Membranes and post-combustion carbon dioxide capture · Pilot absorption unit for gas boiler plants...
Transcript of Membranes and post-combustion carbon dioxide capture · Pilot absorption unit for gas boiler plants...
Membranes and post-combustion
carbon dioxide capture
Laboratoire Réactions & Génie des Procédés (UPR CNRS 3349)
Université de Lorraine Nancy FRANCE
Eric FAVRE
Nancy… somewhere in France
Nancy, Lorraine, France
Membrane contactors for intensified absorption processes:
High flux dense skin composite fibers (ANR Cicadi) Pilot membrane contactor design and test (FP7 CESAR) Membrane contactor for chilled ammonia process (ANR Amélie) Pilot absorption unit for gas boiler plants (ANR Energicapt) Optimization of solvent/gas absorption processes (with EDF)
Membrane gas separations:
Material synthesis Mixed Matrix Membranes (ACI Carbomem) Membrane characterization (mass transfer, separation performances) Process modelling (M3Pro software)
Hybrid processes:
Oxygen enriched air combustion / membrane capture (Cocase ICEEL) Membrane concentration / cryogenic condensation (with EDF)
Membrane team LRGP (EMSP) Current research projects on CCS
Prospective & breakthrough approaches Liquid membranes (TIPS Russia) Impregnated particles (MESR) Electrical swing adsorption (ACI Procap) Cyclic membrane gas separations (ICEEL)
i) Introduction
ii) Single stage parametric sensitivity
iii) Multistage approaches
iv) Hybrid process:
Coal power plant
Gas turbine
v) Conclusion
Outline
0 2 4 60
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4
6
c2
(g
/L)
c1 (g/L)
SMB Classique M3C Continu M3C Moyen
Introduction
Source: Figueirao J. et al. DOE (2007) Int. J. Greenhouse Gas Control
Membranes: a potential 2nd generation carbon capture process
Carbon capture
strategy
Target mixture Conditions First generation
separation
process
Possible
breakthrough
membrane
process
Oxycombustion
O2/N2
P atmospheric
T ambient
Cryogeny
Ion Transfer
Membranes (ITM)
Precombustion
CO2/H2
P up to 80 Bar
T 300 – 500 C
Gas-liquid
absorption in
physical solvent
Membrane reactor
Postcombustion
CO2/N2
P atmospheric
T 100 – 250 C
Gas-liquid
absorption in
chemical solvent
(MEA)
Membrane gas
separation
Membranes & carbon capture strategies
p’ : Upstream pressure
p’’ : Downstream pressure
Qp: Permeate flowrate
y: CO2 mole fraction
pIn: Feed pressure
Qin: Flowrate
xin: CO2 mole fraction
Retentate Feed
Permeate To compression
Qout: Flowrate
xout: CO2 mole fraction
Sweep
Expander
Permeability of A PA = DA SA
where DA = diffusion coefficient
SA = solubility coefficient
Selectivity
/A A A
A B
B B B
P S D
P S D
A classical single stage gas permeation modelling framework
Membrane separation & CCS: a simplified overview
Feed composition x
Capture ratio R
Purity y
Selectivity
challenge
Operating
Conditions (P, T)Energy
GJth/ton
Feed flow
rate vs outlet
performances
Productivity
Maximal flux
OPEX
CAPEX
Energy cost
Membrane cost
(€/m2)
Overall
Capture
Cost
Materials challenge of gas separation membranes
Favre, E. (2007) Carbon dioxide recovery from post combustion processes: Can gas permeation membranes compete with absorption? Journal of Membrane Science, 294, 50-59
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10
100
1000
0.01 0.1 1 10 100 1000 10000 100000
Sele
ctiv
ity
CO
2/N
2
CO2 Permeance, GPU
Upper Bound (Robeson 2008)
Chemical membranes (FSCR, LM)
Inorganic membranes
Polymers
Membrane
type
Material and/or
carrier
CO2/N2
selectivity
CO2 permeability
(Barrer) or
permeance
(GPU)
Gas
separation
membrane
(dense
polymers)
PEO-PBT
PEG/Pebax©
PEG-DME/ Pebax©
PEGDA/PEGMEA
Polaris™
70
47
43
41
50
120 Barrer
151 Barrer
600 Barrer
570 Barrer
1000 GPU
Fixed Site
Carrier
Membrane
(FSCM)
PAAM-PVA / PS
PVAm/PVA
