A Greener chemistry
120 Millions tons of
Ethylene per year
Why, what for, & how
“greener” ?
Michel H. BUFFENOIR
Senior V.P, Technip Ethylene Business Unit
Lille, 2-5 October 2007
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A greener chemistry
A greener chemistry
Ethylene,
What is it, actually?
It’s : C2H4 !!
2 carbons, 4 hydrogens
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Ethylene, what is it??
 Business of
8 to 10 Billion
€/year…
 World
130 Million
t/y
(2006)
Capacity
 Basic chemical for
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1 billion derivatives
 Club of “five”
TECHNIP
Lummus
S&W
KBR
Linde
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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
!!!
 Perspex
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 Teflon
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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
Ethyl Benzene
7%
Oxide/Glycols
13%
EDC/VCM
14%
LLDPE/LDPE
34%
Polyethylene
58%
HDPE
24%
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Other
8%
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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: again, what is it ???
 It is a gazeous hormone produced by fruits and vegetables…
(since 1991), from methionine decomposition…
 It is a gas discovered in 1777, in Amsterdam, by heating sulfuric acid
and wine alcool…:
first name = “oily hydrogenated carbonated gas”,
or: « liquor of the Dutchmen »!
 It is the basis for the whole modern petrochemistry:
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Union-Carbide, Standard Oil NJ, IG Farben et ICI (polymers) have
initiated it in the 1920/30
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World production (2003)
Region
Million
t/y
USA / Canada
35
Asia/Pacific
29
EEC
24
Mid.East / Africa
12
Eastern Europe / CIS
7
S.America
4
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TOTAL world
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The world top producers
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Million t/y
2003
2006
Dow (USA)
13.1
11.8
Exxon/Mobil (USA)
11.4
11.7
Shell (USA/Holland)
6.7
7.0
Equistar/Lyondell (USA)
5.2
5.2
Sabic (S.Arabia)
5.0
6.7
BP/Amoco (UK/USA)
4.6
4.8
Chevron-Phillips (USA)
3.5
3.6
Sinopec (China)
3.0
5.2
Nova (Canada), Total Petrochem. (France)
3.0
3.1
BASF (Germany)
3.0
3.2
NPC Iran
0.7
~5
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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
380 oC
Dilution Steam
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, it’s 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
Material Movements
Mixed
Butanes
Gasoline
Acid Gas
Compressor and
Drier Chilling
Steam
Primary
Fractionator
Quench
Feeds
NAPD
Converter
Propylene
Propane
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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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 :
C 2H 6
C2H6+ CH3
C 2H 5
C 2H 6 + H
CH3 + CH3
CH4 + C2H5
C 2H 4 + H
C2H4 + H … etc … etc …
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Free radical, fugitive, non isolable…
Steam : inert
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Chemistry
but :
CH4 + H2O
CO + 3H2
CO + H2O
CO2 + H2
CH3 , C2H5
C
+ H2
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Coke !
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You wanna check !
« Schutt » formula
Y = yield in ethylene from ethane :
1.67 k
Y=

P TOTAL
=
1 – 2
P TOTAL
1 + 1.2
PH
k
2
1–
2
-1
disappearance of ethane
hydrocarbon partial pressure
k =
equilibrium constant
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PH =
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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
0
35
45
52
60
Butadiene
0
6
1
14
18
Raffinate-1
0
4
4
17
21
Benzene
1
8
9
22
18
Other (fuel)
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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 
1150 °C on the heater tubes
Oh no!!
very cold  - 160 °C in the separation section
high pressures 
low pressures 
powerful 
steam at 120 b
vacuum in condensers
200 MW installed power
large 
x 400
m plot, i.e four giant stadiums...
Four 300
time this
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 (80’s):
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
Göteborg, 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
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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 1950’s …”
”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 other producers of ethylene…
 Products from combustion (incense in China, smoke in Egypt… for
millenniums)
 The Neptune planet…
 All fruits, vegetables & other flowers…
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How ?
 From methionine present in plants, and self-regenerative
Effects ?
 Activates germination, roots & branches growth, formation of
fruits & leaves, blooming of flowers, … as well as fading
 Stimulates the fruits ripening , until they decay !
(Degradation of the green chlorophyll towards ripened pigments)
 Beneficial actions (tomato, rice, banana…) or adverse
(flowers, storage of fruits…) variable with plant types
 Alarm signal for some plants
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Production of ethylene in µL1/kg/hour
(temperature: 20 °C)
Very low
0.01-01
Low
0.1-1.0
Medium
1.0-10.0
High
10.0-100.0
Very high
100.0 and +
Potato
Strawberry
Vegetables roots
Grenadine
Artichoke
Grapes
Pineapple
Rasberry
Kiwi
Cuccumber
Banana
Mango
Cantaloupe/Melon
Tomato
Fig
Lettuce
Orange
Plum
Carnation
Apple
Apricot
Avocado
Nectarine
Pear
Papaya
Peach
Passion fruit
Pomegranate
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(Kader-Kasmire 1984 – D’après Kee 1985)
Combustions in storage areas (in ppm = µl. = 0,0000 01l)
Exhaust gases from :
 Fork-lifts butane-powered
150 ppm
 Diesel engines
60 ppm
 Gasoline engines
200 ppm
 Smoke from cigarettes 100 à 200 ppm
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µl. = 0,0000 01l)
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Fruits & vegetables and ethylene
Sensitivity to ethylene
Ethylene production
Low
High
Low
Pinapple
Artichoke
Strawberry
Rasberry
Root
Grapes
Cuccumber
Kiwi
Potato
Medium
Fig
Oranges
Banana
Mango
Cantaloupe / Melon
Plum
Lettuce
Tomato
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High
Apricot
Avocado
Pomegranate
Papaya
Peach
Pear
Apple
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Undesirable effects from ethylene on the quality of
vegetables
Vegetable
Effects of ethylene
Asparagus
Fibrous texture
Eggplant
Loss of flower
Broccoli
Yellowish + strange savor + loss of
flowers
Bulbs
Inhibition of germination, bulb elongation
+ formation of abnormal flowers
Carot
Bitterness
Cabbage
Yellow + fall of foliage
Cauliflower
Yellow
Cuccumber
Yellow + softening
Spinach
Yellow
Green bean
Yellow
Lettuce
Brown spots
Potato
Prevents germination
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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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A greener chemistry
Steam-cracking: all together, an attractive business!
Thank you / Merci !
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