SUSTAINABLE POLYMERSFROM CO2 AND WATER

WITH LOW-CARBONELECTRICITY

ilkka.hannula@vtt.fi

Neo-Carbon Energy WP3 WorkshopMay 18th 2015ILKKA HANNULA, VTT

18.5.2015

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18.5.2015

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18.5.2015

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”BAU economics”

18.5.2015

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Negative electricity priceleads to negative OPEX

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Negative electricity priceleads to negative OPEX

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Negative electricity priceleads to negative OPEX

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Negative electricity priceleads to negative OPEX

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Negative electricity priceleads to negative OPEX

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Possible future OPEX curve?

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Neo-Carboneconomics?

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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)

Global demand of light olefins by regions in 2011

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

China MTO and MTP projects up and running by early 2012

UOP/Hydro’s Methanol to Olefins processwith Olefin Cracking option

MTO integrationwith Steam Cracker

Kilpilahti Ethene PlantSource: Öljystä muoveihin (1992), Neste Oyj.

MTOcrude

STEAMCRACKER

MTOCONVERSION

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€

KIITOS –THANK YOU

Some additional slides

MTO product integration

Advanced MTO product integration

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€