pp presentation dec 2
TRANSCRIPT
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Overview on Polypropylene Overview on Polypropylene Production and specificationProduction and specification
Kush Kumar Kush Kumar
RanaRana
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Content
• Polypropylene fundamentals
• Polypropylene properties
• Polypropylene technologies
• Polypropylene process
• Additives used in Polypropylene
• Polypropylene application
• Polypropylene producers
• Polypropylene market
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Polypropylene fundamentals
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Polymer - ?
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What is PP ?
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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.
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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
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Polypropylene Properties
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Characteristics of PP
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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
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• Average Molecular Weight
• Molecular Weight Distribution
• Crystallinity
• Processing Conditions
• Additive Recipe used
Property Controlling Parameters
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Molecular Weight
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Molecular Weight Distribution
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Crystallinilty
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Polypropylene Technologies
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-Bulk ProcessesSpheripol
- Gas Phase Fluidized Bed Processes
Unipol Novolen
Spherizone Innovene
PP Polymerization Processes
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Gas Phase Process – Novolen PP
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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
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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
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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.
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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
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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)
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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
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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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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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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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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.
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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
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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
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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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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.
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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
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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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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.
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Extruder:
Powder feed
Extruder
PP Pellets
Pellet water system
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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.
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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
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Polypropylene – Additives used
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Additives used for PP
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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 )
Additives used for PP
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Additives used for PP
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Additives used for PP
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Polypropylene – Application
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Applications - FilmApplications - Film
PP is used extensively in the Film applications primarily because of its
•high strength
•High clarity
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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
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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
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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
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Applications – Consumer DurablesPolypropylene is fast replacing Polystyrene and ABS for use in consumer durables sector.
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Applications - FibresApplications - 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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Applications – Fabrics PP is used in both woven and non woven fabric applications
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Applications - PackagingApplications - 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 UseApplications – Industrial Use
PP is used extensively in the industrial applications because of
•high strength
•High chemical resistance
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Polypropylene Producers
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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
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Polypropylene-Domestic Market Outlook
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5
22.6 24
0
5
10
15
20
25
India China World
Annual Per Capita Polymer Consumption
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