Post-Combustion Processes Employing Polymeric Membranes
21. 06. 2011 / Frankfurt
Torsten Brinkmanna, Thorsten Wolffa, Jan-Roman Paulsb
a: Institute of Polymer Researchb: Institute of Materials Research
2nd International Conference on Energy Process EngineeringEfficient Carbon Capture for Coal Power PlantsJune 20 - 22, 2011 in Frankfurt/Main, Germany
2
Contents
Introduction Permeation data and membrane production Membrane module model Pilot plant experiments Process simulation Upscaling aspects Conclusions
3
Membrane Process Development
Lab. scale investigations Polymer synthesis Polymer modification Permeation behaviour
Pilot scale membraneproduction
Pilot plants
Module design
0
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0 0.4 0.8 1.2 1.6 2 2.4 2.8 3.2
Membrane area Az [m2]
n-C
4H10
Mol
e fr
actio
n y R
,C4 [
-]
Lines: SimulationSymbols: Experiment
hm44.46V
hm34.20V
hm29.05V
3(STP)F
3(STP)F
3(STP)F
0
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0 0.4 0.8 1.2 1.6 2 2.4 2.8 3.2
Membrane area Az [m2]
n-C
4H10
Mol
e fr
actio
n y R
,C4 [
-]
Lines: SimulationSymbols: Experiment
hm44.46V
hm34.20V
hm29.05V
3(STP)F
3(STP)F
3(STP)F
Comp. pilot plant/simulationProcess simulation/design
4
Contents
Introduction Permeation data and membrane production Membrane module model Pilot plant experiments Process simulation Upscaling aspects Conclusions
5
Membrane Data - Laboratory Scale
1. A. Car er al., Adv. Funct. Mater. 18 (2008) 2815-2823 2. S. Kipp, Diploma Thesis, TUHH/HZG, 20103. C. Naderipour, Diploma Thesis, HAW Hamburg/HZG, 20094. 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.
25 (?)
20.0
20.0
20.0
20.0
[°C]
50.0
33.7
48.3
61.1
46.5
CO2/N2
-2.71,3POLYACTIVE®
-0.6653PEBAX®
-0.3633Cellulose Acetate
POLARIS™ 1
POLYACTIVE®
MembraneL [Nm3/(m2 h bar]
-2.744
40.63.61,2
H2OCO2Ref.
-5
-4
-3
-2
-1
0
1
2
3
4
5
0.0028 0.0029 0.003 0.0031 0.0032 0.0033 0.0034 0.0035 0.0036
1/T [K-1]ln
(L)
H2O
CO2
H2
CH4O2
N2
Multilayer composite membranes Single gas permeation data HZG data determined using pressure increase apparatus Temperature dependency can be described by Arrhenius type relationship
POLYACTIVE® composite membrane [1]
73°C 14°C
6
Membrane Production in m2 Scale
2.00
2.20
2.40
2.60
2.80
3.00
0.0 40.0 80.0 120.0
Production Batch Length L [m]
O2/N
2 Sel
ectiv
ity
O2/
N2
[-]
Average
POLYACTIVE® multilayer composite membrane
O2/N2 permeation data for quality control
Casting of porous support
Coating of selective/ protection layers
7
Contents
Introduction Permeation data and membrane production Membrane module model Pilot plant experiments Process simulation Upscaling aspects Conclusions
8
Permeatetube
Membraneenvelope
PressurevesselFeed
Retentate
Permeate Permeate
Top view of a membrane envelope
Feed
Per-meate
Baffle plateO-ring
Feed Permeate
Retentate
FeedRetentate
Permeate
Simulation Model GS Module Boundary conditions
- Module geometry and feed definition Flow patterns: differential balances
- Material- Energy- Pressure drop
Equation of state- Fugacities- Enthalpies- Densities …
Permeation- Arrhenius- Free Volume model
Concentration polarisation- Mass transfer coefficients- Stefan-Maxwell
iP,iR,imolar,iM, ffLn
0naz
niM,
iR,
z
RyR,CH4
vR
9
Equation oriented process simulator- Parameterised models- Numerical mathematics- Physical properties- Dynamic simulation- PDE support- Integrated development environment
Detailed model development Flowsheet and process development
Implementation: Aspen Custom Modeler®
10
Contents
Introduction Permeation data and membrane production Membrane module model Pilot plant experiments Process simulation Upscaling aspects Conclusions
11
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 mbarWater vapour saturation by employing liquid
ring compressor and vacuum pump
PDI
PI2
FI1 PI1 FI2
QI1 QI2
QI3
Gas-chroma-tograph
V1
V2
V3
moduleMembrane
Permeatevacuum pump
Feedvessel
FeedCompressor
Externalvacuum pump
12
Pilot Plant Experimental Results
0
0.03
0.06
0.09
0.12
10 15 20 25 30 35 40
Volumetric Flowrate Feed VF [Nm3/h]
CO
2 Mol
e Fr
actio
n R
eten
tate
y R
,CO
2 [-]
pF = 3 barpF = 2 barpF = 1.4 barpF = 3 bar, SimpF = 2 bar, SimpF =1.4 bar, Sim
0
0.05
0.1
0.15
0.2
0.25
10 15 20 25 30 35 40
Volumetric Flowrate Feed VF [Nm3/h]
Stag
ecut
VF/
V P [-
]
pF = 3 barpF = 2 barpF = 1.4 barpF = 3 bar, SimpF = 2 bar, SimpF = 1.4 bar, Sim
0.5
0.55
0.6
0.65
0.7
0.75
10 15 20 25 30 35 40
Volumetric Flowrate Feed VF [Nm3/h]
CO
2 Mol
e Fr
actio
n Pe
rmea
te
y P,C
O2
[-]
pF = 3 barpF = 2 barpF = 1.4 barpF = 3 bar, SimpF = 2 bar, SimpF = 1.4 bar, Sim
Feed Retentate
Permeate
Gas permeationmodule
VF = 13 to 34 Nm3/hyF,CO2 = 13 to 18%pF = 1.4 to 3barF = 20 to 24 °C
yR,CO2
VPyP,CO2pP = 0.2 bar
A=7.4m2
13
Pilot Plant Results Interpretation
Operating behaviour of module asexpected 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?
