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John Bøgild Hansen , Haldor Topsøe A/S Christian Dannesboe, Aarhus University Brintbranchens Årsmøde, April 18, 2018 SOEC Enabled Biogas Upgrading AARHUS UNIVERSITY DEPARTMENT OF ENGINEERING

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Page 1: SOEC Enabled Biogas Upgrading - brintbranchen.dk¸gild.pdf · 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

John Bøgild Hansen, Haldor Topsøe A/S

Christian Dannesboe, Aarhus University

Brintbranchens Årsmøde, April 18, 2018

SOEC Enabled Biogas Upgrading

AARHUSUNIVERSITY

DEPARTMENT OF ENGINEERING

Page 2: SOEC Enabled Biogas Upgrading - brintbranchen.dk¸gild.pdf · 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

Biogas upgrade by means of SOEC

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

DEPARTMENT OF ENGINEERING

Page 3: SOEC Enabled Biogas Upgrading - brintbranchen.dk¸gild.pdf · 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

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

H2H2O

H2 + CO + O2 H2O + CO2 + electric energy (∆G) + heat (T∆S)SOF

C

SOECDEPARTMENT OF ENGINEERING

Page 4: SOEC Enabled Biogas Upgrading - brintbranchen.dk¸gild.pdf · 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

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.

kW

h p

er

Nm

3 H

2

Minimum Electricity Input

Waste heat which can be utilised to split water

Energy needed to evaporate water

Page 5: SOEC Enabled Biogas Upgrading - brintbranchen.dk¸gild.pdf · 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

CO2 + 4H2 ↔ CH4 + 2H2O (-∆H = 165 kJ/mol)

Syngas = SNG + heat

Energy: 100% = 80% + 20%

SNG100%

80%

20%Heat

SNG Technology

Methanation generates a lot of heat

DEPARTMENT OF ENGINEERING

Page 6: SOEC Enabled Biogas Upgrading - brintbranchen.dk¸gild.pdf · 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

Synergy between SOEC and fuel synthesis

SOEC Synthesis

CO2

H2O

Syn

Gas

Product

Steam

DEPARTMENT OF ENGINEERING

Page 7: SOEC Enabled Biogas Upgrading - brintbranchen.dk¸gild.pdf · 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

Biogas to SNG via SOEC and methanation

of the CO2 in the biogas

Biogas

Oxygen

Water

Condensate

SNG

SteamMethanator

SOEC

DEPARTMENT OF ENGINEERING

Page 8: SOEC Enabled Biogas Upgrading - brintbranchen.dk¸gild.pdf · 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

EUDP project

50 kW SOEC and 10 Nm3/h methane

Participants:

Haldor Topsøe A/S

Aarhus University

HMN Naturgas

Naturgas Fyn

EnergiMidt

Xergi

DGC

PlanEnergi

Ea Energianalyse

Coordinator:

Duration:

June 2013 -

December

2017

Project sum:

5.3 mio €

Location:

Foulum

Page 9: SOEC Enabled Biogas Upgrading - brintbranchen.dk¸gild.pdf · 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

Methanation and SOEC at Foulum

DEPARTMENT OF ENGINEERING

Page 10: SOEC Enabled Biogas Upgrading - brintbranchen.dk¸gild.pdf · 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

Major events during the Project

Page 11: SOEC Enabled Biogas Upgrading - brintbranchen.dk¸gild.pdf · 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

Topsoe Stack Platform (TSP-1) 8 Stacks

75 cells combined with interconnects, spacers and sealings in one stack

Internal fuel

manifold

External air

manifold

Cell group voltage

probing

Compression free

handling (cold)

DEPARTMENT OF ENGINEERING

Page 12: SOEC Enabled Biogas Upgrading - brintbranchen.dk¸gild.pdf · 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

Heat up of SOEC unit from cold10-11 hours, but full production on/off within seconds

0

20

40

60

80

100

120

140

160

180

200

0

100

200

300

400

500

600

700

800

16:00 18:00 20:00 22:00 00:00 02:00 04:00 06:00 08:00 10:00 12:00 14:00 16:00

Vo

lt o

r A

mp

per

15

0 c

ells

Deg

. C

Hour

Out Preheater

In Stacks

Out Stacks

Volt

Amps

Volt

Current

Temperatures

DEPARTMENT OF ENGINEERING

Page 13: SOEC Enabled Biogas Upgrading - brintbranchen.dk¸gild.pdf · 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

Screen dump from Cores

8 Stacks of 75 cells

1.28 V per cell, 65 A = 50 kW

Hydrogen production = 16.3 Nm3/h

3.06 kWh/Nm3

Tinlet = 726 °C

DEPARTMENT OF ENGINEERING

Page 14: SOEC Enabled Biogas Upgrading - brintbranchen.dk¸gild.pdf · 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

Production (100 % = 10 Nm3/h CH4)

vs hours on stream. 3.1 kWh/Nm3 H2

0%

20%

40%

60%

80%

100%

120%

680

700

720

740

760

780

800

820

840

860

0 500 1000 1500 2000 2500

Perc

en

t o

f D

esig

n p

rod

ucti

on

Hours on Electrolysis

Page 15: SOEC Enabled Biogas Upgrading - brintbranchen.dk¸gild.pdf · 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

Screen dump from methanator start up

Page 16: SOEC Enabled Biogas Upgrading - brintbranchen.dk¸gild.pdf · 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

Transient operation of methanator

DEPARTMENT OF ENGINEERING

Page 17: SOEC Enabled Biogas Upgrading - brintbranchen.dk¸gild.pdf · 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

Methanator catalyst very active and stable

DEPARTMENT OF ENGINEERING

Page 18: SOEC Enabled Biogas Upgrading - brintbranchen.dk¸gild.pdf · 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

Average gas compositions June 2, 2016

Position CH4 CO2 N2 H2

Inlet 56 43 1 0

Exit 1st

stage

94.58 0.27 0.91 4.23

Product

gas

97.69 0.00 0.95 1.36

DEPARTMENT OF ENGINEERING

Page 19: SOEC Enabled Biogas Upgrading - brintbranchen.dk¸gild.pdf · 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

Exergy Flows in CO2 case

DEPARTMENT OF ENGINEERING

Page 20: SOEC Enabled Biogas Upgrading - brintbranchen.dk¸gild.pdf · 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

Efficencies

Configuration

Percent effciency

A

CO2 Meth.

Exergy eff gas 80.2

District heating 0.8

Oxygen 2.1

Exergy eff Total 83.1

LHV eff gas 76.3

LHV DH 14.0

LHV eff total 90.3

Page 21: SOEC Enabled Biogas Upgrading - brintbranchen.dk¸gild.pdf · 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

Demonstration Plant - Conlusions

Process values very close to design simulations

Better than SNG quality:

Catalyst for CO2 methanation have high activity and durability

Boiling water reactor design robust and flexible

SOEC close to 100% efficiency (LHV)

Hot start and stop within seconds

Integration of SOEC and methanation unit

Completely automated including all utilities

Operating Strategy:

– Thermoneutral Voltage – Full Production

– Increase Temperature to Counteract Degradation

DEPARTMENT OF ENGINEERING

Page 22: SOEC Enabled Biogas Upgrading - brintbranchen.dk¸gild.pdf · 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

New EUDP project

50 kW SOEC and 10 Nm3/h methane

Participants:

Haldor Topsøe A/S

Aarhus University

Xergi

Duration:

November

2017 -

April 2020

Project sum:

1.5 mio €

Location:

Foulum