Post-Combustion Processes Employing

Polymeric Membranes
Torsten Brinkmanna, Thorsten Wolffa, Jan-Roman Paulsb
a: Institute of Polymer Research
b: Institute of Materials Research

21. 06. 2011 / Frankfurt

2nd International Conference on Energy Process Engineering

Efficient Carbon Capture for Coal Power Plants
June 20 - 22, 2011 in Frankfurt/Main, Germany
Contents

 Introduction
 Permeation data and membrane production
 Membrane module model
 Pilot plant experiments
 Process simulation
 Upscaling aspects
 Conclusions

2
 Membrane Process Development
Lab. scale investigations Pilot scale membrane Pilot plants
 Polymer synthesis production
 Polymer modification
 Permeation behaviour

Module design Process simulation/design Comp. pilot plant/simulation

0.07
  29.05 m3
VF (STP) h

n-C4H10 Mole fraction yR,C4 [-]

0.06   34.20 m3
VF (STP) h

  44.46 m3
V
0.05 F (STP) h

0.04 Lines: Simulation

Symbols: Experiment
0.03

0.02

0.01

0
0 0.4 0.8 1.2 1.6 2 2.4 2.8 3.2
2
Membrane area Az [m ]
3
Contents

 Introduction
 Permeation data and membrane production
 Membrane module model
 Pilot plant experiments
 Process simulation
 Upscaling aspects
 Conclusions

4
 Membrane Data - Laboratory Scale

 Multilayer composite membranes

 Single gas permeation data
 HZG data determined using pressure increase apparatus
 Temperature dependency can be described by Arrhenius type relationship
5
L [Nm3/(m2 h bar]
4
Membrane Ref. CO H2O CO2/N2 [°C] H 2O
2 3

POLYACTIVE® 1,2 3.6 40.6 46.5 20.0 2

1 CO2
POLYACTIVE® 1,3 2.7 - 61.1 20.0

ln(L)
0
H2
PEBAX® 3 0.665 - 48.3 20.0 -1
CH4
-2 O2
Cellulose 3 0.363 - 33.7 20.0
-3 N2
Acetate
-4
POLYACTIVE® composite membrane [1]
POLARIS™ 1 4 2.74 - 50.0 25 (?) -5
0.0028 0.0029 0.003 0.0031 0.0032 0.0033 0.0034 0.0035 0.0036
73°C 1/T [K-1] 14°C
1. A. Car er al., Adv. Funct. Mater. 18 (2008) 2815-2823
2. S. Kipp, Diploma Thesis, TUHH/HZG, 2010
3. C. Naderipour, Diploma Thesis, HAW Hamburg/HZG, 2009
4. T. Merkel et al., Selecting Membranes for Carbon Dioxide Capture from Power Plant Flue Gases
In Book of Abstracts XXVI EMS Summer School 29 September – 2. Oktober 2009 Geesthacht/Ratzeburg, 2009.

5
 Membrane Production in m2 Scale

 POLYACTIVE® multilayer composite membrane

 O2/N2 permeation data for quality control
Coating of selective/ 3.00
protection layers

O 2/N 2 Selectivity O2/N2 [-]

2.80

2.60
Average

2.40

2.20

Casting of porous support 2.00

0.0 40.0 80.0 120.0
Production Batch Length L [m]

6
Contents

 Introduction
 Permeation data and membrane production
 Membrane module model
 Pilot plant experiments
 Process simulation
 Upscaling aspects
 Conclusions

7
 Retentate Membrane Top view of a
envelope membrane envelope
Permeate Feed
Retentate
tube
Permeate Permeate
Per-
meate
Pressure
Feed vessel

O-ring Baffle plate

Feed Permeate Simulation Model GS Module

yR,CH4 R  Boundary conditions
- Module geometry and feed definition
vR  Flow patterns: differential balances
- Material
n R, i
- Energy  a  n M,
i 0
- Pressure drop z
z
Feed  Equation of state
Retentate - Fugacities
- Enthalpies
- Densities …
 Permeation  i  L molar, i  fR,i  fP,i 
n M,
- Arrhenius
- Free Volume model
 Concentration polarisation
- Mass transfer coefficients
Permeate - Stefan-Maxwell 8
 Implementation: Aspen Custom Modeler®

