hybrid membrane based systems for co capture on natural
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Stanbridge CapitalOil & EnergyOil & Energy
Hybrid Membrane Based Systems for CO2Capture on Natural Gas and Coal Power Plants
PCCC2, Bergen, 18th September 2013
Bouchra Belaissaoui, Eric FavreLRGP, Nancy, FranceYann Le Moullec
EDF R&D, Chatou, FranceGilles Cabot
CORIA, Rouen, FranceDavid Willson
Stanbridge Capital, New York, USA
1
Post-combustion carbon capture and storage (CCS) technologyPost-combustion CO2 capture
Challenge: Reduction of the energy requirement of the capture step
Separation unitCOFlue gas CO2 to transportCO2 captureFlue gas
CO2 content : 4 -30%CO2 to transport
CO2 purity >=90%Capture ratio >=90%
Target : 2.5 GJ/ton of recovered CO2
Reference (MEA absorption + compression) : 4 GJ/ton of recovered CO2
Target : 2.5 GJ/ton of recovered CO2
Alternative approaches : Membrane based hybrid processes?
2
Outline
1- Membrane process specification
2. Hybrid process I: Coal power plant
3 Hybrid process II: Natural gas turbine
4. Conclusion and perspectives
3. Hybrid process II: Natural gas turbine
3
Membrane unit Post-combustion carbon capture and storage (CCS) technology1- Membrane process
Upstream P’Feed Flue gas Retentate
N2CO2
Downstream Permeable & CO2selective membrane
material
P’’
CO2/N2
Permeate CO2 rich stream 2
CO and N are separated due to their different permeability in the membrane CO2 and N2 are separated due to their different permeability in the membranematerial
The driving force is ensured by an appropriate transmembrane pressureCO f h N CO i h i d i h CO2 permeates faster than N2 CO2 rich stream is recovered in the permeate
4
Retentate :Feed :
1- Membrane process simulation
NCOUpstream
Downstream
P’
P’’
Qout = (1-).Qin
xout
Qin
xin
Pin
N2CO2
Permeate :Qp = .Qin , y
Modeling : Cross-plug flow model*
- Pressure ratio: =P”/P’Operating t
- CO2 permeate purity, y
- Inlet CO2 content , xin
Energy requirementPerformance
parameter
- CO2 recovery ratio, R
- Membrane selectivity: α=CO2/N2
+Material
parameters
- CO2 permeability: CO2 Membrane surface areaproperties
* Bounaceur R. et al, (2006) Energy, 31, 2556-2570. 5
Membranes and post-combustion CCS:A tentative process selection map
3.5
4.0
Standard MEA absorption process
2.5
3.0
red CO
2)
U.E target : E=< 2+0.5 (compression to 110 bar)GJth/ton CO2 =100
1.5
2.0
on of recove g ( p ) / 2 =100
R = 0.9
0 0
0.5
1.0
E (GJ/to
Coal combustion Biogas Steel industryNatural gas
turbineBiogas
combustion
y = 0.9
0.00.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45 0.5 0.55 0.6 0.65 0.7
Inlet CO2 mole fraction (xin)
Single stage membrane process E < 2.5 GJ/tonMultistage memb.
ce of
rane
s in
trategy Hybrid process ?
Key : There is a substantial benefit fromHybrid process : Membrane as a
preconcentration unit
Plac
mem
bCC
S s t Membrane as a
polishing unit
B. Belaissaoui , D. Willson , E. Favre, Chemical Engineering Journal, 211‐212 (2012) 122‐132
Key : There is a substantial benefit from strategically increasing the inlet CO2 content
6
Outline
1- Membrane process specification
2. Hybrid process I: Coal power plant
3 Hybrid process II: Natural gas turbine
4. Conclusion and perspectives
3. Hybrid process II: Natural gas turbine
7
2- Hybrid process: Membrane preconcentration + cryogeny
Qin
T=30°CQout
x >98%Membrane unitQ’
Retentate
Cryogenic unitPin =1bar
xout >98%
Pout=110barMembrane unit x’CO2
P’=1barIncondensable
xin,CO2
Cryogenic unit
CO2 capture ratio >90%
B. Belaissaoui , Y. Le Moullec, D. Willson , E. Favre, Journal of Membrane Science, 415-416 (2012) 424-434 8
2- Hybrid process: Membrane preconcentration + cryogeny
Qin
T=30°C
Pi =1bar
Qout
xout >98%Membrane unit
Q’
x’CO2
P’ 1b
Retentate
Cryogenic unitPin 1bar out
Pout=110barP’=1bar
Incondensable
xin,CO2
y g
Three-stage compression with intercoolers (Aspen software)with coupled turbine & booster compressor
* B. Belaissaoui , Y. Le Moullec, D. Willson , E. Favre, Journal of Membrane Science, 415-416 (2012) 424-434 9
1- Hybrid process: Membrane preconcentration + cryogeny
Q RetentateOptimisation
variableQin
T=30°C
Pin =1bar
Qout
xout >98%
P =110bar
Membrane unit
Q’
x’CO2
P’=1bar
Retentate variable
x
Cryogenic unitPout 110bar
Incondensable
xin,CO2
Occurrence of a minimum overall energy requirement ?
