POLY OLEFINS

Feedstock : Naphtha / LNG / C2- C3

to light olefins
to
polymers
1

WHY POLYMERS ?
Polymers ensued a new era to the society.
Polymers are the materials of choice due to their
versatility viz:
Physical and Chemical strengths,
Lightness in weight,
Chemical and Corrosion resistance,
Attractiveness,
Easy processability,
Durability in all whether conditions
and finally Economic viability.
.
2

Global Polymer Demand (2005-2020)

.

2005

2013

2020

Polymer

170

220

270

PE
PP
PVC
PS

60
50
30
10

80
70
30
20

90
80
40
30

MMT

Categarization of polymers
Plastics: Formed by application of pressure and heat.
Possess plasticity, rigidity,
high mechanical strength, abrasive
resistance, dimensional stability ,extensibility.
Elastomers: High polymers with elastic properties, low
modulus and molecular cohesion
Fibres : Knitted or woven into dimensionally stable
garments with high modulus and extensibility
Coatings : polymers having low modulus and adhesion
properties. high chemical inertness and
impermeability towards water, solution and
gases.
4

Plastics: PE, PVC, PS, PP, Polycarbonate,

methyl methacrylate, Urea and Melamine
formaldehyde, Polyurethene, Fluorocarbon.

Poly

Elastomers: SBR, PBR, Neoprene.

Fibers: Nylons, Polyesters, Acrylic, Methacrylic
poly olefins, Fluorocarbons, PP, Vinyls.
Coatings: Epoxies, Silicones, Polyamide

Classification of polymer

Stereo polymers are further sub-devided into Atactic, Isotactic and Syndiotactic polymers
6

Olefins
Olefins serve as basic feed stock for many
chemicals, intermediates etc. which are
used in production of polymers, fibers,
rubbers, pharmaceuticals, dyes,
pesticides etc.
Ethylene and Propylene are the most
important light olefins. These are the
building blocks for the chemical industry.
7

Naphtha Cracker
Naphtha cracker remains the fundamental unit of
the global petrochemical industry producing
olefins namely ethylene, propylene, butadiene
and pyrolysis gasoline.
Various technologies for steam cracking across the
world.
1 M W Kellog
2 Stone& Webster
3 ABB Lummus
4 Technil KTJ
5 Linde AG
8

Naphtha Cracker Unit

Process technology :
Cracker comprises of
pyrolysis section, hot fractionation,
compression, refrigeration, drying,
cold separation
and storage.

Details
Pyrolysis heater : consists of convection zone and
radiation zones where naphtha is pyrolytically
cracked at 820c to give a mixture of olefins..
Hot fractionation : Quenching and heavies separation.
Compression section: cracked gases at 30c are
compressed in a 5 stage centrifugal compressor to a
pressure of 40 kg/cmg.
Drying : the gas is then made free of moisture by
means of molecular sieve

10

Cold separation: The gases are liquefied to

sub zero temperatures -165 c by means of
propylene and ethylene refrigeration systems.
The cold liquid then is separated in various
fractionation columns viz de-methanizer, deethanizer, ethylene fractionator, depropanizer, propylene fractionator and debutanizer.
Storage : ethylene propylene and other
separated liquids are stored
either in refrigerated atmospheric tanks or
Horton spheres under pressure
11

12

Offsite & storage

Storage : ethylene, propylene and other
products are stored either in refrigerated
atmospheric tanks are in Horton spheres
under pressure

13

Purity of c, c & c for polymers

production
Propylene: propylene
99.5 mole%
propane
0.4 mole%
MAPD
5 ppm
Ethylene: ethylene
99.95 mole%
ethane
300 ppm
Butadiene: butadiene 1:3 99.6 %
butadiene 1:2 20 ppm
14

PROPERTIES
Mol. Wt.
Melting Temp.
MFI
Particle size distribution
Glass transition temp
Amorphous density
Crystalline density
Softening point
Izod impact
Tensile strength
15

