Novel Polymer Membrane Process For Pre-Combustion CO2 Capture From

Coal-Fired Syngas

Tim Merkel, Sylvie Thomas, Meijuan Zhou,

Haiqing Lin and Adrian Serbanescu

Membrane Technology and Research, Inc.

2010 NETL CO2 Capture Technology Meeting September 17, 2010

www.mtrinc.com

Project Overview

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Award number #: DE-FE0001124Project period: 9/15/09 to 9/14/11Funding: $950k DOE; $150k MTR and $ 90k Tetramer TechnologiesDOE program manager: Richard DunstProject team:MTR --- membrane and process development

Tetramer Technologies --- specialty polymer synthesisSouthern Company NCCC --- field test

Project scope: The goal of this project is to develop a new polymer membrane and membrane separation process that will provide cost-effective CO2management in future coal-based IGCC power plants.

MTR

Southern

Tetramer

Project Objectives

Membrane development• High-temperature stable polymers for use in H2/CO2

• Composite membranes that have H2/CO2 >10 and H2 permeance >200 gpu at syngas cleanup temperatures (100-200oC)

Membrane performance evaluation• Evaluate membrane performance and lab-scale membrane

modules using simulated syngas

• Evaluate membrane stamps in the field using coal-fired syngas

Process design analysis• Optimize membrane process designs and assess the optimal

integration of a membrane system

• Perform a cost analysis of the polymer membrane process vs. current cleanup technologies, e.g., Selexol3

55 bar

600°C

Membrane Options for Syngas Cleanup

• Hot syngas cleanup membranes offer the potential for process intensification• Warm/cool syngas cleanup membranes offer fewer operating challenges

4

GasifierCoal CO2

O2

SyngasQuench

WGSreactors

Steam

ASU

Air

CO2comp

Combustionturbine

210°C 270°C

Syngas cooling

H235°C

2-stageSelexol™

Syngas reheat

40°C

195°C

50 bar

30 bar

150 barCO2storage

N2

Steam

1. Ciferino, J. and Marano, J, “Novel Integration of Gas Separation Membranes for CO2 Capture from IGCC Power Plants,”presented at AIChE New Orleans, April 2008.

55 bar

600°C

Membrane Options for Syngas Cleanup

• Hot syngas cleanup membranes offer the potential for process intensification• Warm/cool syngas cleanup membranes offer fewer operating challenges

5

GasifierCoal CO2

O2

SyngasQuench

WGSreactors

Steam

ASU

Air

CO2comp

Combustionturbine

210°C 270°C

Syngas cooling

150 barCO2storage

N2

Steam

30 bar

H2 membrane150-250°C

50 bar

1. Ciferino, J. and Marano, J, “Novel Integration of Gas Separation Membranes for CO2 Capture from IGCC Power Plants,”presented at AIChE New Orleans, April 2008.

55 bar

600°C

Membrane Options for Syngas Cleanup

• Hot syngas cleanup membranes offer the potential for process intensification• Warm/cool syngas cleanup membranes offer fewer operating challenges

6

GasifierCoal CO2

O2

SyngasQuench

WGSreactors

Steam

ASU

Air

CO2comp

Combustionturbine

210°C 270°C

Syngas cooling

150 barCO2storage

N2

Steam

30 bar

H2 membrane150-250°C

50 bar

5 bar

1. Ciferino, J. and Marano, J, “Novel Integration of Gas Separation Membranes for CO2 Capture from IGCC Power Plants,”presented at AIChE New Orleans, April 2008.

H2 + N2

Pros and Cons of Membranes for Syngas Cleanup

Advantages:

• Simple design; small footprint

• Energy efficient compared to sorption processes

• No water used; no leakage or disposal of chemical solvents

Challenges:

• Membrane reactor for hot/warm gas cleanup --- difficult operating conditions, stability in presence of contaminants

• Inorganic membranes --- lack of reproducible, low-cost module fabrication technology

• Polymer membranes --- thermal stability of membrane materials for hot/warm gas cleanup

7

New high-temperature membranes show promising performance

1. O’Brien K. et al., “Fabrication and Scale-Up of PBI - Based Membrane System for Pre-Combustion Capture of Carbon Dioxide,” DOE NETL project fact sheet 2009.

2. Low, B.T., et al., “Simultaneous Occurrence of Chemical Grafting, Cross-linking, and Etching on the Surface of Polyimide Membranes and Their Impact on H2/CO2 Separation,” Macromolecules 41(4),1297-1309 (2008).

Permeance conversions:

1 gpu = 10-6 cm3(STP)/(cm2 s cmHg)

1 ft3(STP)/(h ft2 psi) = 1,600 gpu

10-6 mol/(m2 s Pa) = 3,000 gpu

10-2 mol/(m2 s bar) = 300 gpu

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0.

