogen
Ethylene
Propylene
From Flash drum
To Recycle gas filter
From recycle C3 Scrubber
GAS PHASE REACTOR
62
POLYMERIZATION - GAS PHASE CO

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.

63
Area 1500/2500
Polymer steaming and drying

64
Polymer Steaming
In the steamer the polymer is
fluidized with live steam. The
steaming is done to
1. Deactivate the residual catalyst
activity.
2. Deactivate the Residual Teal in
the polymer.
3. Recover the residual propylene
in the polymer
Polymer In
LP STEAM
Polymer Out
Steam/ Propylene to
steamer scrubber
M
65
Polymer Drying

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
Dried Polymer To conveying
Fluidised Bed of
Polymer
Hot Nitrogen
Wet Nitrogen to
Scrubber
Polymer Fines to
Conveying system
66
Area 1700/2700

Raw Materials Purification.

67
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
Propylene Drying Unit
21PK 1703
Phosphine/
Sulphur/ Arsine
Removal Column
21C-1702
Light End Stripper
21C-1701
68
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.

69
Ethylene Purification
PP line 1
PP line 2
Ethylene Drying Unit and CO
2
removal unit
50kg/cm2g 21C 2704A/B 21PK 2702
30-45 deg C
Ethylene
from BL
CO & O2 Removal Tower
70
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 O
2
removal towers.

After CO removal, ethylene is sent to drying and CO2 removal unit.
71
Butene Purification
Coalescer
21V-2703
C4 from BL
8 kg/cm2(g)
35-45 deg C
Moisture PP Line 2
21P 2701
Butene Feed Pump
Butene Drying Unit
21C-2731 21PK 2731
Light End Stripper
21V
2710
Butene
Feed
Tank
72
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.

73
Hydrogen Purification and compression
Line 1
17 kg/cm2g
hydrogen filter
21PK2705A/B Line 2
Hydrogen From BL
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.
74
Area 1800/2800

Extrusion and Additivation.

75
Extruder:
Powder feed
Extruder
PP Pellets
Pellet water system
76
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.
77
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.
78
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.

79
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.

80

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
81

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
82
Polypropylene
Additives used
83
Additives used for PP
84
Additives
Modifier Processing Aids Property Extender
Primary Antioxidant (Increases service life) eg 1010
Secondary Antioxidant (Encounter Thermal Degradation) eg
PEPQ / 168
Thermal Stabilizer (Enhance Thermal Stability)
eg DSTDP
UV Stabilizer (Encounter UV Degradation )
85
86
87
Polypropylene
Application
88
Applications - Film
PP is used extensively in the Film applications primarily because of its
high strength
High clarity
89
Applications Molding (Household applications)
PP is used extensively in the Molding applications primarily because of its
high strength
Good flowability
Low density
90
Applications Molding (other applications)
PP is used in specialized Molding applications because of its
high strength
Good Chemical resistance
Good Flexural Strength
91
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
92
Applications Consumer Durables
Polypropylene is fast replacing Polystyrene and ABS for use in consumer
durables sector.
93
Applications - Fibres
PP is used extensively in the Fibre applications primarily because PP fibres are
Light weight
Rot Proof
Resistant to Fading
94
Applications Fabrics
PP is used in both woven and non woven fabric applications
95
Applications - Packaging
PP is used extensively in the Packaging applications both
Flexible packaging- metallized PP film
Containers- Food Grade
Rigid packaging
96
Applications Industrial Use
PP is used extensively in the industrial applications because of
high strength
High chemical resistance
97
Polypropylene
Producers
98
Company Polymer Technology Capacity, KT/Year
Reliance, Hazira Homo &
Copolymers
Unipol, Dow (2 Lines) 450
Reliance,
Jamnagar
Homo PP Unipol, Dow (6 Lines) 2130
IPCL, Nagothane Homo PP & RCP Spheripol I, Basell 140
IPCL, Baroda ICP Montell 40
IPCL, Baroda Homo &
Copolymer
Adipol, Basell 100
Haldia Petrochem,
Calcutta
Homo &
Copolymers
Spheripol II, Basell 300
IOCL, Panipat Homo &
Copolymers
Spheripol II, Basell 600

Total PP Capacity in India (incl. IOCL) : 3760 KT
Polypropylene Capacities in India
99
Polypropylene
Market
100
Polypropylene-Domestic Market Outlook
101
5
22.6 24
0
5
10
15
20
25
India China World
Annual Per Capita Polymer Consumption
102

Overview On Polypropylene Production and Specification: Kush Kumar Rana

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