From MEA to demixing solvents and future steps, a roadmap ...web.mit.edu/sequestration/talloires/2_to_page_pdfs/Talloires_Raynal.… · NB Oil & Gas reference case : high separation

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




� Conclusion


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CCS @ IFP

� PS1 strategic priority

� intensive work on PCC

� 1st & 2ndgeneration processes

� future processes

� involve many research fields


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Outlook

� IFP & CCS




� Conclusion



� Conclusion

� IFP & CCS


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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


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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


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Outlook

� IFP & CCS




� Conclusion


� Conclusion

� IFP & CCS



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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.


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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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absorber

stripper

purified gas

90% CO2 capture

CO2

flue gas

13.5% CO2

lean amine

rich amine

HP CO2 (110 bars)





blower = 5 – 10 %


2 : high capacity solvent with good kinetics

+ adapted mass transfer technology

Opex (2/3) + Capex (1/3)


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absorber

stripper

purified gas

90% CO2 capture

CO2

flue gas

13.5% CO2

lean amine

rich amine

HP CO2 (110 bars)





blower = 5 – 10 %


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




� Conclusion� Conclusion

� IFP & CCS




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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


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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


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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


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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





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




� Conclusion

� IFP & CCS





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Conclusion


� 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 ...


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Thank you !

[email protected]

Documents

From MEA to demixing solvents and future steps, a roadmap ...web.mit.edu/sequestration/talloires/2_to_page_pdfs/Talloires_Raynal.… · NB Oil & Gas reference case : high separation