from mea to demixing solvents and future steps, a roadmap...
TRANSCRIPT
Post-Combustion CO2 Capture Workshop
11th-13th July, 2010, Talloires, France
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Controlled CO2 | Diversified fuels | Fuel-efficient vehicles | Clean refining | Extended reserves
From MEA to demixing solvents and future steps, a roadmap for lowering the cost of post-
combustion carbon capture
Ludovic Raynal, Pierre-Antoine Bouillon, Adrien Gomez and Paul Broutin
+ IFP colleagues
PCC Workshop, 11th-13th July, 2010, Talloires, France2
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Outlook
� IFP & CCS
� 1st generation PCC
� Needs for new processes
� DMX™ and future processes
� Conclusion
� 1st generation PCC
� Needs for new processes
� DMX™ and future processes
� Conclusion
PCC Workshop, 11th-13th July, 2010, Talloires, France3
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PCC Workshop, 11th-13th July, 2010, Talloires, France4
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CCS @ IFP
� PS1 strategic priority
� intensive work on PCC
� 1st & 2ndgeneration processes
� future processes
� involve many research fields
PCC Workshop, 11th-13th July, 2010, Talloires, France5
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Outlook
� IFP & CCS
� 1st generation PCC
� Needs for new processes
� DMX™ and future processes
� Conclusion
� Needs for new processes
� DMX™ and future processes
� Conclusion
� IFP & CCS
PCC Workshop, 11th-13th July, 2010, Talloires, France6
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PCC reference = MEA
� Reference process : MEA 30 wt.%
� proven via Castor pilot test campaigns
� Cost evaluated around 50 to 65 €/t CO2 avoided
� Energetic penalty for the power plant : - 10.5 pts
� High sensibility to O2 : degradation
� IFP solution : HiCapt+™
� increase in MEA concentration + use of additives
� keep reliability and robustness of the reference process
� increase performances
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� HiCapt+™ (40 wt.% MEA +
additives)
� Screening and tests of
inhibitors
� More than 130 products
evaluated
� very good results obtained
� Simulation of Castor results
� use of Aspen (electrolyte NRTL)
� validation vs Castor tests
MEA at 40 wt % after 1000 h pilot test (with and without inhibitor)
0
5000
10000
15000
20000
25000
30000
none U2 V1 V2 Y1
Inhibitors (0,25%-wt)
An
ion
Ca
nc
en
tra
tio
n
(pp
m)
0
50
100
150
200
250
300
350
400
U2 V1 V2 Y1
formiate
acetate
oxalate
nitrate
nitrite
HiCapt+™ process – results 1/2
PCC Workshop, 11th-13th July, 2010, Talloires, France8
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IFFPPPPPPPP
ENEL Site :Coal power plant in Brindisi (4 x 660 MWe)
Pilot Main Data :Flue gas : 10 000 Nm3/hCO2 captured : 2.25 t/hStart-up: 2010
ENEL/ IFP collaboration :Classical MEA processHiCapt+™ process
HiCapt+™ process – results 2/2
PCC Workshop, 11th-13th July, 2010, Talloires, France9
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Outlook
� IFP & CCS
� 1st generation PCC
� Needs for new processes
� DMX™ and future processes
� Conclusion
� DMX™ and future processes
� Conclusion
� IFP & CCS
� 1st generation PCC
PCC Workshop, 11th-13th July, 2010, Talloires, France10
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Targets for a new PCC process
absorber
stripper
purified gas
CO2
lean amine
rich amine
flue gas
HP CO2
flue gas
purified flue gas-90 % CO2
CO2 @ 110 barsy > 95 %
Objective :develop "low-cost" CO2 capture processes(with clearly given boundary counditions)
absorber
stripper
purified gas
CO2
lean amine
rich amine
Too high CO2 costs : 50 €/t - 65 €/t
waste
Flue gas flowrate 78 480 kmole/hFlue gas temperature 45 °CFlue gas pressure 1 bar abs.Flue gas composition
CO2 13% vol.N2 75% vol.O2 5% vol.H20 7% vol.
