john bøgild hansen european bøgild hansen… · reactor volume and byproducts as function of co....
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CO2 utilisation for Fuel and Chemical Production John Bøgild Hansen - Haldor Topsøe
European Methanol Policy Forum
Bruxelles – October 13, 2015
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We have been committed to catalytic process technology for more than 70 years
• Founded in 1940 by Dr. Haldor Topsøe • Revenue: 700 million Euros • 2700 employees • Headquarters in Denmark • Catalyst manufacture in Denmark and
the USA
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Topsoe methanol plants Since 2000
Number of plants: 40 Accumulated capacity, MTPD: 97,075 Number of catalyst charges: 168
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17 12
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Methanol market share
HTAS 28%
Davy 26%
Lurgi 15%
Casale 13%
Chinese Lic. 4%
Others 14%
Awarded capacity 2003-2014
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• Optimising sintering barriers • Cu crystals separated by picket fence of metal oxides • The FENCE™ technology inhibits sintering
Cu ZnO Al2O3
FENCE™ technology
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Increased loop efficiency – Production gain – Increased carbon efficiency – Lower energy consumption
Longer catalyst lifetime – Less replacements – Increased plant availability
Industrial experience
Days on Stream
Cat
alys
t act
ivity
MK-151 FENCE™
MK-121 MK-101
20%
20%
MK-151 FENCE™
MK-121
MK-101
Statoil, Norway, 2500 MTPD 28.8 GJ/MT => 69 % effeiciency Industrial benefits
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Methanol synthesis
• CO + 2H2 = CH3OH + 91 kJ/mol • CO2 + 3H2 = CH3OH+H2O + 41 kJ/mol
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The Active Site of Syngas Catalyst
Cu(111), d=0.21nm
Cu(200), d=0.18nm
ZnO(011), d=0.25nm
ZnO(012), d=0.19nm
Cu(111) Cu(111)
H2 H2/H2O
1.5mbar, 220oC 1.5mbar, H2/H2O=3/1, 220oC
Cu is metallic when catalyzing • WGS • MeOH synthesis • MeOHreforming Catalyst dynamic • Number of active
sites depends on conditions
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Conversion of methanol as function of CO2 content in stoichiometric gas
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0 5 10 15 20 25 30
Percent CO2 in
Car
bon
conv
ersi
on %
J.B. Hansen Data Condensing methanol
K.Klier Data Lab data 225 C
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Reformers for Methanol Plant utilising CO2 ¾CH4 + ½H2O + ¼CO2 = CH3OH
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Fuel Cell and Electrolyser
½O2
H2 H2O
½O2
H2O + 2e- → H2 + O2-
O2-
O2- → 2e- +½O2
H2 + O2- → H2O + 2e-
O2-
½O2 + 2e- → O2-
SOFC SOEC H2 H2O
H2 + CO + O2 H2O + CO2 + electric energy (∆G) + heat (T∆S) SOFC
SOEC
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Methanol From CO2 and Steam
Water
SOEC Oxygen
CO2
Met
hano
l sy
nthe
sis
Sepa
rato
r
Methanol
Purge
Recycle
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Reactor volume and byproducts as function of CO2 converted in SOEC
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Byp
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Rea
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Rel
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Percent CO2 through SOEC
Byproducts
Reactor Volume
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Synergy between SOEC and fuel synthesis Effciencies electricity to MeOH = 76-79 % possible
SOEC Synthesis CO2
H2O
Syngas Product
Steam
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GreenSynFuel Project
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Mass Flows in Wood to MeOH
1000 tons Wood 704 tons CO2
523 tons MeOH 262 tons Oxygen 59 % LHV efficiency
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Mass Flows in Wood + SOEC to MeOH
1000 tons Wood 782 tons Oxygen
1053 tons MeOH 262 tons Oxygen 141 MW electricity 71 % LHV efficiency
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Conclusions
• Haldor Topsøe is a major player within the methanol industry • CO2 is already today used to enhance methanol production based on
natural gas steam reforming • Very efficient methanol plants based on power, steam and CO2 is possible
via SOEC • Co-electrolysis offers the opportunity to reduce methanol synthesis
catalyst volumes by a factor around 5 • Pressurising the SOEC stacks can eliminate synthesis gas compressor and
increase efficiency • Coupling SOEC with biomass gasification can double the biomass potential
by converting excess carbon.
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To find out more or get in contact
www.topsoe.com To stay up to date regarding
upcoming events, product launches, cases and other
developments get connected and follow us:
.com
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SOEC more efficient than present Electrolysers Internal waste heat used to split water
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Deg C.
kWh
per N
m3
H2
Minimum Electricity Input
Waste heat which can be utilised to split water
Energy needed to evaporate water
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CO2 Black Liq.
Water
WGS Sulphur
Guard
MeOH Synthesis
AGR DME
Unit
Methanol from sustainable sources BioDME Black Liqour to Green DME Demo
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DOE Project
Green Gasoline from Wood Using Carbona Gasification and Topsoe TIGAS Processes
Wood to Gasoline
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Results of ”to pressurize SOEC stacks or not”
SOEC Pressure
Syngas Comp, %
CO2 Comp
LHV Efficiency, %
Atmospheric 6.8 0.1 75.8
@50 bar 0.0 1.9 79.5
Max. theoretical 83-88
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Effciencies Stand alone wood gasifier and gasifier plus SOEC
LHV Efficiency %
Wood Gasifier alone
Wood gasifier Plus SOEC
Methanol 59.2 70.8
District Heat 22.6 10.8
Total 81.8 81.6