PEI / PVA
PDMA/PS
PDMAMA
80
145
230
53
80
24 GPU
212 GPU
1 GPU
30 GPU
5 GPU
Liquid
Membrane
(LM)
PVAm-PVA/PS
PVAm/PVA
Amines/PVA
Carbonic anhydrase
Amines / PVA
90
90
500
250
493
22 GPU
15 GPU
250 GPU
80 GPU
693 Barrer
Materials performances for post-combustion carbon capture
Baseline case for simulations
Qin
xin
Pin=1bar
E
Vacuum
pump
Pupstream
Pdownstream
QR
xR
QP
y
Pout = 1bar
Feed compression with ERS on the retentate
Qin
xin
Pin=1bar
EC
Expander
- ET
QR
xR
QP
y
Pout = 1barE=EC-ET
Compressor
Pupstream
Pdownstream
Permeate
CO2 rich stream
Permeate vacuum pumping
Membrane
Single stage simulations: Process alternatives
Permeate
CO2 rich stream
0
2
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12
0.0
0.2
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0.8
1.0
1.2
1.4
1.6
1.8
2.0
0.4 0.5 0.6 0.7 0.8 0.9 1.0
Me
mb
ran
e S
urf
ace
are
a [×
10
3m
2/(
kg
CO
2.s
-1)]
En
erg
y r
eq
uir
em
en
t (G
J/to
n o
f re
cov
erd
CO
2)
Recovery ratio, R
y= 0.9xin=0.3
=100
The feed compression / vacuum pumping dilemma
Procédés de capture du CO2
i) Absorption gaz liquide conventionnelle
ii) Absorption par contacteurs à membranes
iii) Adsorption
iv) Membranes
0 2 4 60
2
4
6
c2
(g
/L)
c1 (g/L)
SMB Classique M3C Continu M3C Moyen
Parametric study of a single stage gas
permeation module
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0.45 0.50 0.55 0.60 0.65 0.70 0.75 0.80 0.85 0.90
En
erg
y r
eq
uir
em
en
t, E
(G
J/t
on
)
CO2 permeate mole fraction, y
xin=0.15
xin=0.3
xin=0.05
= 100
= 100
= 50
= 200
= 50
Strong parametric sensitivity on feed composition
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Energ
y r
eq
uir
em
ent
(GJ/to
n C
O2)
Recovery ratio, R
y=0.4
Standard MEA absorption process
=50 xin =0.15
Tackling the capture ratio / purity challenge
B. Belaissaoui , D. Willson , E. Favre, Chemical Engineering Journal, 211-212 (2012) 122-132
=100
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
0.05 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
E (G
J/to
n o
f re
cove
red
CO
2)
Inlet CO2 mole fraction (xin)
Single stage membrane process E < 2.5 GJ/ton
Standard MEA absorption process
Coal combustionBiogas
Steel industry
U.E target : E=< 2+0.5 (compression to 110 bar)GJth/ton CO2
Hybrid process : Membrane as a preconcentration unit
Multistage memb.
Pla
ce o
f m
emb
ran
es in
C
CS
stra
tegy
Membrane as a polishing unit
Natural gas turbine
Biogas combustion
B. Belaissaoui , D. Willson , E. Favre, Chemical Engineering Journal, 211-212 (2012) 122-132
A tentative process selection map
Procédés de capture du CO2
i) Absorption gaz liquide conventionnelle
ii) Absorption par contacteurs à membranes
iii) Adsorption
iv) Membranes
0 2 4 60
2
4
6
c2
(g
/L)
c1 (g/L)
SMB Classique M3C Continu M3C Moyen
Multistage gas permeation modules for
carbon capture
Herzog et al., Environ. Prog. (1991) 10, 64-74.
CO2 recovery 80%, CO2 purity 90%
Energy requirement 50-75 % of combustion energy of coal
(MEA 47-79 %)
First two stages membrane gas separation process
Module type Operating
conditions
Author
Two stage with
recycle
Compression
(21.4 Bar)
Herzog et al. (1991)
Two stage with
expander
Compression
(54 Bar)
Van der Sluis et
al.(1992)
Two stage with
recycle
Compression
(1.5 Bar) and vacuum
(80 mBar)
Ho et al. (2008)
Multistage with
or without
recycle
Compression (10 bar),
vacuum (0.03 Bar)
Zhao et al. (2009)
Two stage with
recycle
Compression (3 Bar)
and vacuum (0.2 Bar)
Merkel et al. (2009)
Two stage with
or without
sweep
Compression (2-5
Bar) or vacuum (25-
125 mBar)
Hussain et al. (2010)
Multistaged membrane gas separation processes: overview
MTR novel 2 stage membrane flowsheet for post-combustion CCS application
Merkel et al., J. Membrane Science (2010) 359, 126-139.