PCC Workshop, 11th-13th July, 2010, Talloires, France11
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Scientific & Technical information� VLE data + adapted thermodynamic model
� Degradation / Corrosion
� Operational issues
� Kinetics & Mass transfer performances
� Process simulations / cost evaluations
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Case of the MEA 30wt.% process
� Reference case
� Enough data for complete design
� Main focus on reboiler duty
=> 3.7 GJ / t_CO2
� reboiler duty = only cost ?3.0
3.5
4.0
4.5
5.0
5.5
0.16 0.18 0.20 0.22 0.24 0.26 0.28 0.30 0.32
� _lean (mol/mol)
Q_re
b (
GJ/t
_C
O2
)
Sim. Tobiesen et al. (2006)
Sim. Abu-Zahra et al. (2007)
Sim. Present w ork
Exp. Knudsen et al. (2009)
0.6
0.8
1.0
1.2
1.4
1.6
1.8
2.0
2.2
0.18 0.20 0.22 0.24 0.26 0.28 0.30
� _lean (mol/mol)
Q (
GJ/t
_C
O2)
sensitive heat
reaction heat
stripping energy
50
55
60
65
70
75
80
0 5 10 15
distance from top of absorber (m)
Te
mp
era
ture
(°C
)
0
2
4
6
8
10
12
14
Va
po
r C
O2
(D
ry m
ole
%)
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New process : main targets 1/3
absorber
stripper
purified gas
90% CO2 capture
CO2
flue gas
13.5% CO2
lean amine
rich amine
HP CO2 (110 bars)
compressor = 25 – 30 %
regeneration heat = 50 – 60 %
columns + packings = 30 – 50 %
compressors = 30 - 40 %
blower = 5 – 10 %
1 : high capacity solvent with low heat regeneration requirements
Opex (2/3) + Capex (1/3)
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New process : main targets 2/3
absorber
stripper
purified gas
90% CO2 capture
CO2
flue gas
13.5% CO2
lean amine
rich amine
HP CO2 (110 bars)
compressor = 25 – 30 %
regeneration heat = 50 – 60 %
columns + packings = 30 – 50 %
compressors = 30 - 40 %
blower = 5 – 10 %
1 : high capacity solvent with low heat regeneration requirements
2 : high capacity solvent with good kinetics
+ adapted mass transfer technology
Opex (2/3) + Capex (1/3)
PCC Workshop, 11th-13th July, 2010, Talloires, France15
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New process : main targets 3/3
absorber
stripper
purified gas
90% CO2 capture
CO2
flue gas
13.5% CO2
lean amine
rich amine
HP CO2 (110 bars)
compressor = 25 – 30 %
regeneration heat = 50 – 60 %
columns + packings = 30 – 50 %
compressors = 30 - 40 %
blower = 5 – 10 %
1 : high capacity solvent with low heat regeneration requirements
2 : high capacity solvent with good kinetics
+ adapted mass transfer technology
3 : solvent with low temperature degradation (Reg in pressure)
Opex (2/3) + Capex (1/3)
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Outlook
� IFP & CCS
� 1st generation PCC
� Needs for new processes
� DMX™ and future processes
� Conclusion� Conclusion
� IFP & CCS
� 1st generation PCC
� Needs for new processes
PCC Workshop, 11th-13th July, 2010, Talloires, France17
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PDemixing solvents
concepts
amine + H2O + CO2 � ammonium salts
1) high capacity solvents 2) low reaction heat3) regeneration of a fraction of the solvent only 4) CO2 rich phase has an "abnormally" high loading
=> important energy savings
CO2
CO2 lean
phase
CO2
DMX
Solvent
absorption
phase
separation CO2 rich
phase
PCC Workshop, 11th-13th July, 2010, Talloires, France18
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DMX™ solventsThermodynamics
80
60
40
20
0
0 20 40 60 80 100
60 % wt.70 % wt.80 % wt.50% wt.compositions instablesphases demixées
A AH22+, 2HCO3
-
H2O
A_salts
% wt. salts
%w
t.H
2 O
%w
t.A
PCC Workshop, 11th-13th July, 2010, Talloires, France19
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PDMX™ solvents
L/L Decantation
� NB Oil & Gas reference case :
� high separation quality is not needed
� densities and viscosities less in favor
� Step 1 :
� stirred cell tests
� Step 2 :
� lab-scale decanter test
� CFD
PCC Workshop, 11th-13th July, 2010, Talloires, France20
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DMX™ solventsDegradation
• Very low thermal degradation, little influence of CO2 or/and 02concentration (DMX-1 vs 17 molecules) => possibility to increasetemperature at stripper and therefore possibility to increasepressure at stripper + low solvent consumption
0
10
20
30
40
50
60
70
80
90
100
0 20 40 60 80 100
% de dégradation sous O2
% d
e l
a p
op
ula
tio
n t
est
4,2 bar O2
DM
X-1 M
EA
140 C
0
10
20
30
40
50
60
70
80
90
100
0 20 40 60 80 100
% de dégradation sous CO2
% d
e l
a p
op
ula
tio
n t
est
20 bar CO2
DM
X-1
ME
A
140 C
% o
f th
e t
es
t p
op
ula
tio
n
% o
f th
e t
es
t p
op
ula
tio
n
% of degradation % of degradation time (h)
-0,8
-0,7
-0,6
-0,5
-0,4
-0,3
-0,2
-0,1
0
0 100 200 300 400 500
Temps (h)
Ln
([A
min
e]/
[Am
ine]°
)