Polyethylene
Discovered in 1935 by Mr.Gibson
Demand of LLDPE: higher than LDPE & HDPE
LLD : largest grade of commodity polymer in India
LD+HD+LLD prodn in India in MTA
RIL(IPCL) 4,20,000
RIL Hazira 4,00,000
Haldia petrochemicals; 3,20,000
IOC panipat : 3,00,000

16

Catalyst
LDPE is prepared at high pres and high temp
where as LLD. & HD at low pres and low temps.
LD: peroxides
HD: Ziegler Natta organometallic
catalyst (a complex between al alkyl and
transition metal halide such as titanium
tetrachloride)
LD: Copolymer of ethylene with olefins(c-c)

17

Production of LLDPE
There are three major types of LOW PRESSURE processes for
producing LLDPE / HDPE
Slurry, Solution and Gas phase
1.Slurry process: using an inert diluents in which catalyst is affixed to an
inert support. The polymer formed during production remains
suspended in the liquid medium which is later separated.
2. Solution process: both catalyst & polymer remain dissolved in a solvent
which is subsequently separated and recovered
3.Gas phase : monomer, co-monomer, H2, catalyst in pre-polymer form
and inert gas N2 introduced in a fluidized bed type reactor. Gas phase
processes have the widest application in terms of melt flow index and
densities.

18

Limitations of various processes

Slurry:
Limited to densities > 0.937gm/ cm3and MI up to 10.
Bimodal slurry processes have grown due to great demand
for pipe and film production.

Solution:
Wider window in terms of densities and MI
Best suited for higher value added products with Octane-1

Gas phase:
Widest operating window for densities and MI. But
encounters difficulties in resins with very low densities due to
stickiness and agglomerate formation
19

Slurry type
(a) Chevron Phillips
15%
hexene, ethylene and supported catalyst are
introduced in the reactor & isobutene as diluent.
press 37 kg/cmg, temp 100 c
(b) Solvay loop reactor

2%

press 30 kg/cmg, temp 80 c

20

Phillips slurry loop process

21

Solution type
:

(a) SABIC-Compact
hexane as diluent, Ziegler catalyst, ethylene, H2, butene-1
as co-monomer, press 2- 5 kg/cmg, temp 150-200 c
MI range 0.1 -100,density 0.9- 0.967,
(b) BASELL Hostalene
3%
hexane as diluent, H2, monomer, comonomer and catalyst
press 7-10 kg/cmg , temp 75-85 c
(c) Dow
7%
ethylene, octane-1, catalyst
press 27 kg/cmg temp 160 c
(d) Mitsui
9%
uses hexane as diluent, comonomer butane-1
press 7-8 kg/cmg, temp 85 c
(e) Dupont (now with Scaliartech) [NOVA] 5%
cyclohexane. reaction time 2 mts
22

23

24

Gas phase process

1. Union Carbide UNIPOL
29 %
2. BP Amaco (Innovene)
10 %
3. Basell (Technimont) spherilene
2%
Low capital & operating costs. Grade change over with minimum off grade
production.
Wide range of MI . Significant reduction in reactor purges.
Easy reactor operation, grade changes on mathematical
model and Interchangeability of production lines of LLDPE/ HDPE
Low inventory in the process. Low pressure & low temperature process
than conventional high pressure .

25

Gas phase fluidized bed

reactor
The reactor is a vertical type one. operating
pressure 20 kg/cmg and 70c. N, ethylene,
butene and H are circulated in loop using a
cycle gas compressor. Catalyst is made in-situ
and grown to a bigger particle size by ethylene
in a pre-poly reactor separately to reduce the
activity of Ti, improve particle-size distribution
and introduced into the reactor. Polymer powder
is continuously withdrawn from the reactor and
separated in a degasser. The gas is recycled
back to reactor and polymer extruded out in
pellet form for storage into silos
26

