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Solid Oxide Cell Enabled Ammonia Synthesis and Ammonia based Power Production

John Bøgild Hansen

Haldor Topsøe A/S 1

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We have been committed to catalytic process technology for more than 77 years

•  Founded in 1940 by Dr. Haldor Topsøe •  Revenue: 700 million Euros •  2400 employees •  Headquarters in Denmark •  Catalyst manufacture in Denmark and

the USA

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Topsøe Ammonia Catalyst Charges

•  248 current references worldwide

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Topsoe ammonia plants Since 2000

Number of plants: 60 Accumulated capacity, MTPD: 99,505

3

23

1 6

1 7

7 12

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Topsoe ammonia process – alternative with prereformer

Prereforming (optional)

Process cond. Ammonia

product

Purge gas

Stack

Process air

Natural gas

Process steam

Ammonia synthesis Methanation

CO2- removal

Desulphurisation Reforming

Shift

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SynCOR AmmoniaTM

Simplified process layout H

ydro

gena

tion

Sulfu

r rem

oval

Prer

efor

min

g

Aut

o th

erm

al

refo

rmin

g

Air

Natural gas + hydrogen

Fuel

Fired heater

Steam

Super heated steam

Hig

h te

mpe

ratu

re

shift

Hig

h te

mpe

ratu

re

shift

CO

2 rem

oval

Nitr

ogen

was

h

Sepa

rato

r

Process condensate

S-300

Ammonia conversion

Ammonia product

Nitrogen

CO2 Off gases Oxygen

Air separation unit

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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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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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Biogas upgrade by means of SOEC

CH4 + CO2 + 3H2O + El 2CH4 +H2O + 2O2

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Biogas to SNG via SOEC and methanation of the CO2 in the biogas

Biogas

Oxygen

Water

Condensate

SNG

Steam Methanator

SOEC

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Biogas upgrading demonstration unit Operating in Foulum, Denmark

•  50 kW SOEC unit for steam electrolysis •  Catalytic methanisation •  The CO2 in the biogas is upgraded to pure

methane with pipeline quality. •  High Exergy Efficiency of 80%

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SOEC Operating temperatures as function of voltage and ASR ASR = Area specific resistance

Source: O´Brien IMECE 2008

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Synergy between SOEC and fuel synthesis

SOEC Synthesis

Air

H2O

Syn Gas

Ammonia

Steam

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Ammonia Synthesis Gas Generation by SOEC Efficiency = 77 % on exergy basis – 71 % on LHV basis

BFW Condensate

Steam

SOEC

Cooler

1

Recycle to SOEC

Syngas to NH3 loop

2 876543

Recycle to SOEC

Steam from NH3 loop

Air

SOEC SOEC SOEC SOEC SOEC SOEC SOEC

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Breakdown of power consumption in kWh per MT ammonia

6,785

154 20184

SOEC AirComp SyngasComp Refrigera4on

Totalenergy:7223kWh/MTNH3

Haber-BoschSynthesisonly6.0%!

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0

200

400

600

800

1000

1200

0 10 20 30Current in A

Cel

l vol

tage

in m

V

0.0

0.2

0.4

0.6

0.8

1.0

1.2

Pow

er d

ensi

ty in

Ω/c

m2

Hydrogen/nitrogen 3/1Ammonia

850 oC

Direct Ammonia SOFC

Same or better performance with ammonia as with H2+ N2 mixture 2 NH3 ⇒ 3 H2 + N2

0

200

400

600

800

1000

1200

0 5 10 15 20Current in A

Cel

l vol

tage

in m

V

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

Pow

er d

ensi

ty in

Ω/c

m2

Hydrogen/nitrogen 3/1Ammonia

750 oC

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Direct use of Ammonia for SOFC

Flue gas

Air

AmmoniaSOFC

Anod

e

Cath

ode

CatalyticBurner

Expander

Electrical efficiency > 60 % LHV

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Conclusions

•  Haldor Topsøe A/S has been the market leader for both catalyst and ammonia technology for decades

•  Recently introduced process scheme enables capacities above 6000 MTPD capacity based on auto-thermal reforming of natural gas

•  New Solid Oxide Electrolysis based synthesis gas process eliminates air separation unit and have very high efficiency

•  Ammonia is the perfect fuel for Solid Oxide Fuel Cells without the need for water addition or fuel processing

Thank You