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

2

7

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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

0

10

20

30

40

50

60

70

80

90

100

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

0

300

600

900

1200

0

100

200

300

400

500

600

700

0 20 40 60 80 100

Byp

rodu

cts

Rel

ativ

e %

Rea

ctor

Vol

ume

Rel

ativ

e %

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

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SOEC more efficient than present Electrolysers Internal waste heat used to split water

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

0 100 200 300 400 500 600 700 800 900 1000

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