* B. Belaissaoui , Y. Le Moullec, D. Willson , E. Favre, Journal of Membrane Science, 415-416 (2012) 424-434 10
Simulation results10
d C
O2)
of re
cove
red
Feed compression with ERS
CO2/N2=50
E (G
J/to
n o CO2/N2 50
xin=0.15
10.375 0.425 0.475 0.525 0.575 0.625 0.675 0.725 0.775
Intermediate CO2 mole fraction (x')
E Membrane decreases significantly whenE-Membrane decreases significantly when a moderate CO2 permeate purity is aimed
11
Simulation results10
d C
O2)
of re
cove
red
E (G
J/to
n o
10.375 0.425 0.475 0.525 0.575 0.625 0.675 0.725 0.775
Intermediate CO2 mole fraction (x')
E C d i ifi tl hE-Cryogeny decreases significantly when concentrated CO2 flue gase is treated
12
10
Simulation results
E Hybrid = E Membrane +E Cryogenyd
CO
2)E Hybrid E Membrane +E Cryogeny
of re
cove
red
E (G
J/to
n o
10.375 0.425 0.475 0.525 0.575 0.625 0.675 0.725 0.775
Intermediate CO2 mole fraction (x')
Occurrence of a minimum energy requirement towards x’Occurrence of a minimum energy requirement towards x
13
10
Simulation results
d C
O2)
All Cryogeny
St d d MEA b ti i
of re
cove
red Standard MEA absorption+compression
20% energy decrease
E (G
J/to
n o
xin=0.15
CO /N 50
10.375 0.425 0.475 0.525 0.575 0.625 0.675 0.725 0.775
CO2/N2=50
Intermediate CO2 mole fraction (x')
The hybrid process significantly decreases the energy requirement compared to the standalone cryogenic separation and MEA absorption
B. Belaissaoui , Y. Le Moullec, D. Willson , E. Favre, Journal of Membrane Science, 415‐416 (2012) 424‐434 14
Outline
1- Membrane process specification
2. Hybrid process I: Coal power plant
3 Hybrid process II: Natural gas turbine
4. Conclusion and perspectives
3. Hybrid process II: Natural gas turbine
15
3- Integrated membrane / gas turbine process
Proposed concept : Flue gas recirculation + combustion in oxygen enhanced air (OEA)
Separation unit 1 Separation unit 2Gasturbine
Natural gas Power
O2/N2 OEA CO2 captureturbine cycle
FGR
Moderate O2 enrichment CO2 capture on concentrated flue gas
[O2] : 40- 80% [CO2] >= 30%# # Postcombustion (4% CO2)
Oxycombustion(100%O2)
16* Favre, E. Bounaceur, R., Roizard, D.(2009),, Sep. Purif. Technol , 68, 30-36. 16
3- Integrated membrane / gas turbine process
Capture ratio =90%
Flue gas recycling (FGR)
Key variable
Membranemodule
Combustion chamber
Natural gas Gas
Turbine 1‐Z
ZPinxin
C
N2 CO2
Cooler
parameters
Cryogenic
O2 enriched air(OEA) Patm
Yp=0.9Permeate
Compressor
to CO2 transport and sequestration
Air
process
250 MW NGT GE REF = 0.39
Simulation software EES
17
Combustion in air and without FGR]
2- Integrated membrane / gas turbine process
[, reference = - 15%,
4Cost
MEA absorption reference3,5
ost (
GJ/
TCO
2) MEA absorption referenceEnergy integration
Energy Recovery SystemsHeat exchanger
2 5
3
O2
Cap
ture
Co
7 3%
2
2,5
CO - 7.3%
- 6.3%
E= 1.5 GJ/tonE= 2.7 GJ/ton
0 5 10 15 20 25 30PIN (bar)
- Significant improvement of the energy efficiency of the process
B. Belaissaoui, G. Cabot, M.L. Cabot, D. Wilson, E., Favre Energy (2012) 38, 167‐175
Significant improvement of the energy efficiency of the process- Membrane selectivity helps to improve the energy effiency
18
• Major outcome of the study:
3- Conclusion and perspectives
• Major outcome of the study:
Membrane + cryogeny: Potential energy decreaseHigh selectivity is not needed (50 is enough)g se ec v y s o eeded ( s e oug )
Membrane / OEA/ NGT Potential energy decreaseLarge selectivity helps
• The use of membrane unit in hybrid processes can offer attractive performances fordiluted flue gas treatment
• Future work: Experiments +Trade-off CAPEX OPEX to be investigated
