PP Presentation DEc 2

Polypropylene Plant, IOCLPolypropylene Plant, IOCL

1

Overview on Polypropylene Overview on Polypropylene Production and specificationProduction and specification

Kush Kumar Kush Kumar

RanaRana


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 (-CH3) on same side of polymer chain

Methyl Group (-CH3) Randomly placed

Methyl Group (-CH3) 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)

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

C3-(C3-C3-C2-C3-C3-C3-C2-C3)n-C3

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

+

C3-(C3-C3-C2-C2-C3-C3-C3-C2-C2-C2-C3-C2-C3)n-C3

High StiffnessHigh Service Temp.

High Impact Strength

Good Clarity


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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 strengthHigher level of toughnessLow stiffnessLow tensile strengthMore opaqueLow Hardness

Homopolymer PP Random Copolymer High Impact Copolymer

Properties of Polypropylene


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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 ProcessesSpheripol

- 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 Cool

er

Product Discharge System

Reactor FeedCatalystCocatalyst

Reactor Feed

Homopolymer Random Copolymer

Impact Copolymer

Gas Phase Process – Unipol (Dow) PP


23

Gas Phase Process – Borestar Process


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Gas Phase Process – Innovene PP


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Gas Phase Process – Spherizone Process


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Polypropylene Process


27

Plant design highlightsNo. 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 AreasThe different areas of PP plant area

• PP Line 1

• PP line 2

• Common Area


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The major section of PP line 1 are-

1 1 1100 Catalyst Preparation 1100 Catalyst Preparation

22 1200 Precontacting, Pre-polymerization, Bulk 1200 Precontacting, Pre-polymerization, Bulk

PolymerizationPolymerization

3 1300 Polymer degassing, Propylene recovery3 1300 Polymer degassing, Propylene recovery

4 1500 Polymer steaming, drying4 1500 Polymer steaming, drying

5 1600 Blow down area5 1600 Blow down area

6 1800 Polymer Powder extrusion and Additivation6 1800 Polymer Powder extrusion and Additivation

7 1900 Product Homogenization, storage7 1900 Product Homogenization, storage


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The major section of Common Area are-

1 1100 Donor Metering1 1100 Donor Metering

2 2100 Teal storage & Metering, Atmer metering2 2100 Teal storage & Metering, Atmer metering

3 1600 Common Process Utilities3 1600 Common Process Utilities

4 1700 Monomer Purification4 1700 Monomer Purification


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Po

lym

eriz

atio

n 1

Po

lym

eriz

atio

n 2

Extrusion

Bagging /warehouse

TEAL SYSTEM

Homogenization

Main Substation

Common Area

Mineral Oil storage

Battery Limit


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Loop ReactorsRecovery/Steaming

& Drying

Extrusion Building


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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:

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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• 1st Generation - Crystalline α-TiCl3+AlCl3+AlEt2Cl

• 2nd Generation - Crystalline α-TiCl3+AlCl3+AlEt2Cl

• 3rd Generation - Crystalline α-TiCl4+MgCl2+TEAL+Di(Ethyl Benzoate)+De(MPT)

• 4th Generation - Crystalline α-TiCl4+MgCl2+TEAL+Di (Alkylphalate)+De (Alkoxy Silane)

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

• 6th 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.


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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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Area 1200/2200

Pre-contacting, Pre-polymerization &

Bulk Polymerization


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Preontacting, prepoly & bulk polymerization

Jacket cooling pumps

Precontacting pot

Prepoly reactor

1st loop reactor

2nd loop reactor

Jacket water circulation pump

Propylene

Hydrogen

Donor

TEAL

Catalyst


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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 10°C.

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 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 (20°C), 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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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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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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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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Area 1300/2300

Polymer Degassing & Propylene Recovery


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Polymer slurry from reactor

Flash Drum

Recycle gas filter

LP C3 Scrubber

Recycle gas compressor

Polymer degassing & Propylene Recovery


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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 RecoveryPolymer Degassing and propylene Recovery

The slurry discharged from the second reactor is heated in the flash pipe to The slurry discharged from the second reactor is heated in the flash pipe to

vaporize the un-reacted liquid propylene.vaporize the un-reacted liquid propylene.

