Technology for a better society CO 2 separation and utilization via dual-phase high-temperature...

Technology for a better society

CO2 separation and utilization via dual-phase high-temperature membranes

Wen Xing1, Thijs Peters1, Marie-Laure Fontaine1, Rahul Anantharaman2, Anna Evans3, Truls Norby3, Rune Bredesen1

1 SINTEF Materials and Chemistry2 SINTEF Energy3 Department of Chemistry, University of Oslo

Technology for a better society 2

2007 2008 2009 2010 2011 2012 2013 20140

10

20

Mu

mb

er o

f p

ub

licat

ion

Year

Dual phase + CO2+ membrane

Increasingly interesting !!

Scopus

New type of membranes

SINTEF, ASU,

Newcastle Universit

y…


CO2 permeable inorganic porous membranes

Reproduced from talk by Y.S.Lin, July 10, 2013 Pittsburgh, Pennsylvania

High temperature

Non porous membrane

100% selectiveOr partially selective to

both CO2 and O2

Dual-phase CO2 separation membrane


4

Potential applications of membranes

Pre- and post- combustion CO2 capture

• Efficient thermal integration• Expected higher stability towards

contaminants

Catalytic membrane reactor e.g. dry reforming of methane

CO2 + CH4 → 2H2 + 2CO

CO2 +H

2 + H2 O

CO2

CO2 +N

2 +O2 +H

2 O

CO2

Flue gas: CO2+N2+O2

CH4 2 H2 + 2 CO

Pre-combustion

Post-combustion

syngasCO2 + 2CH4 + O2 → 3H2 + 3CO+H2O

Dry reforming

Dry reforming combined with POX

Anderson, M. and Y. S. Lin (2013). AIChE Journal 59(6): 2207-2218.


Non-electronically conducting oxides support infiltrated with Na+ ion conducting melts

One example of dual-phase membrane for pre-combustion decarbonization

Molten salts (eutectic mixtures of carbonates …)

CeO2


Membranes controlled by transport contribution from melt and solid phase

feed

sweep

OeCOeOCO2CO 2222

323

dlnptdlnptt2σL4F

RTj

Pure ionic Pure electronic

CO32- e-

CO2:O2 = 2:1

CO32- O2-

CO2

CeO2 YSZ MetalCO2

e-

Mixed conductors

Mixed ionic & el.

CO32- O2-

CO2 + O2 mixture

CO2+ O2 CO2+ O2

Gradient

Molten salt Molten salt Molten salt


Performance

• Depending on vol.% of carbonates infiltration - Increasing in carbonate vol.%

resulting in increased CO2 flux and decrease the mechanical strength

Membrane thickness: 1 mm

Feed side: 20% CO2 + 20% He + 60% N2

Sweep side: 99.999% Ar

Temperature: between 650 and 550 °C

1.05 1.10 1.15 1.20 1.25

1E-3

0.01

0.1

1000/T (1/K)

50 vol.% carbonates 38 vol.% carbonates 28 vol.% carbonates

C

O2 f

lux

(mL

/cm

2 s

)

Ag

675 650 625 600 575 550 525 oC

• Depending on electronic conduction of the matrix

-transport both CO2 and O2


1.08 1.10 1.12 1.14 1.16 1.18 1.20 1.2210-3

10-2

C

O2

flu

x (m

l / c

m2 m

in)

2.5% in sweep side 0.01% in sweep side

1000/T (1/K)

650 625 600 575 550 oCEffect of steam


Feed side: 20% CO2 + 20% He + 60% N2

Sweep side: Ar + 2.5% steam

Temperature: between 650 and 550 °C

• Depending on the steam content in feed and sweep sides- Increasing steam content in feed and

sweep side increases CO2 flux

- The increase is more significant by introducing steam to the sweep side


Oxide ion addition in molten phase

1 2 3 4 5 6 7

0.003

0.004

0.005

0.006

0.007

0.008

0.009

0.01

0.011

0.012

CO

2 fl

ux

(ml /

min

cm

2 )

High steam in sweep side "Dry" in sweep side

Time (day)

550 oC


Feed side: 20% CO2 + 20% He + 60% N2

Sweep side: Ar + 2.5% steam

Temperature: 550 °C

CsVO3 : MoO3 = 3:1 (molar)CsVO3+MoO3 : (Li0.62K0.38)2CO3 = 1:5 (weight)

• Depending on the oxide ion addition

• Oxide ion addition enhance the CO2 flux under "dry" conditions (0.01% steam).

• Under higher steam condition, the steam effect dominates


1 month

0 500 1000 1500 20000.000

0.001

0.002

0.003

0.004

0.005

CO

2 fl

ux

(ml/

cm

2 min

)

Time (h)

Long term stability in reducing atmosphere

In CO2 + He + N2 at feed side Ar in sweep side550 °C • Feed : 20% CO2 + 20%H2+20% He + 40% N2

• Sweep : 99.999% Ar• 550 °C

Introducing H2 to the feed side

Stable region


Process integration and modeling for a 400MW plant

No capture MEA capture Dual-phase membrane

Net power output (MW) 416.4 354.3 ~333

Net ele. Eff. % LHV 58.13 49.46 ~46.5

Eff. Penalty % 0 8.67 ~11.5

Modelling of post-combustion with NGCC

Membrane thickness: 0.1mm

Membrane temperature: 500 to 550 °C

Operation methods:

-Post combustion (NGCC): with steam sweep

-Pre combustion (IGCC): without sweep (~35 bar in feed)

Details can be found in poster: Rahul Anantharaman et.al.


Process integration and modeling for a 400MW plant

Details can be found in poster: Rahul Anantharaman et.al.


• The estimated membrane area: 13202 m2 (decreases with increasing flux) for a 400MW plant.

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Cost estimation

Molten phase cost (less dominating):- carbonates/salt (low cost)- Infiltration process is simple

and low cost (dip-coating)

Porous support cost:? Depends on materials

and microstructure /processing

Fabrication cost

System Integration cost

Operational cost


• Dual-phase CO2 separation membranes provide high CO2 selectivity (500 to 900 °C).

• Potential for CO2 capture and membrane reactor for chemical production.

• Stable operation for ~1500 h demonstrated.

• Assessment of integration of membranes in a 400MW power plant :

- for post-combustion (NGCC): less efficient as compared to MEA capture

- for pre-combustion (IGCC): outperformed selexol capture

14

Summary


Acknowledgements

15

The support from the Research Council of Norway (RCN) through the CLIMIT program (project number 207841) is gratefully acknowledged.

DECARBIT projectThe support from the European Commission through the FP7/2007-2013 under grant agreement n° 211971


Additional info.

16


Fabrication of planar membranes1 mm thick sample

Dip-coating in molten carbonates at 600°C

(Li0.62K0.38)2CO3

CeO2

Carbonates

Polymer nanoparticles

Corn starch

Chitosan

Best result !100 µm

10 µ10µm


Pressure tolerance calculation

0.1 1 10-10

0

10

20

30

40

50

60

70

p (

bar

)

Pore radius (m) 0.90 0.95 1.00 1.05 1.10 1.15 1.20 1.25 1.30

3.5

3.6

3.7

3.8

3.9

4.0

4.1

4.2

p (

bar

)

1000/T (k-1)

800 750 700 650 600 550 500 oC

1 m pore radius

J. Electrochem. Soc., Vol. 144, No. 3, March 1997


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