19
Stanbridge CapitalOil & EnergyOil & Energy
Hybrid Membrane Based Systems for CO2 Capture on Natural Gas and Coal Power Plants
PCCC2, Bergen, 18th September 2013
Thank you for your attention
Bouchra.belaissaoui@univ-lorraine.fr
20
21
Improved approach: Energy Integration Flowsheet
2- Integrated membrane / gas turbine process
e Z
Flue gas recycling (FGR)
er
Membranemodule
Combustion chamber
Natural gas
O2 enriched air(OEA)
Gas
Turbine 1‐Z Pinxin
PatmYp=0.9
Permeate
Compressor
N2 CO2Ex
pand
e
Heat exchanger
Cooler
to CO2 transport and sequestration
Air
Cryogenic process
1‐ZZ Membrane
Combustion chamber
Membranemodule
PatmYp=0.9Permeate
Heat exchangerCooler
CoolerModified flowsheet:
- Energy Recovery System
CMemb
OEA
Gas
Turbine
CFGR CFuelCOEANet Power
Pinxin
Expander
(Expander on the retentate)
- Heat exchanger(R t t t h ti i t
Air
Natural gas
Cryogenic process
OEA
N2, O2
Patm (Retentate heating prior to the expander)
22
Integrated approach: Performances
2- Integrated membrane / gas turbine process
3.5
O2)
Reference gas turbine cycle (config. A), =50
3
ent (GJ/ to
n CO
Reference gas turbine cycle (config .A), =100Reference gas turbine cycle (config. A), =200
Config.B, =50
2
2.5
rgy requ
ireme
Config.B, =200
Config.B, =100
1.5
2
E, overall en
e
10 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
E
- 6.3%
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
(heat exchanger efficiency)
B. Belaissaoui, G. Cabot, M.L. Cabot, D. Wilson, E., Favre Chemical Engineering Science (2013) 97, 256‐263 23
Influence of the membrane selectivity
1000Upper Bound(Robeson 2008)
Prospectives
100
CO2/N2
membranes
Polaris TM (MTR)Commercial membranes
10Selectivity
C membranes
11 10 100 1000 10000
CO2 Permeance, GPU
Membrane selectivity 50‐100‐200
CO2 membrane permeance (GPU) 1000 24
A membrane / MEA absorption hybridprocess is (probably) not relevant
5
p (p y)
4.5
4
3.5
30 0.05 0.1 0.15 0.2 0.25 0.3 0.35
% CO2% CO2
Specific energy requirement of a MEA carbon capture processas a function of CO2 inlet concentration in the flue gas 25
Hybrid process: Membrane preconcentration + cryogeny
8
9
)
5
6
7
of re
cove
red
CO
2
Cryogenic CO2 capture is not efficient for low CO2 content
2
3
4
ryog
enic
uni
t (G
J/to
n
Cryogenic CO2 capture can be very
0
1
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Inlet CO2 mole fraction (x')
E c efficient for high CO2 content
Qin
Xin
P =1bar
Qout
X t >90%
EMmembrane
ECCryogeny
QP
X’
P’ 1b
Retentate
Pin =1bar Xout >90%
Pout=110bar
CryogenyP’=1barT=30°C
Incondensable outlet 26
Hybrid process NGT / OEA / FGR: Selectivity helps
0.9
1
3500
4000Cost
0 7
0.8
0.9
3000
3500
MJ/
TCO
2) O2
CO2
0 5
0.6
0.7
2000
2500
X IN
-CO
2-
X O2
Cap
ture
Cos
t (
0 3
0.4
0.5
1000
1500
CO
2C
0.310000 5 10 15 20 25 30
PIN
Si ifi t i t f th ffi i f th
B. Belaissaoui, G. Cabot, M.L. Cabot, D. Wilson, E., Favre Energy (2012) 38, 167-175
Significant improvement of the energy efficiency of the processMembrane selectivity helps
27
Simulation results of the hybrid process (2)Energy requirement = f(x’CO2) xin, CO2
Feed compression with ERS =50 (available performances)
100ed
CO
2)
xi CO =0 05
All Cryogeny, xin,CO2 =0.05
10
on o
f rec
over
e xin, CO2 =0.05
xin,CO2 =0.15
All Cryogeny, xin,CO2 =0.15
E (G
J/to
xin,CO2 =0.3Standard MEA absorption
All Cryogeny, xin,CO2 =0.30
10.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Intermediate CO2 mole fraction x'
The hybrid process appears to be particularly interesting for intermediate CO2 contents, i.e. around 15%, the main target of carbon capture studies.