The gas and polymer mixture is discharged into flash drum where the operating The gas and polymer mixture is discharged into flash drum where the operating

pressure is 18kg/cmpressure is 18kg/cm22g.g.

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

scrubbed and recycled.scrubbed and recycled.

The polymer from the flash drum bottom can be sent to The polymer from the flash drum bottom can be sent to

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

polymer polymer Production).polymer polymer Production).

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

where copolymer reaction takes place. The Gas phase reactor where copolymer reaction takes place. The Gas phase reactor

discharges to Bag filter.discharges to Bag filter.


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Polymer Degassing and propylene Recovery

In Bag filter, the pressure is further reduced to 0.6 kg/cmIn Bag filter, the pressure is further reduced to 0.6 kg/cm22g thereby g thereby recovering propylene through LP recovery.recovering propylene through LP recovery.

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


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Area 2400

Gas Phase Polymerization &

Ethylene Striper


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Recirculation compressor Gas phase reactor

JW Circulation pump

Hydrogen

Ethylene

Propylene

From Flash drum

To Recycle gas filterFrom recycle C3 Scrubber

GAS PHASE REACTOR


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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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Area 1500/2500 Polymer steaming and drying


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Polymer Steaming Polymer Steaming

In the steamer the polymer is In the steamer the polymer is fluidized with live steam. The fluidized with live steam. The steaming is done to steaming is done to

1.1. Deactivate the residual catalyst Deactivate the residual catalyst activity.activity.

2.2. Deactivate the Residual Teal in Deactivate the Residual Teal in the polymer.the polymer.

3.3. Recover the residual propylene Recover the residual propylene in the polymerin the polymer

Polymer In

LP STEAM

Polymer Out

Steam/ Propylene to steamer scrubber

M


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Polymer DryingPolymer Drying

In the dryer the polymer which is In the dryer the polymer which is moist because of the steaming is moist because of the steaming is dried by fluidizing with hot nitrogen.dried by fluidizing with hot nitrogen.

The Dryer discharges the dry The Dryer discharges the dry polymer to the conveying system polymer to the conveying system for transfer to the intermediate for transfer to the intermediate powder silos.powder silos.

Wet NitrogenWet Polymer

Dried Polymer To conveying

Fluidised Bed of Polymer

Hot Nitrogen

Wet Nitrogen to Scrubber

Polymer Fines to Conveying system


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Area 1700/2700

Raw Materials Purification.


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Propylene Purification

Feed tank PP line 1

Coalescer21V-1701 Feed tank PP line 2

C3 from BL26 kg/cm2(g)35-45 deg C

Moisture

Propylene Drying Unit

21PK 1703Phosphine/

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 Unitand CO2 removal unit

50kg/cm2g 21C 2704A/B 21PK 270230-45 deg C

Ethylene from BL CO & O2 Removal Tower


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2. Ethylene Purification:

Since ethylene pressure is 50 kg/cm2 g, ethylene doesn’t 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.


71

Butene Purification

Coalescer21V-2703

C4 from BL8 kg/cm2(g)35-45 deg C

Moisture PP Line 2

21P 2701Butene Feed Pump

Butene Drying Unit21C-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 filter21PK2705A/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.


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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.


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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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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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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


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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 )



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Polypropylene – Application

8888

Applications - FilmApplications - Film

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

•high strength

•High clarity

8989

Applications – Molding Applications – Molding (Household applications)(Household applications)

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

•high strength

•Good flowability

•Low density

9090

Applications – Molding Applications – Molding (other applications)(other applications)

PP is used in specialized Molding applications because of its

•high strength

•Good Chemical resistance

•Good Flexural Strength

9191

Applications –Molding Applications –Molding (Automotive applications)(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 DurablesPolypropylene is fast replacing Polystyrene and ABS for use in consumer durables sector.

9393

Applications - FibresApplications - 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

9595

Applications - PackagingApplications - Packaging PP is used extensively in the Packaging applications both

Flexible packaging- metallized PP film

Containers- Food Grade

Rigid packaging

9696

Applications – Industrial UseApplications – 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


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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

PP Presentation DEc 2

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