180 C
NHOHOH
NOHOH
NOH
DMX-1
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PDMX™ Process
Process evaluation
AB
SOR
BE
R
STR
IPPER
Decanter
Flue Gas
Gas Treated
CO2 lean amine
Rich amine
Lean amine
CO2 richamine
LP CO2
Reboiler
Leanamine
HP CO2
2.3 GJ/ton CO2 (-38% !)
-25 % in CO2 total cost
important decrease in reboiler duty=> a more complex cost repartition...=> more work needed on all items for further cost reduction !
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DMX™ ProcessMini-pilot tests
� Tests in a laboratory test rig
� complete loop
� comparison of solvents (qualitative)
� degradation/corrosion tests
� 30% MEA
� 110°C
Vcorr = 4.5 mm/year
� DMX-1 solvent
� 105°C (mini-Pilot)
Vcorr < 2 µm/year
� 180°C, 20 bar CO2 (CSTR)
Vcorr = 10 µm/year
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Chilled Ammonia Process 1/2
Exisiting
FGD
Existing
Stack
2 stage
Cooling
Chiller
CO2
Absorber
Regenerator
HX
CO2
HP
Pump
Wash
Wash
Reboiler
Flue Gas
Water
Rich Slurry
Lean Slurry
CO2
Flue Gas
Purge
Lean AC
Rich ABC
120F
35F
Cooling & Cleaning of FG CO2 Absorption CO2 Regeneration
1.2-2.4 GJ/ton CO2 (-35 -68%)
-64% electrical energy� a process with very low reboiler duty
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Exisiting
FGD
Existing
Stack
2 stage
Cooling
Chiller
CO2
Absorber
Regenerator
HX
CO2
HP
Pump
Wash
Wash
Reboiler
Flue Gas
Water
Rich Slurry
Lean Slurry
CO2
Flue Gas
Purge
Lean AC
Rich ABC
120F
35F
Cooling & Cleaning of FG CO2 Absorption CO2 Regeneration
Chilled Ammonia Process 2/2
1.2-2.4 GJ/ton CO2 (-35-68%)
-64% electrical energy
additional CAPEX + OPEX !!
for appropriate boundary conditions
� a process with very low reboiler duty
� BUT with pre/post conditionning
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Hydrates process 1/2
� a process with no OPEX at
reboiler !
Hydrates F
ormation R
eactor
Hydrates D
issociationR
eactor
FlueGas
Reboiler
HP CO2
Gas Treated
0 GJ/ton CO2 !!!
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Hydrates process 2/2
� a process with no OPEX at
reboiler !
� BUT with pre-conditionning
=> importance of thermodynamic
promoters
Hydrates F
ormation R
eactor
Hydrates D
issociationR
eactor
FlueGas
Reboiler
HP CO2
Gas Treated
0 GJ/ton CO2 !!!
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Technologies 1/2
absorber
stripper
purified gas
CO2
flue gas
lean amine
rich amine
HP CO2
compressor = 25 – 30 %
regeneration heat = 50 – 60 %
columns + packings = 30 – 50 %
compressors = 30 - 40 %
blower = 5 – 10 %
columndesign
column design : - optimum packing / distribution- minimum pressure drop- maximum mass transfer characteristics
Opex (2/3)
Capex (1/3)
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Technologies 2/2
random / structured packings
original G/L contactors
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Outlook
� IFP & CCS
� 1st generation PCC
� Needs for new processes
� DMX™ and future processes
� Conclusion
� IFP & CCS
� 1st generation PCC
� Needs for new processes
� DMX™ and future processes
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Conclusion
� 1st generation PCC
� MEA 30wt.% ready for demos and more but high CO2 cost
� HiCapt+™
� cost repartition => drivers
� 2nd generation PCC
� lots of required data / steps
� clear boundary conditions for smart comparison
� DMX™
� Technologies
� Long term studies
� hydrates, membranes, ionic liquids, sorbents ...