CO2 CAPTURE BY SUB-AMBIENT MEMBRANE OPERATION Library/Research/Coal/ewr/co2/22Aug11... · Capture...
Transcript of CO2 CAPTURE BY SUB-AMBIENT MEMBRANE OPERATION Library/Research/Coal/ewr/co2/22Aug11... · Capture...
2011 NETL CO2 Capture Technology Meeting22 August 2011
CO2 CAPTURE BY SUB-AMBIENT
MEMBRANE OPERATION
E. Sanders D. Hasse E. Corson D. Kratzer S. Kulkarni
DOE/NETL Proj. Manager: Andrew O’Palko
Air Liquide DRTC August 2011 AIR LIQUIDE 2
Air Liquide: Key Information
Proposed new technology leverages AL strengths
• Air Liquide core expertise in gas separation, cryogenics and gas handling
•MEDAL – Established membrane manufacturer for N2, H2 and CO2applications
•Strong program related to coal oxy-combustion
A world leader in industrial and medical gases
> 42,000 employees
€ 13.5 billion sales (2010)
Air Liquide DRTC August 2011 AIR LIQUIDE 3
CO2 Capture by Sub-Ambient Membrane Operation
Bench scale test of CO2 separation using a hollow fiber membrane module at sub-ambient temperatures
Funding Request:
DOE: 1.266 M$ ; Cost share: 0.32 M$
Duration – 24 months
Air Liquide America Process and Construction (Engineering process design)
American Air Liquide Delaware Research & Technology Center (Separations, Combustion, Analysis..)
Air Liquide Advanced Technologies US – MEDAL (membrane manufacturing)
Air Liquide DRTC August 2011 AIR LIQUIDE 4
Project Main Tasks and Timeline
Task 1 : Demonstrate commercial scale bundle operation at sub-ambient temperature
Task 2 : Laboratory Scale Flue Gas Contaminant Testing
Task 3 : Sub-ambient Membrane/Cryogenic System Design
Q1 Q2 Q3 Q4 Q5 Q6 Q7 Q8
1
Demonstrate commercial scale bundle operation at sub-ambient temperature
1.1
Design and fabrication of a closed loop sub-ambient test system for CO2/N2
M1
1.2
Test mechanical integrity of bundle/housing assembly at sub-ambient temperature
1.3
Map bundle performance as a function of temperature, pressure and composition
1.4
Demonstrate enhanced membrane performance over long term at cold temperature
M3
2Laboratory Scale Flue Gas Contaminant Testing
2.1Modify lab cryo-test bench for low temperature SOx and NOx testing
2.2Measure SOx and NOx membrane performance on mini-permeator
M2
3Sub-ambient Membrane/Cryogenic System Design
3.1
Use Phase I data to design commercial facility and estimate LCOE increase for CO2 capture.
3.2
Use Phase I data to design and develop budget estimate of a slip-stream demonstration unit.
M4
In progressFinished
Projected
PHASE 1: Experimental work
PHASE 2: Design work
Air Liquide DRTC August 2011 AIR LIQUIDE 5
Detailed Project Objectives
1. Verify mechanical integrity of commercial scale membrane module structural components at sub-ambient temperatures.
2. Demonstrate high permeance - selectivity performance with a commercial scale membrane module in a bench-scale test skid
3. Demonstrate long term operability of the sub-ambient temperature membrane skid
4. Evaluate effect of expected contaminant levels (SOx, NOx) on membrane performance (lab tests)
5. Refine process simulation for integrated process with flue gas conditioning and liquefier
6. Design slip-stream-scale unit for possible field test
Air Liquide DRTC August 2011 AIR LIQUIDE 6
Cold Box(-20 to -40 C)
After CoolerCompressor(8-16 bar)Remixing Tank Ballast Tank Membrane Module
StepDown Valve
F
Retentate Flow Measurement
F
Permeate Flow Measurement
F
Feed Flow Measurement
Heat Exchanger
Sample Port
Sample Port
Sample Port
Cold Membrane Test Skid
1. Verify mechanical integrity of commercial membrane module structural components at sub-ambient temperatures.
2. Demonstrate high permeance - selectivity performance with a commercial membrane module in a bench-scale test skid.
3. Demonstrate long term operability of the sub-ambient temperature membrane skid without external source of refrigeration.