1

10

100

1 10 100 1,000

Upper bound

H2 permeance (gpu)

H2/CO2

selectivity

MTR Proteus TM

mixed-gas; 150°C

PBI (2500C)1

Amine modified PI 2

Membrane performance has improved significantly

9

0

5

10

15

20

0 200 400 600 800 1000

H2/CO2 Selectivity

H2 Permeance (gpu)

Target (200, 10)

Initial performance

2nd quarterperformance

3rd quarterperformance

1st quarterperformance

150°C

Mixed-gas performance at 50 psig, 150°C with a 50%/50% H2/CO2 mixture

Key objectives are to• Examine membrane performance with real syngas, including gases difficult to

study in the lab (CO, H2S)

• Investigate the membrane performance, stability and, if degradation occurs, try to identify mechanisms

Two types of membranes were tested• CO2-selective Polaris modules (tested at 40°C, 165 -190 psia)

• H2-selective Proteus membranes (tested at 120°C or 135°C, 165 – 190 psia)

Total of three field tests to date; each test lasted 3 to 6 weeks• November 2009, April 2010 and August 2010

Two types of syngas streams were provided • Unshifted syngas: 10%H2, 69%N2, 1%CH4, 7%CO, and 13%CO2

• Shifted syngas: 13%H2, 69%N2, 1%CH4, 2%CO, 15%CO2 and 780ppm H2S.

Field Tests at the National Carbon Capture Center (NCCC)

MTR Test Unit at NCCC

11RESIDUE GASFEED GASPERMEATE GAS

12

1

10

100

1,000

0 5 10 15 20

Mixed-gaspermeance

(gpu)

Time (days)

CO2

H2

Permeance Selectivity

NCCC Results 1: Stable Performance with Desulfurized Syngas

Tests were conducted on membrane stamps (area = 30.2 cm2) with a coal-derived syngas mixture at 150 psig and 135°C. Average H2 permeance = 260 gpu and H2/CO2selectivity = 16.

0

5

10

15

20

25

30

35

40

0 5 10 15 20

Time (days)

H2/CO

2

selectivity

135°C

13

NCCC Results 2: Stable Performance with High Sulfur Syngas

1

10

100

1,000

0 5 10 15 20 25

Mixed-gas permeance

(gpu)

Time (days)

CO2

H2

135°C120°C

120°C

135°C

0

5

10

15

20

25

30

35

40

0 5 10 15 20 25

Time (days)

Mixed-gas H2/CO2

selectivity

120°C

135°C

Permeance Selectivity

Tests were conducted on membrane stamps (area = 30.2 cm2) with a coal-derived shifted syngas mixture at 175 psig and 120°C or135°C.

H2 content was enriched from ~10% to ~60 – 80%. H2/gas selectivities (CH4, N2, CO and H2S) are higher than H2/CO2.

Current membranes show potential to approach the DOE LCOE target

14

5

10

15

20

25

30

0 10 20 30 40 50 60

Increase in LCOE

(%)

Membrane H2/CO2 selectivity

90% CO2 capture

300 gpu

600 gpu

900 gpu

H2 permeance

DOE target

Calculations are for shifted syngas from a GE gasifier (case 2 in the DOE Bituminous Coal Baseline Report).

Selexol™ installation and contingency factors were used for the membrane cases.

Base case

SelexolTM

Milestones

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Confirmed that composite membranes made from novel polymers give hydrogen permeances of at least 200 gpu and H2/CO2 selectivities of greater than 10 in bench-scale tests as well as in field tests.

Completed scale up of composite membranes on a commercial coater.

Identified the membrane performance requirement in order to meet the DOE program targets. Determined the overall technical and economic competitiveness of the proposed process as compared to alternative technologies.

Develop bench-scale membrane modules and demonstrate module performance and lifetime consistency with small-scale membrane stamp studies.

Lab-scale module development is on-going

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Lab-scale prototype module: 12’’ length with a membrane area of 0.14 m2

Module components were stable after cycling from 20 to 160°C

Module housing

Lab-scale prototype module

Project timeline: original

Sept 2009 Sept 2010 Sept 2011

Composite membrane development

Membrane process design and optimization

Membrane optimization and scale up

Lab-scale module development

Stamp field test @ Southern

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Sept 2009 Sept 2010 Sept 2011

Composite membrane development

Membrane process design

Lab-scale module development

Stamp field test @ Southern

Membrane optimization scale-up

Project Timeline: update

Module development

Module field test @ Southern

Improve membrane selectivity

All milestones achieved18

Next Steps toward Commercialization

19

Improve membrane performance

Develop commerical-scale modules

Evaluate long-term high temperature stability

Test membrane modules

at NCCC in 2011

→ 50 lb/h syngas run

→ 500 lb/h syngas run

Summary

Bench and field tests show that the performance of MTR Proteus™ membranes exceeds the project targets.

NCCC field results demonstrate the membrane performance is stable at high temperature treating coal-derived syngas containing up to 780 ppm H2S.

Average field performance gives a mixed-gas H2/CO2selectivity of 15-25, and a hydrogen permeance of 150-300 gpu at 120-150°C.

Current membrane performance yields an increase in LCOE of ~15%. Higher H2/CO2 selectivity and higher H2permeance are both needed to achieve DOE LCOE targets.

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Acknowledgements

• U.S. Department of Energy,National Energy Technology Laboratory– Richard Dunst

• Southern Company– Tony Wu– Frank Morton– John Wheeldon

• Tetramer Technologies– Earl Wagener, Jack Jin – Viktor Klep, Adam Haldeman