Overview European CCS activities andR&D work at ECN
CCS Workshop RITE
February 15th and 16th, 2007

Overview presentation

Introduction ECN (Energy research Centre, The Netherlands)• European CCS Projects¾ CASTOR¾ ENCAPE¾ CACHET• Activities in the Netherlands¾ CATO¾ Other initiatives• ECN CCS activities¾ Membrane reactors¾ Sorption enhanced reactors

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The Netherlands PettenKyoto

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ECN key data

Employees:
Annual turnover:
Government funding:patent portfolio:
External publications:
ISO 9001 & 14001 certified422-1-2007

620 fte68 Meuro
24 Meuro
78 (34 granted, others pending)
617 (90 peer reviewed)

ECN programme units

Hydrogen & Clean Fossil Fuels

Policy Studies

Biomass, Coal & Environmental Studies
Solar Energy

Wind Energy

Energy Efficiency in Industry
Energy In the Built Environment

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European initiatives

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European initiatives
Timing722-1-2007

European Capture Projects

CASTOR: CO2, from Capture to Storage• Post combustion capture technology development• CO2 geological storage

ENCAP: Enhanced capture of CO2• Research and development on pre-combustion CO2 capture
mainly for hard coal and lignite• Oxy fuel also seen as pre combustion CO2 capture

CACHET• Pre combustion capture technologies for gaseous fuels (naturalgas)
Reduce cost of CO2 capture to EU target of 20 to 30 €/tonne at
90% capture rate822-1-2007

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1022-1-2007

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European Capture Projects:

ENCAP

Objective:• ENCAP aims at technologies that meet the targetof at least 90% CO2-capture-rate and 50% CO2capture-cost reduction.
• Pre combustion decarbonisation¾IGCC for hard coal and lignite¾IRCC for natural gas• CO2/O2 combustion technologies (oxy fuel)¾PC for hard coal and lignite¾CFB for hard coal, lignite and pet-coke• Chemical looping

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European Capture Projects:

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ENCAP

European Capture Projects:

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ENCAP

European Capture Projects:

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ENCAP

European Capture Projects:

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ENCAP

European Capture Projects:

CACHET

Objective:• Develop technology to reduce cost of CO2 capture to EU
target of 20 to 30 €/tonne at 90% capture rate– Industrial application to natural gas fired 400 MWe CCGTwith (H2 side-stream)– 4 main technology areas:- Advanced SMR- Chemical looping and One-step- Membranes- SEWGS• Novel technology evaluation, HSE and dissemination• 3 year project duration, commencing 1st April 2006
15 M euro, 50 % from EU, 20% from CCP
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European Capture Projects:

CACHET

Secondary combustion
Reforming SteamLP Fuel gas After burner
NG +Steam

BFW

Jet Engine Gas Generator

Tertiarycombustion

H2 + CO...
Catalytic Reactor / Exchangers

2122-1-2007

PowerEuropean Capture Projects:CACHET

chemical looping reforming

autothermalsmr
flue gasflue gas

22H2Osyngas toshift/separation

11CO233

4

5

fluidizing gas

fuelH2/CO2fuelair

12322natural gas

6air

Air
reactor/riser
CycloneFuel reactor

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1) air reactor/riser, 2) cyclone, 3) fuel reactor,4) fluidized bed heat exchanger/reformer (FBHE/R), 5) shift reactor6) hydrogen separation (one pure hydrogen flow, one CO2/H2 flow)
NOTE: return of particles from 4 to 1 not shown because of 2 D view,
Fluidizing gas for FBHE/R can be gas recycled from outlet of fuel or air
reactor or air.

H2

European Capture Projects:

CACHET

One-step decarbonisation
CO 2 (H O)
2CH4H2R1

H2 to utilization

R2Depl.Air

CH4R3

CO2To storage

H 2O
H 2O

Air

Circulating "redox" solid material that can be oxidized via water
splitting thereby producing H2, and reduced by a carbon-containing
stream, typically hydrocarbons, producing CO2
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European Capture Projects:

CACHETsewgs process concept
CO + H2O Ù CO2 + H2
Feed stepsyngas
adsorbent
57% H216% H2O
16% CO
10% CO2
0.5% CH4

adsorbent
and catalyst

90% C removal

decarbonizedfuel gas
87% H2
8% H2O
0.5% CO
2% CO2
0.5% CH4• Water gas shift catalyst + high temperature CO2 adsorbent• Removes CO2 from hot syngas (400-500oC), drives CO towards
extinction• Multiple beds undergo cyclic process steps (reaction/adsorption andregeneration
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European Capture Projects:

CACHETcombined reaction and separation
CO or CH 4

CO 2Capture

H2

HydrogenUtilisation

reaction

H 2O or O 2
Membrane reactor

Operatingtemperature

Type of reaction

Active membrane

300-400°C
400-600°C

Water gas shift
Metal membrane
Low temperature reforming of methane Metal membrane

thin palladium supported membranes
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CCS projects in The Netherlands• CATO project• CRUST of-shore storage project GdF• OCAP re-use project• New initiatives

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CCS projects in The Netherlands

CATO

Unique Dutch knowledge network in the area of CO2 capture,transport and storage• Partners: 17• Budget: 25.6 million € (50% govt. support)• In line with Dutch government policy: Ministries EZ(Economic Affairs) and VROM (Environment)• Embedded in international networks (CO2NET, IEA, CSLF)• Over 15 PhD students• Period: 2004-2009• Manager: UCE (within Utrecht University)27

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CCS projects in The Netherlands
WP Subject

WP Leaders

1 System analysis & Transition

UU-Copernicus
Ecofys and ECN

CATO

2 Capture of CO2
TNO S&I
2.1 Post-combustion
ECN
2.2 Pre-combustion
TNO S&I
2.3 Denitrogenated conversion
3 Storage of CO2
3.1 Storage gas fields
TNO-NITG
3.2 Storage coal fields (ECBM)
Shell (SIEP)
4 Mineralisation
4.1 Subsurface mineralisation
Shell (SIEP)
4.2 Surface mineralisation
ECN TNO S&I
5 Monitoring, safety and regulations
TNO-NITG
6 Communication
Leiden University
7 Management and knowledge transfer UU-UCE

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CCS projects in The Netherlands
System analyses

CATO~

North Sea
Gasfields (816 Mt)
Aquifers (~350 Mt)

North
Aquifers (85 Mt)
Groningen gasfield (7512 Mt)
H2~
West(570 Mt)

Aquifers~

Large scalehydrogen plant
Large scale
power plant
CO2 grid/pipeline
Hydrogen pipeline

H2Southwest
Aquifers (200 Mt)~CentralAquifers(155 Mt)~152922-1-200730

456075km

SoutheastAquifers (204 Mt)

Residential
hydrogen market
Industrialhydrogen market
Automotivehydrogen market
UU, van Troost & Daamen

CCS projects in The Netherlands

CATO
SIDE VIEWTOP VIEW

Main gas distributor
Vgas = 25 -30 m/s• CATO pilot plant in E.on PC boiler
Maasvlakte in the Roterdam area
• 50% capture cost reduction• Design for membrane aborberwhich is 4 times compactor theconventional absorbent

30

22-1-2007= Membrane module gas channel
Vgas = 2 m/s

The distributor
is arranged asa close endcolumn

Direction ofinlet gas flow
into main gas
distributor.

Vgas = 25 -30 m/s

Radial outlet flow ; Vgas = 25 - 30 m/s• CO2 capture with solvent andmembrane contactors

Radial outlet flow ; Vgas = 25 - 30 m/s

Post combustion capture

CCS projects in The Netherlands

CATO

Pre combustion capture; Pd alloy membrane reactor
Steam reform ing: CH 4 + H 2 O

3 H 2 + CO (∆H = 206 kJ/m ol)

W ater-gas shift: CO + H 2 O

H 2 + CO 2 (∆H = - 41 kJ/m ol)

CH 4 + 2 H 2 O

4 H 2 + CO 2Shifting the equilibrium to the product side
• System analyse• Membrane development• Membrane reactor design• Catalyst screening• PDU tests

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CCS projects in The Netherlands

CATO

Pre combustion capture; Sorption Enhanced Reaction Process
Steam reform ing: CH 4 + H 2 O

3 H 2 + CO (∆H = 206 kJ/m ol)

W ater-gas shift: CO + H 2 O

H 2 + CO 2 (∆H = - 41 kJ/m ol)

CH 4 + 2 H 2 O

4 H 2 + CO 2

Shifting the equilibrium to the product side
• Hydrotalcite materials suitable for SE water gas
shift reaction, not for SE reforming• Hydrotalcites not stable > 450 oC• Temperatures between 550 en 750 oC are
needed for steam reforming• New HT sorbents under development

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CH4 + H2O

H2CO
CO2CO2CO2 2COCO2sorbent catalyst sorbent 2CO2
Sorption-enhanced Reforming

CCS projects in The Netherlands

CATO

System evaluations : Pre combustion capture technologies
Results

Performance of selected systems

System efficiency (%)