5-20% CO2 in
N2
-30 to -40C, 8-16 bar
Air Liquide DRTC August 2011 AIR LIQUIDE 7
Conventional Membrane Pre-concentration
Power plant
Flue gas
-
systemPower plant
Flue gasConditioning &Compression
-
MembraneSystem
CO2 PartialCondensation
CO2 depleted vent
LCO2
Cryogenic heat exchanger
Recompressed CO2 enriched permeate
Power plant
Flue gas
-
systemPower plant
Flue gasConditioning &Compression
-
MembraneSystem
CO2 PartialCondensation
CO2 depleted vent
LCO2
Cryogenic heat exchanger
Cryogenic heat exchanger
Recompressed CO2 enriched permeate
Hybrid system required to economically meet 90% CO2 recovery + sequestration purity ( 95 - 99 % ) requirements for air fired coal flue gas
Membrane pre-concentration of CO2 followed by CO2 Liquefier
With Membrane alone, difficult to produce high purity ( >95% CO2 )
Membrane needed to operate CO2 Liquefier at moderate pressures
Air Liquide DRTC August 2011 AIR LIQUIDE 8
Cold Membrane Concept
Pre-concentration of CO2 by highly selective cold membrane before CPU Liquefier
Energy integration between membrane / liquefier through heat exchange
Partial recovery of compression energy
Power plant
Low-temperature Membrane system
CO2 Liquefier
Power plant
Flue gas Conditioning &Compression
Low-temperature Membrane system
CO2 Partial Condensation
CO2 depleted vent
LCO2
Cryogenic Heat
Exchanger system
Recompressed CO2enriched permeate
Power plant
Low-temperature Membrane system
CO2 Liquefier
Power plant
Flue gas Conditioning &Compression
Low-temperature Membrane system
CO2 Partial Condensation
CO2 depleted vent
LCO2
Cryogenic Heat
Exchanger system
Recompressed CO2enriched permeate
Air Liquide DRTC August 2011 AIR LIQUIDE 9
Cold Membrane Process Based on Existing AL Membrane
Hollow fiber membrane
provides most cost effective
solution for large gas separation
applications
Flue Gas
CO2
Air Liquide DRTC August 2011 AIR LIQUIDE 10
Intrinsic permeability at -30C inferred from known film data at RT + fiber data at RT and -30C
Sub-ambient Temperature Membrane Performance
Existing AL Membrane operated at < -10 C has unique combination of
high CO2 permeance and CO2 / N2 selectivity
0.1
1
10
100
1000
-60 -50 -40 -30 -20 -10 0
T (oC)
Per
mea
nce α(CO2/N2)=50
α(CO2/N2)=150
CO2
N2
FEEDHigh Pressurepo
PERMEATELow Pressurep1
MEMBRANENONPOROUS
Robeson, JMS, 2008
EP = ED + ∆HS
Air Liquide DRTC August 2011 AIR LIQUIDE 11
Hybrid Membrane + CPU Configuration
232 Psi
215 Psi
-30oC
17 Psi
-57oC
Air Liquide DRTC August 2011 AIR LIQUIDE 12
Why High Membrane Selectivity Pays Off
Permeate stream is smaller and higher CO2 purity
- Increases efficiency of CO2 liquefaction
- Decreases internal recycle.
Membrane Operating Temperature
Ambient
(20-30oC) -30oC
Feed Compression 94.6 94.6Permeate Compression 40 21.1
Cryogenic Turbo-expansion 0 22.3Ambient Turbo-expansion 36.2 31.2Boiler Feed Water Credit 16.4 15.8
Specific energy kW-hr/Ton[CO2] 326 204
Energy Credit [kW]
Overall energy for CO2 capture
Energy Use [kW]
Air Liquide DRTC August 2011 AIR LIQUIDE 13
Expected Development Challenges
Challenges specific to sub-ambient membrane operation Module materials Permeance-selectivity of commercial module Long term module performance stability
Integration of membrane process Energy integration with CPU Energy integration with power plant
• Compression and Turbo-expansion schemes• Heat economizers and Exergy conservation
Large but feasible membrane area production
Contaminant specific challenges Acid gas (NOx, SO2) separation Compressor materials Particulate removal Hg Water handling
Air Liquide DRTC August 2011 AIR LIQUIDE 14
Non-Permeate
Components of a Membrane System
POLYMER SCIENCE:Membrane Separation
Technology
MEMBRANETECHNOLOGY
BUNDLE DESIGNAND HOUSING
PROCESS DESIGN:Integration of MembraneInto Commercial System
Support Structure
Thin Outer Membrane
Permeate
FeedFlue Gas
CO2
Air Liquide DRTC August 2011 AIR LIQUIDE 15
