a greener chemistry 120 millions tons of ethylene per year why, what for, & how “greener” ?
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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. Ethylene, What is it, actually? It’s : C 2 H 4 !! 2 carbons, 4 hydrogens. 130 Million t/y (2006). - PowerPoint PPT PresentationTRANSCRIPT
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!