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

2

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

1

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

4

6

8

10

12

0.0

0.2

0.4

0.6

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)


Parametric study of a single stage gas

permeation module

0

2

4

6

8

10

12

14

16

18

20

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




iii) Adsorption

iv) Membranes

0 2 4 60

2

4

6

c2

(g

/L)

c1 (g/L)


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




iii) Adsorption

iv) Membranes

0 2 4 60

2

4

6

c2

(g

/L)

c1 (g/L)


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

1

2

3

4

5

6

7

8

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

1

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)

0.3

0.4

0.5

0.6

0.7

0.8

0.9

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?

Thank you for your attention!

[email protected]

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

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0

0.05

0.1

0.15

0.2

0.25

0.3

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

membranes and post-combustion carbon dioxide capture · pilot absorption unit for gas boiler plants...

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