P&ID of Test Skid
Compressor
Analytical skid
Cold box
Air Liquide DRTC August 2011 AIR LIQUIDE 16
Compressor
Gas handling: flow and temperature modulation Cold box with
membrane, heat exchanger and expansion valve
Control panel and data-logging
IR analysers
Skid in Operation
E. Corson D. Kratzer
Air Liquide DRTC August 2011 AIR LIQUIDE 17
Gas Cooling Scheme
Incremental cooling of feed gas by heat-
exchange with expanded residue stream & permeate
JT Valve Performance
-30
-20
-10
0
10
20
30
40
0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0
Time ( Hours )
Tem
pera
ture
(C
)
To JT Valve
From JT Valve
Air Liquide DRTC August 2011 AIR LIQUIDE 18
Gas Cooling Scheme : Approach temperature
Retentate T minus Feed T
-10
-9
-8
-7
-6
-5
-4
-3
-2
-1
0-60 -50 -40 -30 -20 -10 0 10 20 30 40
Feed T (C)
Del
ta T
(C)
• Accumulation of cooling effect allows feed to be cooled to < -50 C. Operating target is -30 to -40°C
• Temperature maintained by adjusting pressure expansion ratio across J-T valve
Air Liquide DRTC August 2011 AIR LIQUIDE 19
Mechanical Integrity Test
Largest commercial MEDAL bundle (12”)Most rigorous test of mechanical integrity
Leak-free operation particularly important for high selectivity
CTE analysis to choose bundle assembly components Several O-rings (materials / hardness / type) have been shortlisted on
recommendation of vendor experts
Laboratory verification of tube-sheet epoxy to fiber adhesion
Figure 5. Cold exposure: N2 Permeance monitoring of 3 minipermeators made with Manufacturing Epoxy and stored in -40C freezer
2.5
3.0
3.5
4.0
4.5
3-Mar 8-Mar 13-Mar 18-Mar 23-Mar 28-Mar 2-Apr
Date
N2
perm
eatio
n ra
teAL52-134-1
AL52-134-2
AL52-134-3
Air Liquide DRTC August 2011 AIR LIQUIDE 20
Mechanical Integrity Test Under Way
12” bundle has been operating since 7/5/11
Exposed to pressures up to 15 bar , temperatures down to -60 C and CO2 concentrations of 15 – 30%.
Withstood several shut-downs and re-starts
Performance has been stable ( 1st week separation data similar to 6th week separation data)
Various techniques (pure gas vs. mixed gas, varied stage cut and pressure, tracer molecules) used to diagnose performance
Target date is 12/2011 for completion of mechanical integrity test(s)
Air Liquide DRTC August 2011 AIR LIQUIDE 21
Temperature Response for Bundle Matches Lab Data
As temperature is decreased:
CO2 permeance is relatively constant
N2 permeance declines ~ 3x
Normalized permeance - Temperature scans
0.1
1
10
100
0.0033 0.0034 0.0035 0.0036 0.0037 0.0038 0.0039 0.004 0.0041 0.0042 0.0043
1/T K-1
GPU
rela
tive
to In
itial
N2
@
25C
CO2 Init P N2 Init P CO2 Init R N2 Init R
CO2 Cond P N2 Cond P CO2 Cond R N2 Cond R
Air Liquide DRTC August 2011 AIR LIQUIDE 22
Separation Performance Over First Month Testing
0
10
20
30
40
50
60
70
-50 -40 -30 -20 -10 0 10 20 30
Feed temp C
CO
2/N
2 (P
)14-Jul10-Aug
• Tracer molecule and stage cut performance being used to differentiate possible small leak vs flow non-ideality
Air Liquide DRTC August 2011 AIR LIQUIDE 23
Parametric Study of Separation Performance
Membrane performance back-calculation with larger bundle is less reliable Pinch effects from low driving pressure
After completion of mechanical integrity test, expect to change to 6” bundle for parametric studies of membrane performance
CO2 driving force 205 / 28 psia
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
0 0.2 0.4 0.6 0.8 1
Axial length (dimensionless)
CO
2 dr
ivin
g pr
essu
re (p
si)
CO2/N2 = 70
CO2/N2 = 100
Air Liquide DRTC August 2011 AIR LIQUIDE 24
Path Forward
Proceed with planned skid testingComplete 12” bundle mechanical integrity test (Q5)
Performance mapping with 6” bundle (end Q5 and Q8)
Long term test (Q5 – Q8)
Revise process simulations using actual bundle performance data to reassess potential to meet DOE targets
Field test will be proposed if revised simulation results are still positive