MTR DOE two stages membrane gas separation process
Procédés de capture du CO2
i) Absorption gaz liquide conventionnelle
ii) Absorption par contacteurs à membranes
iii) Adsorption
iv) Membranes
0 2 4 60
2
4
6
c2
(g
/L)
c1 (g/L)
SMB Classique M3C Continu M3C Moyen
Hybrid processes with membrane
modules for carbon capture
3
3.5
4
4.5
5
0 0.05 0.1 0.15 0.2 0.25 0.3 0.35
Influence %CO2 sur E (psot-combustion MEA 30%)
% CO2
A membrane / absorption hybrid process is (probably) not relevant
0
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7
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9
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
ryo
gen
ic u
nit (
GJ/t
on
of
rec
ove
red
CO
2)
Cryogenic CO2 capture can be very
efficient for high CO2 content
Cryogenic CO2 capture is not efficient
for low CO2 content
Hybrid process: Membrane preconcentration + cryogeny
Qin
Xin
Pin =1bar
Qout
Xout >90%
Pout=110bar
EM
membraneEC
Cryogeny
QP
X’
P’=1barT=30°C
Retentate
Incondensable outlet
Three-stage compression with intercoolers (Aspen software)
Cryogenic separation: simulation
CO2 capture ratio >0.95
CO2 purity (xout) >0.98
x’CO2
P’out= 1 bar
xout >98%
Pout=110bar
Pump Isentropic
efficiency : 0.8
Compressor isentropic
efficiency : 0.85
B. Belaissaoui , Y. Le Moullec, D. Willson , E. Favre, Journal of Membrane Science, 415-416 (2012) 424-434
Hybrid process: performances
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10
0.375 0.425 0.475 0.525 0.575 0.625 0.675 0.725 0.775
E (
GJ/t
on o
f re
cove
red
CO
2)
Intermediate CO2 mole fraction (x')
The hybrid process significantly decreases the energy requirement compared to the
standalone cryogenic separation and MEA absorption.
20% energy decrease
All Cryogeny
Standard MEA absorption+compression
Membranemodule
Combustion chamber
to CO2 transport and sequestration
Air
Natural gas
Cryogenic process
O2 enriched air(OEA)
Gas
Tu
rbin
e 1-ZZ
Pin
xin
Patm
Yp=0.9
Permeate
Flue gas recycling (FGR)
Compressor
N2
CO2
Cooler
Hybrid process: Membrane / OEA / FGR on Gas turbine
There is a substantial benefit from increasing the inlet CO2 content: flue gas recirculation and/or combustion in oxygen enhanced air (OEA)
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1
1000
1500
2000
2500
3000
3500
4000
0 5 10 15 20 25 30
XIN
-CO
2-
XO
2
CO
2C
ap
ture
Co
st (
MJ
/TC
O2)
PIN
Cost
O2
CO2
Improved energy efficiency Selectivity helps
B. Belaissaoui, G. Cabot, M.L. Cabot, D. Wilson, E., Favre Energy (2012) 38, 167-175
Membranemodule
Combustion chamber
to CO2 transport and sequestration
Air
Natural gas
Cryogenic process
O2 enriched air(OEA)
Gas
Tu
rbin
e 1-ZZ
Pin
xin
Patm
Yp=0.9
Permeate
Flue gas recycling (FGR)
Compressor
N2
CO2
Exp
and
er
Heat exchanger
Cooler
Combustion chamber
CMemb
Air
Natural gas
Cryogenic process
OEA
N2, O2
Ga
s Tu
rbin
e
1-ZZ
CFGRCFuelCOEA
Membranemodule
Patm
Yp=0.9Permeate
Net Power
Pin
xin
Heat exchangerCooler
Exp
and
er
Cooler
Patm
1
1.5
2
2.5
3
3.5
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
E, o
vera
ll en
ergy
req
uir
emen
t (G
J/ t
on
CO
2)
(heat exchanger efficiency)
Reference gas turbine cycle (config. A), =50
Reference gas turbine cycle (config .A), =100
Reference gas turbine cycle (config. A), =200
Config.B, =50
Config.B, =200
Config.B, =100
Integrated approach: Performances
Conclusion
• Membranes processes offer a large variety of potential applications in a CCS
framework (separation, concentration, polishing)
• Very large number of publications on materials, few on process, very few on technico-
economical studies. The interest of selective vs permeable materials remains controversial
•Investigations are mostly limited to model mixtures and at laboratory scale
• Crucial need for studies on real flue gases (dust, water, SOx, O2), ideally at pilot scale
• Hybrid and/or integrated processes should be more systematically investigated
Membranes processes and post combustion CCS: utopy or opportunity?
36
Thank you for your attention!
Air Liquide DOE project
Unconventional approach : Reverse selective membranes
CO2 selective membrane N2 selective membrane
y
Favre, E., Roizard, D., Koros, W.J. (2009) Ind. Eng. Chem. Res., 48 (7) 3700-3701.
0
0.1
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0.8
0
0.05
0.1
0.15
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0.25
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0.35
0.4
0 0.2 0.4 0.6 0.8 1
XIN
CO
2 an
d X
O2
-OEA
the
rm
Z
OEA feeding
AIR feeding
sto
ech
.lin
e
ref
B. Belaissaoui, G. Cabot, M.L. Cabot, D. Wilson, E., Favre Energy (2012) 38, 167-175
Hybrid process: Impact on energy efficiency
Membrane Gas Separation: Applications & Market