John Bøgild Hansen - Haldor Topsøe

Columbia Unviersity, New York City – April 14, 2014

Methanol Synthesis from CO2

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

Topsoe Fuel Cell A/S

Founded in 2004 after more than

20 years of research and

development

Located in Lyngby, Denmark

(north of Copenhagen)

Employees 105

Development, manufacturing and

marketing of the Solid-Oxide

Fuel Cell technology (SOFC

technology)

Subsidiary of Haldor Topsøe

A/S (100%)

Topsoe Fuel Cell Employees

Headquarters in Lyngby, Denmark

Supported by funding under the

LIFE Programme

of the European Union

Methanol synthesis

CO + 2H2 = CH3OH + 91 kJ/mol

CO2 + 3H2 = CH3OH+H2O + 41 kJ/mol

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

The Active Site of Syngas Catalyst

Cu is metallic

when catalyzing:

- WGS

- MeOH synthesis

- MeOH reforming

Catalyst dynamic:

- Number of active sites depends on conditions

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

Ca

rbo

n c

on

ve

rsio

n %

J.B. Hansen Data

Condensing methanol

K.Klier Data

Lab data 225 C

Ageing of methanol catalyst in

Normal and Dry Syngas

120

80

40

0 0 200 400 600 800

Time on stream, hours

Rela

tive a

cti

vit

y

10/1-gas

5/5-gas

Reformers for Methanol Plant utilising CO2

¾CH4 + ½H2O + ¼CO2 = CH3OH

GreenSynFuel Project

Mass Flows in Wood to MeOH

Mass Flows in Wood + SOEC to MeOH

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

Methanol from CO2 and Steam

P 1

SOEC

Purge

Water

E 3

E 6

E 7

E 4

E 1

CO2

Methanol

Methanol

Reactor

K 2K 1

K 3

Recycle

Oxygen

Synergy between SOEC and fuel synthesis

SOEC Synthesis

CO2

H2O

Syn

Gas

Product

Steam

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

rod

ucts

Rela

tive %

Reacto

r V

olu

me R

ela

tive %

Percent CO2 through SOEC

Byproducts

Reactor Volume

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

Conclusions

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.