CO2 CAPTURE BY SUB-AMBIENT MEMBRANE OPERATION Library/Research/Coal/ewr/co2/22Aug11... · Capture by Sub-Ambient Membrane Operation Bench scale test of CO 2 ... modulation Cold box

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)


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)


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


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


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


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



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


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


CO2 Partial Condensation

CO2 depleted vent

LCO2

Cryogenic Heat

Exchanger system

Recompressed CO2enriched permeate

Power plant


CO2 Liquefier

Power plant

Flue gas Conditioning &Compression


CO2 Partial Condensation

CO2 depleted vent

LCO2

Cryogenic Heat

Exchanger system

Recompressed CO2enriched permeate


Cold Membrane Process Based on Existing AL Membrane

Hollow fiber membrane

provides most cost effective

solution for large gas separation

applications

Flue Gas

CO2


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


Hybrid Membrane + CPU Configuration

232 Psi

215 Psi

-30oC

17 Psi

-57oC


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]


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


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


P&ID of Test Skid

Compressor

Analytical skid

Cold box


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


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


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


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


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)


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


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


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


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

Documents

CO2 CAPTURE BY SUB-AMBIENT MEMBRANE OPERATION Library/Research/Coal/ewr/co2/22Aug11... · Capture by Sub-Ambient Membrane Operation Bench scale test of CO 2 ... modulation Cold box