Within petrochemical industry the combination of synthetic methanol manufacture with MTO technology would make it possible to produce light olefins (ethylene and propylene) CO2 and water with low-carbon electricity. To satisfy global demand (206 Mt/a) of light olefins through P2X route 644 GW electricity and 924 Mt/a CO2 (3 % of annual global emissions) would be required. With today’s electricity market price scenarios the profitability of this concept is however very low in comparison to steam cracking of fossil hydrocarbon feedstocks. Based on cursory capital cost estimates, the levelised production cost of olefins would be 2000 €/t at current electricity prices.

1. SUSTAINABLE POLYMERS
FROM CO2 AND WATER
WITH LOW-CARBON
ELECTRICITY
ilkka.hannula@vtt.fi
Neo-Carbon Energy WP3 Workshop
May 18th 2015
ILKKA HANNULA, VTT

2. 18.5.2015
h/a
Price
Operating expense

3. 18.5.2015
Price
Operating expense
h/a

4. 18.5.2015
Price
Operating expense
h/a

5. ”BAU economics”
18.5.2015
Price
Operating expense
h/a

6. Price
Negative electricity price
leads to negative OPEX
h/a

7. Price
Negative electricity price
leads to negative OPEX
h/a

8. Price
Negative electricity price
leads to negative OPEX
h/a

9. Price
Negative electricity price
leads to negative OPEX
h/a

10. Price
Negative electricity price
leads to negative OPEX
h/a

11. Price
Possible future OPEX curve?
h/a

12. Price
h/a

13. Price
h/a

14. Price
h/a

15. Price
Neo-Carbon
economics?
h/a

16. Light Olefins
Olefins 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)

17. Global demand of light olefins by regions in 2011

18. Platts Global ethylene
price index $/tonne
Source: http://bit.ly/1CcAGNb
Platts Global propylene
price index $/tonne
Source: http://bit.ly/1MxG9xE

19. Naphtha
Condensate
Ethylene
Propylene
Metathesis
Gas
Oil
Dehydro
Steam
Cracker
LNG
by-product
Refining
by-product
Olefin routes

20. Naphtha
Condensate
MTOAEC
Electricity
Methanol
Synthesis
Ethylene
Propylene
Metathesis
Gas
Oil
Dehydro
Steam
Cracker
LNG
by-product
Refining
by-product
Olefin routes
CO2

21. Naphtha
Condensate
MTOAEC
Renewable
Naphtha
Electricity
SOEC
Fischer
Tropsch
Methanol
Synthesis
Ethylene
Propylene
Metathesis
Gas
Oil
Dehydro
Steam
Cracker
LNG
by-product
Refining
by-product
Olefin routes
CO2
CO2

22. CO2 to Methanol
- Synthesis conditions
250 °C and 80 bar.
- Recycle until overall H2
efficiency 95 % reached.
- Highly active copper-ceria
catalysts (see next page)
- Water removal and
final purification by
conventional distillation
WATER
ELECTROLYSIS
METHANOL
CONVERTER
COMPRESSION DISTILLATION
Methanol
Purge
gas
H2O
O2 CO2
H2O

23. “The transformation of CO2 into alcohols or
other hydrocarbon compounds is
challenging because of the difficulties
associated with the chemical activation of
CO2 by heterogeneous catalysts.”
“Pure metals and bimetallic systems used
for this task usually have low catalytic
activity.“
“The combination of metal and oxide sites
in the copper-ceria interface affords
complementary chemical properties that
lead to special reaction pathways for the
CO2 CH3OH conversion.”

24. Methanol to Light Olefins
UOP/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

25. China MTO and MTP projects up and running by early 2012

26. UOP/Hydro’s Methanol to Olefins process
with Olefin Cracking option

27. MTO integration
with Steam Cracker

28. Kilpilahti Ethene Plant
Source: Öljystä muoveihin (1992), Neste Oyj.
MTO
crude

30. STEAM
CRACKER
MTO
CONVERSION

31. Naphtha replacement: 1.7 kg/kg MeOH/naphtha
10 t/h naphtha replacement = 135 kton/a MeOH = 183 MWe
Case Example: Kilpilahti cracking ovens

35. Global approach
To 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€

36. KIITOS –
THANK YOU

37. Some additional slides

38. MTO product integration

39. Advanced MTO product integration

41. 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

42. 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

43. 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

44. 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

45. 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

46. 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€