A Greener chemistry120 Millions tons of Ethylene per yearWhy, what for, & how “greener” ?

Lille, 2-5 October 2007

Michel H. BUFFENOIRSenior V.P, Technip Ethylene Business Unit

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Ethylene,What is it, actually?

It’s : C2H4 !!2 carbons, 4 hydrogens

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Ethylene, what is it??

Business of8 to 10 Billion €/year…

Business of8 to 10 Billion €/year…

WorldCapacity

Basic chemical for1 billion derivatives

Club of “five” TECHNIPTECHNIP LummusLummus S&WS&W KBRKBR LindeLinde

130 Million t/y

(2006)

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ALL FROM AN

ETHYLENE

UNIT !!!

ALL FROM AN

ETHYLENE

UNIT !!!

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 Perspex 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

Oxo-reaction: herbicides

Pure: ripening agent

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Polimeri Europa

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HDPE24%

LLDPE/LDPE34%

Ethylene derivatives

Polyethylene58%

EDC/VCM14%

Other8%

Oxide/Glycols13%

Ethyl Benzene7%

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Molecule of polyethylene

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Types of Polyethylene

HDPEHigh density polyethyleneDensity 935-965 mg/cm3

LLDPELinear low density polyethyleneDensity 915-930 mg/cm3

LDPELow density

polyethyleneDensity 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: 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

TOTAL world 111

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The world top producers

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 the word 'steam-cracking'

Cracking furnace

Boiler Feed Water

Radiant Section

Convection Section

~~

Hydrocarbon

Feed

Dilution Steam

HP Steam

Desuper-heater

Cracked Gas to

Separation Section

Transferline Exchanger

BFW

Radiant efficiency: 40 – 42%

Overall efficiency: 92 – 95 %

850 oC1250 oC

120 oC

620 oC

380 oC

520 oC

Steam Drum

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

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Olefins complex: a steam-cracking unit

MixedProducts

Quench

Drier

Fuel Oil

Hydrogen

Compressor andChilling

Steam

Quench Methane

AcetyleneConverter

Ethane

Ethylene

PropanePropylene

NAPDConverter

MixedButanes

Gasoline

CrackingFurnaces

Ethane

Naphtha

Acid Gas

PrimaryFractionator

Feeds

Material Movements

Utilities

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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 Ethane (USA, Middle East)

C CC Propane, LPG

CC…..……… Naphtha (CEE, Japan, Far East)…

…

Gasoil, HVGO (Shell)

……

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Chemistry

Simple : C C C C + H2

heat

(C2H6

Ethane)800 °C

0.1 second

In fact :

C2H6 + H

C2H6 CH3 + CH3

C2H6 + CH3 CH4 + C2H5

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

Coke !

CH3 , C2H5 C + H2

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You wanna check !

« Schutt » formulaY = yield in ethylene from ethane :

Y =1.67 k

P TOTAL

1 – 2

P TOTAL

1 + 1.2PH

k

2

1 – 2-1

= disappearance of ethane

PH = hydrocarbon partial pressure

k = equilibrium constant

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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) 24 73 141 129 216

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

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Oh no!!

low pressures vacuum in condensers

gigantic ~ 175 000 kg/h ethylene

large 300 x 400 m plot, i.e four giant stadiums...

powerful 200 MW installed power

sophisticated product purity over 99.95 % wt.

Potentially hazardous H2S, NOx, CO, H2, Methane…

yet very safe very few accidents

high pressures steam at 120 b

very cold - 160 °C in the separation section

very hot 1150 °C on the heater tubes

even bigger Vessels as large as a 38 m2 appartment

Four time this stadium

A process of extremes !

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A process of extremes !

Costly noble metallurgies, complexmachinery, lenghty construction, sophisticated instrum/controls

Very clean CO2 , waste waters, coke, noise…

But very reliable 8 000 h/y, 6/7 y of operations without major shutdown

Ethylene is now : Necessary, unavoidable, basis for thewhole petrochemical

industry

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Key items: 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 emissionsNOx emissions

1550 kg per ton of ethylene180/200 mg/Nm3 effluent

790 kg per ton of ethyleneLess than 120 mg/Nm3 effluent

Operators 7 per shift 7 per shift

Noise ~92 dBA (compressors) ~85-87 dBA (compressors)

How “greener” these days ?

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From Ethylene to “ greener” plastics :sustainable developmentCRUDE OIL: 70% : diesel & heating oil 20% : naphtha, i.e. 13% gasoline & 7% chemical raw products, of which 4% plastics, 3% other chemicals 10% others

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

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 … “

“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 »…

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…

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 low0.01-01

Low0.1-1.0

Medium1.0-10.0

High10.0-100.0

Very high100.0 and +

PotatoStrawberryVegetables rootsGrenadineArtichokeGrapes

PineappleRasberryKiwiCuccumber

BananaMangoCantaloupe/MelonTomatoFigLettuceOrangePlumCarnation

AppleApricotAvocadoNectarinePearPapayaPeach

Passion fruit Pomegranate

(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

11 µl. = 0,0000 01l)

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Fruits & vegetables and ethylene

S e n s i t i v i t y t o e t h y l e n e

Ethylene production Low High

Low PinappleArtichokeStrawberryRasberryRootGrapes

CuccumberKiwiPotato

Medium Fig OrangesBananaMangoCantaloupe / MelonPlumLettuceTomato

High ApricotAvocadoPomegranatePapayaPeachPearApple

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Undesirable effects from ethylene on the quality of vegetables

Vegetable Effects of ethylene

Asparagus Fibrous texture

Eggplant Loss of flower

BroccoliYellowish + 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

attractive field of activity

Here it is why:

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Thank you / Merci !

Steam-cracking: all together, an attractive business!