CO2 Separation withMolecular Gate Membrane
Research Institute of Innovative Technology for the EarthChemical Research Group
Shingo KAZAMA
April 27, 2004GCEP Energy WorkshopsAt Stanford University
Established in July 1990, as a core research organization with support of METI as well as regional governments and private companies
Objectives; - The Development of Innovative Environment-Related Technologies- The Expansion of CO2 Sinks
Research Institute of Innovative Technologyfor the Earth (RITE) :
- Systems Analysis Research Group (Comprehensive and systematic evaluation of global warming mitigation technologies and proposal of optimal scenarios for the above technologies.)
- Plant Physiology Research Group (Improving the photosynthetic functions of plants targeted for use in dry area)
- Microbiology Research Group (Research related to the utilization of microorganisms to convert biomass into useful substances and to reduce or eliminate environmental pollutants)
- Chemical Research Group (Research for CO2separation /fixation technologies)
- CO2 Sequestration Research Group (Research for geologic and ocean CO2 sequestration)
Research Groups and Research Fields :
URL: http://www.rite.or.jp/ for more information
‚b‚n‚Q
‚b‚n‚QCO2
CO2CO2
TransportSeparation/Capture Injection
Injection
Onshore aquifer
Offshore
�aquifer
Large scale�Emission source
CO2 Aquifer Sequestration :
CO2 CaptureTotal 54 - 60$/t-CO2
40 - 48$/t-CO2
RITE Cost Estimates (In Japan)
IEA Cost Estimates (presented at CSLF)
CO2 CaptureTotal 17 - 45$/t-CO2
15 - 40$/t-CO2
Geological CO2 Sequestration Cost Estimates:
Cost reduction in CO2 capture is a key issue of success incarbon sequestration !
- 90%
70% -80%
CO2 Separation & Capture Technologies:
Absorption
Absorber StrippingColumn
AmineSolution
Reboiler
SteamFlueGas
TreatedGas
Adsorption Membrane
VacuumPumpFlue
Gas
TreatedGas
Adsorbent
FlueGas
TreatedGas
VacuumPump
Chemical AbsorptionAmine Solution,Alkali Carbonate
SolutionPhysical AbsorptionAbsorption-Membrane
Hybrid
Physical AdsorptionPSA, TSA
Chemical Adsorption
Polymeric MembraneInorganic Membrane
(Ceramic, Carbon,Zeolite)
Molecular Gate Type
CO2
CO2
CO2
CO2
Membrane
:R&D in RITE
FeedSide
PermeatedSide
Pressure
High
Low
Solubility
Diffusivity
Permeability
X
Model of Gas Separation by Polymeric Membrane:
PCO2 >> PN2
Membrane
CO2
N2
Polyimide Containing Loop Shaped Moiety
Fluorene Moiety (RITE Cardo Polyimide)
1. Good Gas Permeability
2. Good Solubility
3.Good Thermal Stability
Excellent CO2/N2 SeparationProperty Asymmetric Membrane Preparation High Temperature Usage
Cardo Polyimide:
NC
C
CN
CO O
OO
* *
n
NC
CO
C
O
O
CN
CO
O
n
NC
C
CN
C**
O
O
O
O
n
n
NC
C CC
NC
O
O
O
O
* *CF3
CF3N
C
CO
C
O
O
CN
CO
O
n
* *
CH3 CH3
CH3H3C
* NC
CO
C
O
O
CN
CO
O
n
(H2C)6
NC
CO
C
O
O
CN
CO
O
nCOOCH3
NC
C
CN
CO O
OO
60
NC
C
CN
CO
O
O
O
40
CH2X CH2X
CH2XXH2C
CH2X CH2X
CH2XXH2C
PMDA-typeBTDA-type BPDA-type
6FDA-type 4Me-type Cardo-less
Br-type(PMBP64(4Me)-Br) Ester-type(BT-COOMe)
Chemical Structures of Cardo Polyimides:
80% of X is Br
PCO2 / Barrers
PC
O2
/ PN
2/ -
10
20
30
40
50
0.1 1 10 100 1000
Ester-type(BT-COOMe)
Br-type(PMBP64(4Me)-Br)
PMDA-type
BTDA-type
BPDA-type
6FDA-type
4Me-type
Cardo-less
Cardo PolymersExcept for Polyimide
�
Press Difference�101 kPa, Measured at 25 C1 Barrer = 7.5 x 10-18 m3 m m-2 s-1 Pa-1
CO2 Separation Property:
Conventional Polymers
Inner Coagulant: Water
Polymer Dope
Air Gap
Inner CoagulantPolymer Dope
CoagulationBath (1st)
CoagulationBath (2nd)
RinsingDry & Anneal
Tube-in-orifice Spinneret
Schematic Representation of Spinning Set:
CO2 Separation Property of Hollow Fiber Membrane Made from Br-type Cardo Polyimide(PMBP64(4Me)-Br)
SEM ImageCross Section
100 micro meter
CO2 Permeation 1 x 10-3 cm3(STP) cm-2 s-1 cmHg-1
Rate: (=7.5 x 10-9 m3 m-2 s-1 Pa-1)CO2/N2 Selectivity: 40
Measured at 25 C
Cardo Polyimide Asymmetric Hollow fiber:
Module of Cardo Polyimide Hollow Fiber:
Capacity : 1.6 Nm3/h (Flue Gas)Membrane Area: 8 m2
Hollow Fibers: 25,600 pieces
For Steel Works: CO2=26.5%
For Coal-Fired Power Plant:CO2=14.1%
CO2 Amount Captured: 180t-CO2/hCO2 Concentration: 99.5%
CO2Separation Cost/JPY/t-CO2
RITE Membrane (Cardo)
Amine Solution (KS)
Cost Comparison:
0 2000 4000 6000 8000
Liquefied Separation
17 33 6750$/t-CO2
Liquefied Separation
Liquefied Separation
Liquefied Separation
RITE Membrane (Cardo)
Amine Solution (KS)
Further Cost Reduction in CO2 Capture:
-CO2 recovery from atmospheric pressure gasstream might have a cap on cost reduction.