 Equation oriented process simulator

- Parameterised models
- Numerical mathematics
- Physical properties
- Dynamic simulation
- PDE support
- Integrated development
environment
 Detailed model development
 Flowsheet and process development

9
Contents

 Introduction
 Permeation data and membrane production
 Membrane module model
 Pilot plant experiments
 Process simulation
 Upscaling aspects
 Conclusions

10
 Pilot Plant Operating Conditions

Operating data:
 Membrane area: 7.38 m2
 Feed pressures: 1.4 to 3 bar
 Feed flowrates: 13 to 34 Nm3/h
 Feed CO2 mole fraction: 13.7 to 18.0 %
 Feed temperatures: 20 to 25°C
 Permeate pressure: 200 mbar
 Water vapour saturation by employing liquid
ring compressor and vacuum pump

V1 PDI

FI1 PI1 FI2

V2 Feed
Membrane vessel
QI1 module QI2

Feed
Compressor
QI3 PI2
Permeate
External V3 vacuum pump
vacuum pump
Gas-
chroma-
tograph

11
 Pilot Plant Experimental Results
0.75 0.12

CO 2 Mole Fraction Retentate

CO 2 Mole Fraction Permeate

0.7
0.09
pF = 3 bar pF = 3 bar
pF = 2 bar

yR,CO2 [-]
pF = 2 bar
yP,CO2 [-]

0.65
pF = 1.4 bar pF = 1.4 bar
0.06
pF = 3 bar, Sim pF = 3 bar, Sim
0.6 pF = 2 bar, Sim pF = 2 bar, Sim
pF = 1.4 bar, Sim pF =1.4 bar, Sim
0.03
0.55

0.5 0
10 15 20 25 30 35 40 10 15 20 25 30 35 40

Volumetric Flowrate Feed VF [Nm3/h] Volumetric Flowrate Feed VF [Nm3/h]

0.25
yR,CO2
Gas permeation
0.2
module

Stagecut V F/V P [-]

pF = 3 bar
Feed Retentate 0.15 pF = 2 bar
pF = 1.4 bar
A=7.4m2 pF = 3 bar, Sim
0.1 pF = 2 bar, Sim
VF = 13 to 34 Nm3/h pF = 1.4 bar, Sim
Permeate
yF,CO2 = 13 to 18% 0.05
pF = 1.4 to 3bar
F = 20 to 24 °C VP 0
yP,CO2 10 15 20 25 30 35 40
pP = 0.2 bar Volumetric Flowrate Feed VF [Nm3/h]

12
Pilot Plant Results Interpretation

 Operating behaviour of module as

expected
 Module and membranes were used in
biogas pilot plant before
 Simulation model predicts performance
satisfactorily
 Single gas permeation data to predict
multicomponent mass transfer
 Deviations experiment – simulation
- Influence of water permeation on other
components correctly considered?

13
Contents

 Introduction
 Permeation data and membrane production
 Membrane module model
 Pilot plant experiments
 Process simulation
 Upscaling aspects
 Conclusions

14
 Input Data

Power plant [1] Process simulation

 Coal fired power plant  Aspen Custom Modeler®
 Nominal power: 600 MW  Membrane module model
 Efficiency: 45.9% - Cross flow with free permeate withdrawal
 Flue gas: - Permeances as function of temperature,
V = 1 704 000 Nm3/h pressure and composition based on single
p = 1.013 bar gas experiments
 = 48°C - Real gas and Joule Thomson effect
yCO2 = 0.133 considered
yH2O = 0.113 - No pressure drops and mass transfer
yN2 = 0.754 resistances
 Rotating equipment
- Isentropic efficiency of 85 %
- Assumed as adiabatic compressors or
turbines
- No specific type assumed
1. Notz et al., Chem. Ing. Tech. 82 No.10 (2010) 1639-1653
15
 Performance of POLYACTIVE® Composite
Membranes: Humid Flue Gas

 Permeation data (average values at 30°C):

