1. A Greener chemistry 120 Millions tons of Ethylene per year Why, what for, & how “greener” ? Lille, 2-5 October 2007 Michel H. BUFFENOIR Senior V.P, Technip Ethylene Business Unit

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3. 3 Ethylene, What is it, actually? It’s : C 2 H 4 !! 2 carbons, 4 hydrogens

4. A greener chemistry 4 Ethylene, what is it?? Business of 8 to 10 Billion €/year… Business of 8 to 10 Billion €/year…  World Capacity  Basic chemical for 1 billion derivatives  Club of “five” TECHNIPLummusS&WKBRLinde 130 Million t/y (2006)

5. A greener chemistry 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

6. 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

7. A greener chemistry 7 Polimeri Europa

8. A greener chemistry 8 Making polymers from steam-cracking of oil & gas

9. A greener chemistry 9 Ethylene derivatives

10. A greener chemistry 10 Molecule of polyethylene

11. A greener chemistry 11 Types of Polyethylene HDPE High density polyethylene Density 935-965 mg/cm 3 LLDPE Linear low density polyethylene Density 915-930 mg/cm 3 LDPE Low density polyethylene Density 910-925 mg/cm 3

12. A greener chemistry 12 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

13. A greener chemistry 13 World production (2003) Region Million t/y USA / Canada35 Asia/Pacific29 EEC24 Mid.East / Africa12 Eastern Europe / CIS7 S.America4 TOTAL world111

14. A greener chemistry 14 EEC Country Million t/y Allemagne5,4 Hollande3,9 France3,4 Royaume-Uni2,8 Italie2,1 Belgique2,1 Espagne1,4

15. A greener chemistry 15 The world top producers Million t/y20032006 Dow (USA)13.111.8 Exxon/Mobil (USA)11.411.7 Shell (USA/Holland)6.77.0 Equistar/Lyondell (USA)5.2 Sabic (S.Arabia)5.06.7 BP/Amoco (UK/USA)4.64.8 Chevron-Phillips (USA)3.53.6 Sinopec (China)3.05.2 Nova (Canada), Total Petrochem. (France)3.03.1 BASF (Germany)3.03.2 NPC Iran0.7~5

16. A greener chemistry 16 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'

17. 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 o C 1250 o C 120 o C 620 o C 380 o C 520 o C Steam Drum

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20. A greener chemistry 20 GK6 - Y pieces connecting 8 coils to TLE

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22. A greener chemistry 22 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)

23. A greener chemistry 23 Olefins complex: a steam-cracking unit

24. A greener chemistry 24 Iran 10 th : ethylene fract., diam. 6 m, 800T

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26. A greener chemistry 26 A little bit of chemistry !

27. A greener chemistry 27 Characteristics of olefins production  Strongly endothermic process  Absorbed duty: Q ~1.6 Gcal / tonne of feed  For 1.350 kta cracker: fired heat ~ 840 MW FeedProducts Q

28. A greener chemistry 28 Chemistry Steam cracking = cracking of hydrocarbon molecules having, at least, 2 atomes of carbon : CCEthane (USA, Middle East)CCCPropane, LPGCC…..………Naphtha (CEE, Japan, Far East) …… Gasoil, HVGO (Shell) ……

29. A greener chemistry 29 Chemistry Simple : CCCC+ H 2 heat (C 2 H 6 Ethane) 800 °C 0.1 second In fact : C2H6C2H6 +H C2H6C2H6 CH 3 + C2H6C2H6 + CH 4 +C2H5C2H5 C2H5C2H5 C2H4C2H4 +H C2H4C2H4 +H2H2 … etc … etc … Free radical, fugitive, non isolable… Steam : inert

30. A greener chemistry 30 Chemistry but : CH 4 +H2OH2OCO+3H 2 CO+H2OH2OCO 2 +H2H2 Coke ! CH 3, C 2 H 5 C+H2H2

31. A greener chemistry 31 You wanna check ! « Schutt » formula Y = yield in ethylene from ethane : Y = 1.67 k  P TOTAL 1 –  2 P TOTAL 1 + 1.2 PHPH kk 22 1 –  2  = disappearance of ethane P H =hydrocarbon partial pressure k  =equilibrium constant

32. “Cracking” is:  non-catalytic  governed by reaction kinetics  intrinsically non-selective Hence:  looking primitive and unsophisticated, but  requires advanced engineering modelling  Very sophisticated yield prediction softwares Cracking technology

33. A greener chemistry 33 Feedstock selection and ethylene yields EthaneC3-LPGC4-LPGNaphthaGasoil Feed125226300334433 Ethylene100 Propylene035455260 Butadiene0611418 Raffinate-10441721 Benzene1892218 Other (fuel)2473141129216 (Feed and Products in tons per 100 ton of ethylene product)

34. A greener chemistry 34 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  H 2 S, NOx, CO, H 2, 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 m 2 appartment Four time this stadium A process of extremes !

35. A greener chemistry 35 A process of extremes ! Costly  noble metallurgies, complex machinery, lenghty construction, sophisticated instrum/controls Very clean  CO 2, 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 the whole petrochemical industry

36. A greener chemistry 36 Key items:Reference Plant (80’s): 600 kt/y Mega-Cracker (2006): 1000 + kt/y Energy input8000 kWh per ton of ethylene5300 kWh per ton of ethylene Product lossesLess than 1%Less than 0.25% CO 2 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 Operators7 per shift Noise ~92 dBA (compressors) ~85-87 dBA (compressors) How “greener” these days ?

37. A greener chemistry 37 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 CO 2 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

38. A greener chemistry 38 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)

39. A greener chemistry 39 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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41. A greener chemistry 41 Ethylene is also intrinsically « green »… Other major producers :

42. A greener chemistry 42 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

43. A greener chemistry 43 Production of ethylene in µL 1 /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 (Kader-Kasmire 1984 – D’après Kee 1985) Combustions in storage areas (in ppm = µl. = 0,0000 01l) Exhaust gases from :  Fork-lifts butane-powered150 ppm  Diesel engines60 ppm  Gasoline engines200 ppm  Smoke from cigarettes 100 à 200 ppm 1 1 µl. = 0,0000 01l)

44. A greener chemistry 44 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 productionLowHigh LowPinapple Artichoke Strawberry Rasberry Root Grapes Cuccumber Kiwi Potato MediumFigOranges Banana Mango Cantaloupe / Melon Plum Lettuce Tomato HighApricot Avocado Pomegranate Papaya Peach Pear Apple

45. A greener chemistry 45 Undesirable effects from ethylene on the quality of vegetables VegetableEffects of ethylene AsparagusFibrous texture EggplantLoss of flower Broccoli Yellowish + strange savor + loss of flowers BulbsInhibition of germination, bulb elongation + formation of abnormal flowers CarotBitterness CabbageYellow + fall of foliage CauliflowerYellow CuccumberYellow + softening SpinachYellow Green beanYellow LettuceBrown spots PotatoPrevents germination

46. A greener chemistry 46 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:

47. A greener chemistry 47 Thank you / Merci ! Steam-cracking: all together, an attractive business!