LLDPE Reactor
Fluidised bed

27

Development in catalyst for

ldpe/hdpe/lldpe
1.oxygen & peroxide
2 chromium
3. ziegler
4.supported catalyst for gas phase
5.metallocene
6.transition metal single site

28

Extrusion/
blending& transportation
- powder silos
- extrusion
- sieving
- transportation
- storage and blending
- off grade silos & recycling
- packing
29

colouring & compounding

- master batch preparation
- extrusion to colour pelleting
- packaging

30

Safety criteria in design

-site & layout :- fire protection: -OSBL , -ISBL,
-building & structures
-process equipment and piping
flare system
drainage
emergency shut down systems
misc: safety showers, hot surfaces, noise
levels ,escape provision
31

-Polymerisation: fire hydrant, sprinkler, flare,

s/v, rov, co system, TEAL area,
Plant emergency shut down system: cw ,power
I.air, steam failure, external fire,
-sensors and alarms.
Pelletising section: dust explosion relief,
-Bagging area: fork lifts, trucks movement
-Monomer storage area: drainage, dykes, ROV,
-Chemical storage and handling area
32

LLDPE / HDPE share

by capacity & process

33

Capabilities of different processes

per Density & Melt Index

34

Additives used in polymers

Broad classification:
(1) processing:
stabilizers, slip agents, lubricants,
accelerators, nucleating agents, impact
modifiers, heat stabilizers.
(2) functional:
fillers, colorants, flame retardants, antistatic
agents, antioxidants, antimicrobials.
Market is dominated by plasticizers and flame
retardants
35

Additive- commercial name

Manufacturing stage (u/s & d/s of extrusion)
1. Anti oxidants- Irgonox
2. Lubricants: - Calcium stearate,
zinc stearate
3.UV stabilizers
4. Antiblock agents: (silicons) - Gasil
5. Slip agents: (olemides) - Erucylamide
6. To prevent discoloration( thioesters) - DSTDP
36

Polymer properties / Applications

Injection moulding:
Mw/Mn <5
Toughness
:
lower MI
Stress cracking resistance: lower density
Easy processability :
higher MFI
Roto moulding:
narrow mol.wt distibution
High impact strength
-doLow warpage
-doLow shrinkage
-do-

37

Plastics & uses

PE

LDPE

Free radical initiate

HDPE

Ziegler natta

LLDPE

Ziegler natta

HMWHDPE
PP

Homo
Random

PVC

film sheet, house ware, pipe,

toys, containers

Ziegler natta
Ziegler natta
Fibre products, automobile
parts, tyres, appliance parts,
Ziegler natta
toys house ware
Free radical initiation
wires cables, insulation, ,sheets
adhesives, automobile parts,
coatings, pipe fittings
Free radical
emulsion, paints, adhesives

PVA
PS

film sheet, house ware, pipe, toys

GP
HI
Expanded

Free radical

packing, disposable containers,

appliance parts
packing
38

plastics & uses- contd

Poly isobutylene

cationic chain

lubricating oils,

poly acrylonitrile (AF)

free radical

fibres in apperal, house ware

Polyamide (Nylon 6)

bulk

Poly urethene

poly conden

oriented fibre, heavy cast parts,

fabrics ,fishing line, furniture
rubber, foam, coatings

ABS

free radical

Styrene acrylonitrile (SAN )

free radical

automobile aplliances, camera

bodies, telephone parts
electric equipment, house ware

PMM

free radical

fixtures, aircraft windshield, cock pit

cover , lenses

poly carbonate

poly conden
trans esterifi
step conden

aircraft parts, CD, helmets, beverage

dispencers
dinnerware, table top

poly conden

particle wood binder, paper, textile

Melamine formaldehyde
urea formaldehyde

39

Many other polymers viz. epoxy resins, PBR, SBR, PET,

polyester, PTFE, acrylic fibres, fluoro plastics etc. are yet
to be covered

There is no failure except in no longer trying

Thank you
40