28
Simulation results of the hybrid process (3)Minimum energy requirement = f(xin, CO2 ) CO2/N2
Feed compression with ERS 10
over
ed C
O2)
Standard MEA absorption+compression
GJ/
ton
of r
eco
10.05 0.1 0.15 0.2 0.25 0.3
Em
in(G
Inlet CO mole fraction x
The minimum energy requirement decreases when CO2 inlet content increases and also when membrane selectivity increases.
Inlet CO2 mole fraction xin
The minimum energy consumption is slightly influenced by membrane selectivity (50 or 100) specially for xin, CO2 > 0.15.
29
Th t i ith i t l ( )
Cryogenic separation: simulation
Three-stage compression with intercoolers (Aspen software)
P’out= 1 barx’CO2
xout >98%Pout=110bar
CO2 capture ratio >0.952 pCO2 purity (xout) >0.98
Pump Isentropic efficiency : 0.8 Compressor isentropic
efficiency : 0.8530
3- Integrated membrane / gas turbine process
Natural gas ECO2
Key variable parameters
O2 Enriched Air
Membrane separation
N2
GasTurbine
ZEOEA
1‐Z
PINXIN
Cryogenicseparation N2, O2
CO2
Z
Flue gas
OEA
CO2 purity=90%Air recycling Capture ratio =90%
250 MW NGT GE REF = 0.39
Simulation software EES
31
PerspectivesPerspectives
For medium oxygen purity production, alternative technology (PSA,membrane air separation) could be investigated
32
2- Gas turbine efficiency
III- Performances for OEA feeding condition
2 Gas turbine efficiency
0,80,4ref
Membrane selectivity CO2/N2=100, yCO2= 0.9
0,5
0,6
0,7
0,25
0,3
0,35ref
0,3
0,4
0,5
0,15
0,2
0,25
X IN CO2
therm
AIR feeding
toech.line
0
0,1
0,2
0
0,05
0,1
OEA feedingst
- The thermal efficiency passes through a maximum value as Z increases.
000 0,2 0,4 0,6 0,8 1
Recycling ratio , Z
y p g- Concentrated CO2 in the flue gas can obtained (xin, CO2 > 0.2)
33
A single stage membrane module
Membrane unit Post-combustion carbon capture and storage (CCS) technologyMembrane process principal
P
Membrane
RQin Pupstream
PdownstreamCompressor
P t
Retentate
ExpanderPin =1barxin,CO2 =0.15
Q
x’CO2
P’out= 1 barPermeate
CO2 rich streamQin
Y= 90%CO2 capture ratio = 90%
Modeling framework :Cross-plug flow model 1 (M3Pro software)g p g ( f )
Model hypothesis : Binary dry CO2/N2 mixture
I th l diti A t t i iti it f
1 Bounaceur R. et al, (2006) Energy, 31, 2556-2570. 2 N. Matsumiya et al, (2005) Separation and Purification Technology, 46, 26-32.
Isothermal conditions. Isobaric condition in each side.
A strong parametric sensitivity of both units and y and xin
34
Three-stage compression with intercoolers (Aspen software)
Cryogenic separation
P’out= 1 barx’CO2
xout >98%Pout=110bar
CO2 capture ratio >0.952 pCO2 purity (xout) >0.98
Pump Isentropic efficiency : 0.8 Compressor isentropic
efficiency : 0.8535
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