sustainable polymers from co2 and water with low-carbon electricity
TRANSCRIPT
SUSTAINABLE POLYMERSFROM CO2 AND WATER
WITH LOW-CARBONELECTRICITY
Neo-Carbon Energy WP3 WorkshopMay 18th 2015ILKKA HANNULA, VTT
Light OlefinsOlefins ethylene and propylene form the main petrochemical platform• Main plastics (polyethylene and polypropylene), elastromers, rubbers• Ethylene is used for monomers like ethylene glycol, ethylene oxide , styrene, vinyl- and
fluoromonomers• Propylene is used also for monomers like acrylic acid, acrylnitrile, propylene oxide• Several base chemicals like acitic acid, surfactants, base oils, etc.
Ethylene (C2H4)
Propylene (C3H6)
Platts Global ethyleneprice index $/tonneSource: http://bit.ly/1CcAGNb
Platts Global propyleneprice index $/tonne
Source: http://bit.ly/1MxG9xE
Naphtha
Condensate
Ethylene
Propylene
Metathesis
Gas
Oil
Dehydro
SteamCracker
LNGby-product
Refiningby-product
Olefin routes
Naphtha
Condensate
MTOAECElec
tric
ity
MethanolSynthesis
Ethylene
Propylene
Metathesis
Gas
Oil
Dehydro
SteamCracker
LNGby-product
Refiningby-product
Olefin routes
CO2
Naphtha
Condensate
MTOAEC
RenewableNaphtha
Elec
tric
ity
SOECFischerTropsch
MethanolSynthesis
Ethylene
Propylene
Metathesis
Gas
Oil
Dehydro
SteamCracker
LNGby-product
Refiningby-product
Olefin routes
CO2
CO2
CO2 to Methanol
- Synthesis conditions250 °C and 80 bar.
- Recycle until overall H2efficiency 95 % reached.
- Highly active copper-ceriacatalysts (see next page)
- Water removal andfinal purification byconventional distillation
WATERELECTROLYSIS
METHANOLCONVERTERCOMPRESSION DISTILLATION
Methanol
Purgegas
H2O
O2 CO2
H2O
“The transformation of CO2 into alcohols orother hydrocarbon compounds ischallenging because of the difficultiesassociated with the chemical activation ofCO2 by heterogeneous catalysts.”
“Pure metals and bimetallic systems usedfor this task usually have low catalyticactivity.“
“The combination of metal and oxide sitesin the copper-ceria interface affordscomplementary chemical properties thatlead to special reaction pathways for theCO2 CH3OH conversion.”
Methanol to Light OlefinsUOP/Hydro’s MTO process• Fluidised-bed reactor at 410 °C and 3 bar• Ethylene and propylene mass ratio 1:1• 99.8 % conversion of methanol• Coke formation 4.5 wt% of feed MeOH• Catalyst continuously regenerated in a combustor• Multi-column cryogenic distillation required
Fast-fluidised MTO reactor
Naphtha replacement: 1.7 kg/kg MeOH/naphtha10 t/h naphtha replacement = 135 kton/a MeOH = 183 MWe
Case Example: Kilpilahti cracking ovens
Global approachTo satisfy global demand (206 Mt/a) of light olefins• Required resources:
– Electricity: 644 GW– CO2: 924 Mt/a (3 % of annual global emissions)
• Total capital investment:– For methanol production: 710 mrd€– For MTO: 220 mrd€– For the combined production chain: 930 mrd€
CO2-to-Methanol- First described by Patart [43] and soon after produced by BASF chemists in Leuna,
Germany in 1923. [44]- Low pressure methanol synthesis, pioneered by engineers at ICI has become
the exclusive production process since 1960’s- Methanol is the largest product from synthesis gas after ammonia- Can be utilised as chemical feedstock or to supplement liquid fuels.- Can also be converted to various chemicals or used as a portal to hydrocarbon fuels
through the conversion to dimethyl ether (DME) or gasoline (MTG).- In 2011 the annual consumption of methanol amounted to 47 million tons
Methanol-to-Olefins- MTO was first developed by Mobil in the mid-1980s as a spin-off to
MTG in New Zealand.- Technology went unused until the mid-1990’s when UOP & Norsk
Hydro build a pilot plant in Norway.- A successful 100 bbl/d demonstration later operated in Germany.- Since then, Lurgi has also developed its own version (MTP).- Dalian Institute of Chemical Physics has recently developed a
similar process (DMTO).
The proposed concept
Design parameters
Alkaline Electrolyser Cell– System efficiency: 62 % (LHV)– Specific investment
• Now: 1000 €/kWe• Future: 600 €/kWe
– Mass balance for 1 MWe system• Water input: 268 kg/h• H2 output: 30 kg/h• O2 output: 238 kg/h
Design parameters
CO2 Methanol synthesis– Thermal efficiency: 83 %– Specific investment:
• Now 1000 €/kWMeOH
• Future 650 €/kWMeOH *– Mass & energy balance from Aspen
• Compression work: 1.8 MW• CO2 input: 7.4 kg/s• MeOH output: 100 MW (LHV)• DH output: 0 MW (Large reboiler duty requirement!)
*Based on ETOGAS data on methanation: 400 €/kWe
Methanol to olefins– MTO specific investment: 4-8 M€ per tLO/h– Mass & energy based on Aspen
• Methanol input: 0.06 t/h• Light olefin yield: (E+P): 0.397 kg/kgMeOH
• Light olefin output: 0.02 t/h
Design parameters
Financial parameters
• Installation cost: 15 % of TCI• Annuity factor: 0.12 (20 a & 10 %)• Annual O&M factor: 0.04 of TCI• Consumables
– Value of O2: 27 €/t– Value of CO2: 40 €/t– Value of water: 1 €/t– Value of DH: 0 - ? €/MWh
Possible plant sizes• 20 MWe electrolyser plant produces
– 10.2 MW (0.51 kg/s) of methanol– 0.2 kg/s (0.7 t/h) light olefins (E+P)– Total Capital Investment:
• NOW: 32 M€• FUTURE 20 M€
• 270 kton/a (olefins) MTO plant– 85 t/h (470 MW) MeOH input– 46 methanol plants (20 MWe input)– Total Capital Investment: 290 M€