VF = 1 704 000 Nm3/h yF,CO2 = 0.133 LCO2 = 4.3 Nm3/(m2 h bar)
Expander
pF = 1.013 bar yF,H2O = 0.113 LH2O = 43.4 Nm3/(m2 h bar)
F = 48°C yF,N2 = 0.754
CO2/N2 = 36
S15
MembraneStage_1
Blower GLSep_2
GLSep_1 Cooler_1 Retentate_OffGas
Feed S4
S10 S5 S2 Recycle
S1 B5 S13
Cooler_3
Permeate_1
p = 4 bar
p = 1.1 bar
Water_1
Water_2 p = 0.1 bar S6  = 30°C
 = 30°C
400 3000000 VacuumPump_1 S7
Cooling
350
2500000 Compressor
Specific Energy for Capture

S8 MembraneStage_2
300
S3 GLSep_4
Membrane Area [m ]
2

2000000 GLSep_3 S12

250 Cooler_2
[kWh/t CO2 ]

200 1500000
S9
Compression
150
1000000
100
Water_3 Water_4 CO2
500000
50

0 0
yP,CO2 = 0.95
0.65 0.7 0.75 0.8 0.85 0.9 0.95 1
CO2 Recovery [-] Flowsheet: Zhao et al., J. Membr. Sci. 359 (2010) 160-172
16
 Performance of POLYACTIVE® Composite
Membranes: Operating Temperatures
Recycle

MembraneStage_1
Blower GLSep_2
GLSep_1 Cooler_1 Retentate_OffGas
Feed S13 S4
S10 S5 S2
S1 B5

Permeate_1

Water_1
p = 1.1 bar
Water_2 p = 0.2 bar
VF = 1 704 000 Nm3/h yF,CO2 = 0.133 VacuumPump_1
yP,CO2 = 0.95
pF = 1.013 bar yF,H2O = 0.113
F = 48°C yF,N2 = 0.754 S8 MembraneStage_2
Cooler_2
450 1.40E+07
S3 p = 0.2 bar
S9
400
1.20E+07 GLSep_4
GLSep_3 Cooler_3
Specific Energy for Capture

350 CO2
S7

Membrane Area [m 2]
1.00E+07 Water_3
300
VacuumPump_2
[kWh/t CO2 ]

Compression 8.00E+06
250 Water_4
30°C
200 6.00E+06
 [°C] L [Nm3/(m2 h bar] CO2/N2
150
20°C 4.00E+06
Membrane area
100 CO2 H2O
2.00E+06
50
30°C 20 3.6 40.6 46.5
0 0.00E+00
0.65 0.7 0.75 0.8 0.85 0.9 0.95 1 30 4.2 43.2 36.0
CO2 Recovery [-]

17
Contents

 Introduction
 Permeation data and membrane production
 Membrane module model
 Pilot plant experiments
 Process simulation
 Upscaling aspects
 Conclusions

18
 Possible Module Design

 Envelope type modules allow for easy scale-up  Membrane sheets are thermally welded:
no additional components as e.g. adhesives
 Possible to minimise permeate side pressure
drops: important for vacuum assisted operation  Proven technology for the manufacture of
flat sheet membranes on industrial scale

19
 Vacuum Pumps

Steam ejector vacuum pumps [1]

 Max. capacity: 2 106 m3/h (about half of
the flowrate required for 1st stage)
 One stage vacuum: 100 mbar
 High motive steam demand 1 motive medium connection
2 motive nozzle
3 head
4 diffuser inlet
5 diffuser outlet
A pressurised motive medium
pRetentate > pd > pPermeate
B suction flow (permeate) at
pressure pPermeate
C mixed flow at pressure pd

Liquid rings vacuum pumps [2]

 Sterling SIHI: 11 500 m3/h at 100 mbar
 ZM Engineering: 47 100 m3/h at 180 mbar

New vacuum pump concepts required

1. Körting Hannover AG, Arbeitsblätter für die Strahlpumpen-Anwendung,

www.koerting.de
2. Sterling SIHI GmbH, www.sterlinsihi.com

20
Conclusions

 POLYACTIVE® composite membrane

- Permeance and selectivity are suitable
- Can be produced on large scale
 Accurate module models are required to develop efficient process designs
 Piloting is essential
- Process performance
- Influence of various components
- Determination of unknowns (level of filtration necessary,…)
 Competitive process designs have been developed (Merkel et al., Zhao et al.)
- Important to consider water
- Cooling has to be accounted for
- Integration with power plant process
 New vacuum pump concepts required
 Novel module concepts would be advantageous

21