53.0
Steam reforming, Sorption

52.0
Auto thermal reforming, Sorption

51.0
Water gas shift, Sorption, Air

Water gas shift, H2 membrane

50.0
Steam reforming, H2 membrane

49.0

Water gas shift, Sorption, O2

Post combustion, Amine adsorption

48.0
60.0

70.0

80.0

90.0

100.0

Carbon capture ratio (%)

Reference power plant without CO2 capture: 57.1% efficiency
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CCS projects in The Netherlands

CRUSTThe K-12B gas field

1st test: K12-B8 - Injector

2nd test: K12-B5 - Producer
2nd test: K12-B1 - Producer
2nd test: K12-B6 - Injector

courtesy GdF Netherlands
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CCS projects in The Netherlands

OCAPIndustrial CO2 re-use in greenhouses•CO2 from Shell Pernis,•170 kton CO2 reduction

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CCS Initiatives in The Netherlands

Nuon MAGNUM capture ready IGCC

SEQ oxy fuel ZEPP in Drachten

Nuon WAC Pre-combustion demo

NAM CO2 storage in de Lier

36

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ECN CCS activities• Pre-combustion decarbonisation– Sorption-enhanced reaction– Hydrogen-selective
membrane reactors– CO2 selective
membrane reactors• Oxyfuel combustion– SOFC + afterburner– Oxygen conductingmembranes• CO2 re-use/storage– Mineralisation
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DECAFF

Participation ECN in programs & projects• CATO: Dutch national CO2 program– Co-ordination Utrecht University– Running time 2004 – 2009
– ECN co-ordinates the pre-combustion CO2 capture work
package: hydrogen membranes and CO2 sorbents• CACHET: EU FP6 Integrated Project– Co-ordination BP– Running time 2006 until 2009
– ECN co-ordinates membrane WP and participates in WP on
sorption-enhanced Water Gas Shift coordinated by Air Products
and is co-financed by CCP.

• GCEP (Global Climate and Energy Program)– Co-ordination: Stanford University– Running time 2005 -2008– Sponsors: ExxonMobil, Toyota, Schlumberger, GE– ECN carries out the project ‘Advanced membrane reactors forhydrogen production’ together with TU Delft. Development of a
CO2 separating membrane reactor.

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Participation ECN in programs & projects
National EOS projects• C- CLEAR– Continuous SERP for “ZEPP”– Co-ordination: ECN– running time 2005-2008• CATHY– Catalysts for Separation enhanced reformers– Co-ordination:ECN– running time 2006 –2009• CAPTECH: extension to CATO
– Capture technologies for IGCC and PC– Co-ordination: ECN– running time 2006 -2009

LuchtH2Stripper• CO2ReMOVE (Policy studies, H2&CFF)– CO2 monitoring and verification• ACCEPT (Policy studies)– Public Acceptance of CO2 storage, economics, Policy and technology

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Waterstof
Gasturbine

KWS

EU IP projects

39

Electriciteitsproductie

CO2Reformer
Lucht
H2O(g)SERP for hydrogen production with CO2capture

SERP reactor
in adsorption
mode

steam
natural gas

PSA
steam

SERP reactor
in desorptionmodewaterknock out

CO240

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PurehydrogenSERP for electricity production withCO2 capture
H2 + steam
SERP reactor
in adsorption
modesteamnatural gas

airgasturbinesteam
SERP reactor
in desorption
modewater
knock out

CO24122-1-2007

generator

Shifting the equilibrium

Steam reforming
CH4 + 2H2O

4H2 + CO2

[CO2 ][H 2 ]K eq =[CH 4 ][H 2O]21000000
100000
10000
1000
CO2 slip [ppm]4SE-SMR: lab-scale experiment(S/C=6, 1 bar)

100
10
10%

10%

20%

30%

40%

50%

60%

70%

80%

90%

0.1
0.01
0.001
0.00014222-1-2007

SE-SMR: S/C=3, 17 bar

CO, CH4 conversion

100%

SERP: Shifting the equilibrium

Steam reformingCH4 + 2H2O

4H2 + CO2

[CO2 ][H 2 ]K eq =[CH 4 ][H 2O]21000000
100000CO + H2O

H2 + CO2[CO2 ][H 2 ]K eq =[CO ][H 2O ]4322-1-2007

SEWGS: Coal gas
20 barSE-WGS: Air-ATR, 17 bar

10000
1000
CO2 slip [ppm]4

Water gas shift

SE-WGS: lab-scale experiment
1 bar

SE-SMR: lab-scale experiment(S/C=6, 1 bar)

