From ethylene to plastics & other usages

The 10 plastic products most used in the world:

Polyethylene : PE
Polypropylene: PP
Polystyrene: PS
Polyurethane
PVC
Polyester
Nylon
Kevlar

ALL FROM AN
ETHYLENE
UNIT !!!

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Perspex
Teflon

From ethylene to plastics & other usages

The mostly used chemical reactions from ethylene:

Polymerisation = polymers
Oxydation = polyesters, urethane, glycols, acetate,...
Halogenation: PVC
Alkylation: Styrene
Hydration: proteins, ethanol...
Oligomerisation: plasticizer

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Oxo-reaction: herbicides
Pure: ripening agent

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Polimeri Europa
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Ethylene derivatives

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Molecule of polyethylene

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Types of Polyethylene

HDPE
High density
polyethylene
Density 935-965 mg/cm3

LLDPE
Linear low density
polyethylene
Density 915-930 mg/cm3

LDPE
Low density
polyethylene
Density 910-925
mg/cm3

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Ethylene: how is it made?

In cracking furnaces, getting larger & larger:

180,000 t/y per furnace,
by heating, and cracking, very quickly (0.1 second), at high temp. (800 to

850 C), 'hydrocarbons', i.e compounds containing carbon and hydrogen,

In presence of steam, inert, which 'controls' the cracking reactions, hence

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the word 'steam-cracking'

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Cracking furnace

Convection Section

Hydrocarbon
Feed

120 oC

~
Steam Drum
~

Boiler Feed Water

Dilution Steam

380 oC

Cracked Gas to
Separation Section

Desuperheater
BFW

520 oC
HP Steam

620 oC

1250 oC

Transferline Exchanger

850 oC
Radiant efficiency: 40 42%
Overall efficiency: 92 95 %

Radiant Section

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Ethylene : how is it made?

Then, its only separation of the by-products, also produced during the

cracking reactions in the furnaces: hydrogen, methane, propylene,

butadiene, fuel-oil, etc
By means of compression, cooling/refrigeration, distillation, in order to

isolate each component

Problems: coke deposits (soot/carbon layers) in the heaters: cyclic shut-

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down (2/3 days every other 30/50 days)

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Olefins complex: a steam-cracking unit

Hydrogen
Utilities

Mixed
Butanes
Gasoline

Material Movements
Acid Gas
Compressor and
Drier Chilling

Steam
Primary
Fractionator
Quench

Feeds

Propylene
NAPD
Propane
Converter
Ethylene

Mixed
Products

Acetylene
Converter

Ethane

Ethane

Methane

Quench

Fuel Oil
Cracking
Furnaces

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Naphtha

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Iran 10th: ethylene fract., diam. 6 m, 800T

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KEY EQUIPMENT IN ETHYLENE CRACKER PLANT (FURNACES)

Additional one furnace-In Y-2008 (8)
KBR-Furnace-USA)
Increase capacity (From 520 to 600 KTA)

Additional another one furnace (9)

LUMMUS (end-2015)
Increase capacity
(From 600 to 860 KTA)
Original
7- LUMMUS Furnaces-USA (520 KTA)

2 TRAINS - POLYETHYLENE PLANT

1. PE-Unipol Union Carbide
Process (USA)
2. PE-Showadenko Process (Japan)

PE Unipol-USA
Gas phase
fluidized bed process
PE Showadenko-Japan
Slurry process

PE WAREHOUSE
50,000 T (55,300 M2)
[10 Times Soccer Field]

Overview Picture PP plants

Three trains Polypropylene plant (Unipol process (USA) with total
combined capacity of 480 KTA
PP-T1
PP-WAREHOUSE
15,000 Tons (15,600 M2)

PP-T2

PP-T3

Train-3 Polypropylene plant

Two reactors in series capable
To produce Impact/Block Polypropylene

Product purge Bin

Reactor-2
Reactor-1

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P.T. Chandra
Asri

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Nomenclature & Product Range

S F 50 08 E
U : Unipol

S: SHOWA DENKO
INDICATOR: REACTOR TYPE

FILM

D = 0.950

APPLICATION

MI (190, 2.16) = 0.05

DENSITY

Linier Low Density Polyethylene

Film
UF1810 Barefoot
UF1810T Slip/AB
UF1810S1 High Slip/AB
UF1820S1 MI (190, 2.16) = 2
Injection Molding
UI2420 High Impact & Stiffness
UI2650 High Flow & Better
ESCR

MELT INDEX

ENVIRONMENTALLY
DEGRADABLE

SPECIAL CHARACTERISTIC

High Density Polyethylene

Film
SF5007 General Film
SF5008E Degradable Film
Tape/Monofilament
SM5508
Injection Molding
SI5230 High Flow
SI6008 High Impact
Blow Molding
UB5206H High Stiffness
(<100L)
UB4806H High ESCR (<60L)
Pipe

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A little bit of chemistry !

