A Greener chemistry 120 Millions tons of Ethylene per year Why, what for, & how “greener” ?

1. A Greener chemistry120 Millions tons of Ethylene per yearWhy, what for, & how “greener” ? Michel H. BUFFENOIRSenior V.P, Technip Ethylene Business Unit Lille, 2-5 October 2007

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3. Ethylene, What is it, actually? It’s : C2H4 !! 2 carbons, 4 hydrogens A greener chemistry

4. 130 Million t/y (2006) TECHNIP Lummus S&W KBR Linde Ethylene, what is it?? • Business of 8 to 10 Billion €/year… • WorldCapacity • Basic chemical for1 billion derivatives A greener chemistry • Club of “five”

5. 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 A greener chemistry

6. 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 A greener chemistry

7. Polimeri Europa A greener chemistry

8. Ethylene derivatives A greener chemistry

9. Molecule of polyethylene A greener chemistry

10. Types of Polyethylene A greener chemistry LDPE Low density polyethylene Density 910-925 mg/cm3 HDPE High density polyethylene Density 935-965 mg/cm3 LLDPE Linear low density polyethylene Density 915-930 mg/cm3

11. 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 A greener chemistry

12. World production (2003) A greener chemistry

13. The world top producers A greener chemistry

14. 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' A greener chemistry

15. Convection Section Hydrocarbon Feed 120 oC ~ Boiler Feed Water Steam Drum ~ Cracked Gas to Separation Section Dilution Steam 380 oC Desuper- heater BFW 520 oC HP Steam Transferline Exchanger 620 oC 850 oC 1250 oC Radiant efficiency: 40 – 42% Overall efficiency: 92 – 95 % Radiant Section Cracking furnace

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19. 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) A greener chemistry

20. Hydrogen Utilities Mixed Butanes Gasoline Material Movements Acid Gas Compressor and Chilling Propylene Steam Drier NAPD Converter Propane Primary Fractionator Ethylene Quench Feeds Mixed Products Ethane Acetylene Converter Ethane Methane Quench Fuel Oil Cracking Furnaces Naphtha Olefins complex: a steam-cracking unit A greener chemistry

21. Iran 10th: ethylene fract., diam. 6 m, 800T A greener chemistry

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23. A little bit of chemistry ! A greener chemistry

24. C • C • Ethane(USA, Middle East) • C • C • C • Propane, LPG • C • …..……… • C • Naphtha(CEE, Japan, Far East) Chemistry • Steam cracking = cracking of hydrocarbon molecules having, at least, 2 atomes of carbon : • …… A greener chemistry • …… • Gasoil, HVGO (Shell)

25. heat • C • C • C • C • + H2 • (C2H6 • Ethane) • 800 °C • 0.1 second • C2H6 • CH3 • + • CH3 • C2H6 • + • CH3 • CH4 • + • C2H5 • C2H5 • C2H4 • + • H Chemistry • Simple : • In fact : • C2H6 • + • H • C2H4 • + • H2 • … etc … etc … A greener chemistry • Free radical, fugitive, non isolable… • Steam : inert

26. CH4 • + • H2O • CO • + • 3H2 • CO • + • H2O • CO2 • + • H2 • CH3 • , C2H5 • C • + • H2 Chemistry • but : A greener chemistry • Coke !

27. You wanna check ! • « Schutt » formula • Y = yield in ethylene from ethane : • 1.67 k • 1 – 2 • PH • 2 • Y = • 1 + 1.2 • -1 • P TOTAL • P TOTAL • k • 1 – 2 • = disappearance of ethane • PH = hydrocarbon partial pressure • k = equilibrium constant Questions ? A greener chemistry

28. Feedstock selection and ethylene yields A greener chemistry (Feed and Products in tons per 100 ton of ethylene product)

29. Oh no!! Four time this stadium A process of extremes ! very hot 1150 °C on the heater tubes very cold- 160 °C in the separation section high pressures steam at 120 b low pressuresvacuum in condensers powerful200 MW installed power large300 x 400 m plot, i.e four giant stadiums... gigantic  ~ 175 000 kg/h ethylene even bigger Vessels as large as a 38 m2 appartment sophisticated  product purity over 99.95 % wt. A greener chemistry Potentially hazardous  H2S, NOx, CO, H2, Methane… yet very safe  very few accidents

30. Ethylene is now :Necessary, unavoidable, basis for the whole petrochemical industry 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 A greener chemistry

31. How “greener” these days ? A greener chemistry

32. 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 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 A greener chemistry

33. 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) A greener chemistry

34. 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 …” A greener chemistry

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36. Ethylene is also intrinsically « green »… Other major producers : A greener chemistry

37. 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 A greener chemistry

38. Production of ethylene in µL1/kg/hour (temperature: 20 °C) • (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 A greener chemistry • 11 µl. = 0,0000 01l)

39. Fruits & vegetables and ethylene A greener chemistry

40. Undesirable effects from ethylene on the quality of vegetables A greener chemistry

41. 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: A greener chemistry

42. Steam-cracking: all together, an attractive business! A greener chemistry Thank you / Merci !