100
10
10%

10%

20%

30%

40%

50%

60%

70%

80%

90%

0.1
0.01
0.001
0.0001

SE-SMR: S/C=3, 17 bar

CO, CH4 conversion

100%ECN CCS activities
DECAFF
Hydrogen-selective membrane reactors
Fuel + air

HeatLow-CO2 fluegas
Natural gas+ H2O

Combustion

Flue gasHeat

CO to clean-CH4+H2O

CO+3H2

CO+H2OMembrane
H2

H2

H2

H2O

Permeate (incl. H2)Heat recoverysteam
CH4 100%
generator

2
Retentateup andCO2, H2O,
(H2, CO, CH4) compression

CO2+H2H2Heat

Natural gas

Sweep
Membranereactorconversion
75%

H,HO22MR experiment

Air

H2O

50%

Thermo

25%
0%
0,0GT
turbineNo permeation

22-1-2007~Generator

1,02,0444GTcompressor3,04,05,0ECN CCS activities
DECAFF
Power generation in SOFC with H2-MR
CO2richstream

FuelSMBSOFCAir

ShiftOxTout~Impact of fuel utilisation

Q1

Membrane temperature
difference [C]Total efficiency [-]

400

0.63

350

0.62

300
0.61

•Efficiency up to 62% LHV

250
0.6
2000.59•Fuel utilisation SOFC is key
parameter

150
0.58
100

0.57

50
EFFTOT
DELTAT

0.56
0.7

00.71

0.72

0.73

0.74

0.75

Fuel uti l i sati on [-]4522-1-2007

0.76

0.77

0.78

0.79

0.8

CCS projects at ECNGCEPCO2 separating membranes for advanced energy systems• Part of the GCEP project managed by Stanford Stanford
University– Sponsors: GE, EXXON, Toyota, and Schlumberger• 3 years (2.3 million $) project in cooperation with TU-Delft
overall efficiencies
economics

systemstudiesreactorrequirements

experimental
results

patentsIP

membrane& catalyst
development

fundamental knowledge
characterizationIPpublications

46

reactordesigndesired specifications

materials
research

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newdevelopments

reactor tests

Task 1.
Task 2.
Task 3.
Task 4.
Task 5.

System analysis and thermodynamic evaluations
Hydrogen membrane research & development
CO2 membranes research & development
Catalyst screening
Reactor modelling and design

Executed by ECN
Executed by TUD
Executed by ECN+TUD
Executed by ECN
Executed by ECN

CCS projects at ECN

GCEPSteam reformer
membrane reactor

Pre-reformer
Natural gas

SteamReforming

H2O

CO2

Steamsweep¾ Conversion relatively easy enhanced byseparation of H2 Æ favourable kinetics

Membrane reformer: Residual partial pressure of permeating compontent
in retentate as a function of conversion.
8.0

H2 and CO 2 retentate partialpressure (bar)Combined Cycle

H2/7.06.0¾ CO2 selective membranes show a too
low conversion and are therefore notsuitable, as opposed to H2 selectivemembranes

H2 membrane

5.0
4.0
3.0
2.0

CO2 membrane

1.0
0.0
0

10

20

30

40

50

60

70

80

90

100

Overall conversion (%)@ 600 oC, 40 bar, S/C = 3,Sweep: steam 5 bar, 600 oC, Sweep flow/Feed flow = 0.11 (mole/mole)47

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ECN CCS activities

DECAFF

Mineral CO2 sequestration in alkaline solid waste

CaSiO3 (s) + CO2 (g)→ CaCO3 (s) + SiO2 (s)∆Hr = -87 kJ/mol & ∆Gr = -44kJ/mol

Steel slag
CO2-sequestrated [g/kg]

Main route of natural CO2 sequestration:→ weathering of (Ca,Mg)-silicates160
1208040Wollastonit
e02575125

175

225

T [°C]

d < 106 µm, pCO2 = 20 bar

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ECN CCS activities

DECAFF

IPCC special report CCS

Down load: WWW.IPCC.CH

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Overview European CCS activities and R&D work at ECN
Acknowledgement• RITE• CASTOR team (Pierre Le Thiez, IFP)
• ENCAP team (Kristin Jordal, Sintef)• CACHET team (Richard Beavis, BP)• Nils.A.Rokke (Sintef.no)• CATO team ( Erik Lyssen)• Ruud van den Brink (ECN)• Jan Wilco Dijkstra (ECN)• Paul Cobden (ECN)• Paul van Beurden (ECN)• Wouter Huijgen(ECN)• Wim Haije (ECN)50

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