-Pressurized gas stream might have potentialfor further cost reduction.
- Pressurized gas stream- IGCC Process gas (e.g. FutureGen)- Natural gas
Approaches to Cost Reduction:
0 25 50 75 100Cost Breakdown(percentage)/%
Vacuum Pump Elect.& Blower Power
PlantConstruction
Max. 75% Cut in Cost
Membrane Etc.AtmosphericPressureGas Stream
PressurizedGas Stream(IGCC ProcessGas)
Cost Breakdown of Membrane Separation
CO2/H2Selectivity H2 Rich Flow CO2 Rich Flow
H2: 94%CO2: 6%
H2: 4%CO2: 96%
0.3Polymeric Membrane
H2: 80%CO2: 20%
H2: 55%CO2: 45%
0.1Ceramic Membrane
H2: 90%CO2: 10%
H2: 38%CO2: 72%
Selectivity Required for IGCC Process Gas:
In the case of feed gas composition, CO2:40% and H2:60%
After Membrane Separation
100New Concept
Membrane
What is Ideal Membrane Material?
Gas A Gas BFeed
Permeate
Pressure
High
Low
Layer of Gas A
Gas Permeation Blockade by Moisture:
Micro PorousMembrane
H2O Gas BGas B
Gas B LargePermeation
Very Small Permeation
Without Moisture With Moisture
H2O Large Permeation
CO2 N2, H2etc.Feed
Permeate
Pressure
High
Low
CO2 Molecular Gate Membrane:
PAMAM Dendrimer (Generation 0):
H2N
NH
N N
HN O
H2N
ONH
O
H2N
HN
O
NH2
- CO2/N2 Selectivity: 19000A. S. Kovvali, H. Chen, and K. K. SirkarJ. Am. Chem. Soc. 2000, 122, 7594-7595
In Situ Module Modification:
SupportingMembrane
Solution ofMembraneMaterials
CommercialUF, RO Module
Solution
ReducedPressure
Pump
ReducedPressure
Conc.Gradient
MembraneMaterial
Selectivity CO2/N2=1 Selectivity CO2/N2=67
600nm
QCO2=1.0x10-3* QCO2=3.9x10-5*
PSFUF Membrane
PAMAM DendrimerComposite Membr.
020000400006000080000
100000
020040060080010001200Binding Energy (eV)
cps
C1s
S2pS2s
O1s
01000020000300004000050000600007000080000
020040060080010001200Binding Energy (eV)
cps N1s
In Situ Module
Modification
*�cm3/(cm2 s cmHg) = 7.5x10-6 m3/(m2 s Pa)
Result of In Situ Module Modification:
On-Going R & D:
-Research and Development of Materials fora CO2 Molecular Gate Function
- Chemical Modification of Dendrimer- Other Different Material
-Improvement of In-Situ Module Modification- Pin-Hole Free Thin Layer- Garter Layer
Japan
USA
RITE
National Energy Technology Laboratory-DOECarbon Sequestration Science Focus Area-Modular CO2 Capture Facility -Field Test of Module
International Collaboration:
-Molecular Gate Materials & Membranes-Module Development -System Analysis
The University of Texas at Austin-Information Exchange in Membrane Fabrication
Cooperative Research
Meiji University (Commission)-Membrane Fabrication
-CO2 molecular gate membrane has a potentialfor reducing CO2 capture cost in combinationwith a pressurized gas stream.
-RITE contributes for developing modules of CO2 molecular gate membranes with International collaboration.
-This research project is funded by METI.
Conclusions & Acknowledgement:
Shingo [email protected]