14
Contents
Introduction Permeation data and membrane production Membrane module model Pilot plant experiments Process simulation Upscaling aspects Conclusions
15
Input Data
Power plant [1] Coal fired power plant Nominal power: 600 MW Efficiency: 45.9% Flue gas:
V = 1 704 000 Nm3/hp = 1.013 bar = 48°CyCO2 = 0.133yH2O = 0.113yN2 = 0.754
Process simulation Aspen Custom Modeler®
Membrane module model- Cross flow with free permeate withdrawal- Permeances as function of temperature,
pressure and composition based on single gas experiments
- Real gas and Joule Thomson effect considered
- No pressure drops and mass transfer 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
16
Performance of POLYACTIVE® Composite Membranes: Humid Flue Gas
FeedCooler_1 GLSep_2Blower
MembraneStage_1
VacuumPump_1
Cooler_2GLSep_3
MembraneStage_2
B5
Compressor
Cooler_3
GLSep_4
Expander
S1S2
Water_2
S4S5
Retentate_OffGas
Permeate_1
S8
S9
CO2Water_3
S3
RecycleS13
S6
S7
S12
Water_4
S15
GLSep_1
S10
Water_1
VF = 1 704 000 Nm3/h yF,CO2 = 0.133pF = 1.013 bar yF,H2O = 0.113F = 48°C yF,N2 = 0.754
yP,CO2 = 0.95
p = 1.1 bar = 30°C
p = 4 bar = 30°Cp = 0.1 bar
0
50
100
150
200
250
300
350
400
0.65 0.7 0.75 0.8 0.85 0.9 0.95 1
CO2 Recovery [-]
Spec
ific
Ener
gy fo
r Cap
ture
[k
Wh/
t CO
2]
0
500000
1000000
1500000
2000000
2500000
3000000
Mem
bran
e A
rea
[m2 ]
Compression
Cooling
Permeation data (average values at 30°C): LCO2 = 4.3 Nm3/(m2 h bar)LH2O = 43.4 Nm3/(m2 h bar)CO2/N2 = 36
Flowsheet: Zhao et al., J. Membr. Sci. 359 (2010) 160-172
17
Performance of POLYACTIVE® Composite Membranes: Operating Temperatures
0
50
100
150
200
250
300
350
400
450
0.65 0.7 0.75 0.8 0.85 0.9 0.95 1
CO2 Recovery [-]
Spec
ific
Ener
gy fo
r Cap
ture
[k
Wh/
t CO
2]
0.00E+00
2.00E+06
4.00E+06
6.00E+06
8.00E+06
1.00E+07
1.20E+07
1.40E+07
Mem
bran
e A
rea
[m2 ]
20°C
30°C
30°C
Compression
Membrane area
FeedCooler_1 GLSep_2Blower
MembraneStage_1
VacuumPump_1
Cooler_2
GLSep_3
MembraneStage_2
B5
VacuumPump_2
Cooler_3GLSep_4
S1S2
Water_2
S4S5
Retentate_OffGas
Permeate_1
S8
S9
Water_3
S3
Recycle
S13
S7CO2
Water_4
GLSep_1
S10
Water_1
VF = 1 704 000 Nm3/h yF,CO2 = 0.133pF = 1.013 bar yF,H2O = 0.113F = 48°C yF,N2 = 0.754
yP,CO2 = 0.95
p = 1.1 barp = 0.2 bar
p = 0.2 bar
L [Nm3/(m2 h bar]
36.043.24.230
46.540.63.620
CO2/N2
H2OCO2
[°C]
18
Contents
Introduction Permeation data and membrane production Membrane module model Pilot plant experiments Process simulation Upscaling aspects Conclusions
19
Possible Module Design
Envelope type modules allow for easy scale-up
Possible to minimise permeate side pressure drops: important for vacuum assisted operation
Membrane sheets are thermally welded: no additional components as e.g. adhesives
Proven technology for the manufacture of flat sheet membranes on industrial scale
20
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
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 motive medium connection2 motive nozzle3 head4 diffuser inlet5 diffuser outlet
A pressurised motive mediumpRetentate > pd > pPermeate
B suction flow (permeate) at pressure pPermeate
C mixed flow at pressure pd
1. Körting Hannover AG, Arbeitsblätter für die Strahlpumpen-Anwendung, www.koerting.de
2. Sterling SIHI GmbH, www.sterlinsihi.com
21
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