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Chemistry
Steam cracking = cracking of hydrocarbon molecules
having, at least, 2 atomes of carbon :

C C
C C C

Ethane (USA, Middle East)

Propane, LPG

C.. C

Naphtha (CEE, Japan, Far East)

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Gasoil, HVGO (Shell)

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Chemistry
heat

Simple :

C C

C C + H2

(C2H6
800 C
Ethane) 0.1 second

In fact :

C2H6
C2H6 + CH3
C2H5

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C2H6 + H

CH3 + CH3
CH4 + C2H5
C2H4 + H
C2H4 + H2 etc etc

Free radical, fugitive, non isolable

Steam : inert

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Chemistry

but :

CH4 + H2O

CO + 3H2

CO + H2O

CO2 + H2

CH3 , C2H5

+ H2

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Coke !

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Feedstock selection and ethylene yields

Ethane

C3-LPG

C4-LPG

Naphtha

Gasoil

Feed

125

226

300

334

433

Ethylene

100

100

100

100

100

Propylene

35

45

52

60

Butadiene

14

18

Raffinate-1

17

21

Benzene

22

18

Other (fuel)

24

73

141

129

216

(Feed and Products in tons per 100 ton of ethylene product)

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A process of extremes !
very hot
very cold
high pressures
low pressures
powerful

1150 C on the heater tubes

Oh no!!
- 160 C in the separation section
steam at 120 b
vacuum in condensers
200 MW installed power

large
300 this
x 400
m plot, i.e four giant stadiums...
Four time
stadium
gigantic ~ 175 000 kg/h ethylene
even bigger Vessels as large as a 38 m2 appartment
sophisticated product purity over 99.95 % wt.

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Potentially hazardous H2S, NOx, CO, H2, Methane

yet very safe very few accidents

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A process of extremes !
Very clean CO2 , waste waters, coke, noise
Costly noble metallurgies, complex
machinery, lenghty construction,
sophisticated instrum/controls
But very reliable 8 000 h/y, 6/7 y of operations
without major shutdown
Ethylene is now :

Necessary,

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unavoidable,

basis for the

whole petrochemical
industry
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How greener these days ?

Reference Plant (80s):
600 kt/y

Mega-Cracker (2006):
1000 + kt/y

Energy input

8000 kWh per ton of ethylene

5300 kWh per ton of ethylene

Product losses

Less than 1%

Less than 0.25%

CO2 emissions
NOx emissions

1550 kg per ton of ethylene

180/200 mg/Nm3 effluent

790 kg per ton of ethylene

Less than 120 mg/Nm3 effluent

Operators

7 per shift

7 per shift

Noise

~92 dBA (compressors)

~85-87 dBA (compressors)

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Key items:

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From Ethylene to greener plastics :

sustainable development
CRUDE OIL:
70% : diesel & heating oil
20% : naphtha, i.e. 13% gasoline & 7% chemical raw products, of which
4% plastics, 3% other chemicals
10% others

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200 kg OF PLASTICS IN A CAR: (average today: ~ 140 kg/car)

Save 2 to 3 times more steel
Will save more than 20 millions tons of crude oil per year for W. Europe
Will reduce the CO2 emissions by 100 million tons/year in W. Europe
PACKAGING:
Recycled plastics now supply up to 70 % of collective urban heating in
Gteborg, Sweden, & already close to 45 % in Paris
Domestic waste plastics make up only 9 % by weight, but over 30 % of the
energy generated by waste incinerators
Ensures hygiene, safety, taste & odour protection, lightness for food
distribution & storage
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From ethylene to greener plastics

A greener chemistry

MEDICAL:
Over 75% of all medicines are protected/delivered by plastics
Synthetic arteries, prosthesis, and contact lenses
Biologic drug delivery systems: intravenous blood bags
OTHER:
Mobile phones, anti bacterial & time/temp. indicator packages, diapers
Firemen protection: helmets & suits!!
Insulation for buildings and humans (polar garments)
Toys, sporting & outdoor goods,
Electronics & electrical parts
1 paper bag generates 70 % more air & 50 times more water pollutants, as it
takes 4 times as much energy to generate, & 85 times to recycle it (EPA)
150 000 paper bags: 60 m3; 150 000 plastic bags: 1.5 m3(carrying cost)

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Plastic bags: an endangered species ??

(From ICIS , P. Jones)

~7 000 billions plastic bags made in the world in 2004

(i.e. ~ 2 % of all plastics )
Plastic bags first appeared, in the USA, back in the late 1950s
Plastic bags are being taken hostage for the general attitude of our
throw-away society
The key is getting people to reduce, re-use, recycle & recover

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France used 85 000 tons of (low-density) plastic bags in 2003, down

to 45 000 tons in 2005
Plastic bags are now a valuable resource to be reused & recycled
over & over again Plastic recycling becomes a job-creating business
with a 15% growth per year, now, in the USA
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Ethylene is also intrinsically green

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Other major producers :

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The effects from ethylene

In conclusion
The chemical industry has a bad image in the media & in the public

(the worst one after nuclear and waste treatment !)

But it generates + than 3000 billions $ business per year worldwide
It is vital for the world health, safety, environment (recycling!), sustainable

development, despite its visible nuisances, sometimes

And yet, it remains, specifically with the ethylene business, a most

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attractive field of activity

Here it is why:

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