Transformational Membranes for

Pre-combustion Carbon Capture

DE-FE0031635

Winston Ho / Yang HanWilliam G. Lowrie Department of Chemical & Biomolecular Engineering

Department of Materials Science and Engineering

The Ohio State University

2019 NETL Technologies Integrated Review Meeting

Pittsburgh, PA, August 27, 20191

Project Objective

• Develop a cost-effective design and fabrication process for a novel transformational membrane and its membrane modules that capture CO2 from coal-derived syngas

• 95% CO2 Purity

• >99% H2 Recovery

• COE 30% Less than Baseline Approaches

2

2-Budget Period Project

• BP1: 10/01/2018 – 03/31/2020– Laboratory-scale membrane synthesis, characterization and

transport performance studies– High-level preliminary techno-economic analysis

• BP2: 04/01/2020 – 09/30/2021– Laboratory-scale membrane synthesis, characterization and

transport performance studies to continue– Fabrication, characterization and transport performance

studies of scale-up membrane (14″ wide by 20′ long) – Fabrication, performance and stability testing of spiral-wound

membrane modules– Update techno-economic analysis performed in BP 1

3

• Integrated program with fundamental studies, applied research, synthesis, characterization and transport studies, and high-level techno-economic analysis

4

Funding and Performance Dates

• Total Budget: 10/01/2018 – 09/30/2021 DOE: $799,988; OSU: $199,998 (20% cost share)

• BP1: 10/01/2018 – 03/31/2020 DOE: $386,694; OSU: $96,674

• BP2: 04/01/2020 – 09/30/2021 DOE: $413,294; OSU: $103,324

5

Technical Background: Proposed Process

•Proposed membrane process does not require significant syngas cooling (compared to competition)

31.7 bar

54.1 bar, 31% CO2

50 bar 153 bar

>95% CO2

31.7 bar

4% CO2

<10 ppm H2S

H2S

Removal

(Selexol)

6

Location of Proposed Technology in

IGCC Plant

Selective Amine Polymer Layer / Polymer Support

Simplicity of Membrane for Low Cost

7

≈ ≈

≈

Selective amine polymer layer

(~15 µm, dense layer)

Nonwoven fabric backing

(~100 μm)

Polymer support(~20 μm, Ø ~10 nm)

8

Amine Polymer Layer Contains Mobile and Fixed Carriers: Facilitated Transport

CO2 CO2

Membrane

CO2+

CO2

CO2

CO2

Mobile

Carrier

Facilitated Transport

Feed Side Permeate Side

Non-Reacting

Gas: H2H2

Physical Solution-Diffusion

Mobile

Carrier

CO2

Mobile

Carrier

CO2

Mobile

Carrier

9

Tunable Amine-CO2 Chemistry

• Reaction of CO2 with Unhindered Amines

CO2 + R–NH2 ⇌ R–NH2+–COO–

R–NH2+–COO– + R–NH2 ⇌ R–NH–COO– + R–NH3

+

Overall:

CO2 + 2 R–NH2 ⇌ R–NH–COO– + R–NH3+

• Reaction of CO2 with Hindered Amines

CO2 + R1–NH–R2 ⇌ R1R2–NH+–COO–

R1R2–NH+–COO– + H2O ⇌ R1R2–NH2+ + HCO3

-

Overall: Can double the CO2 capacity

CO2 + R1–NH–R2 + H2O ⇌ R1R2–NH2+ + HCO3

-

Facilitated Transport vs.Solution-Diffusion Mechanism

• CO2 Facilitated Transport Flux: Very High– CO2-amine reaction enhances CO2 flux

• H2 Flux: Very Low– H2 does not react with amine

– H2 transport follows conventional physical solution-

diffusion mechanism, which is very slow

10

10

100

1000

180 200 220 240 260 280 300 320

CO

2/H

2s

ele

cti

vit

y

CO2 permeance (GPU)11

Membrane Performances

BP1Q1

BP1Q2

BP1Q3

Enhanced

Physical

Solubility

Enhanced

Chemical

Solubility

12

Membrane Performances

Simulated Syngas at 107°C and 31.7 bar

Effect of Carrier Saturation Phenomenon on Performance

13

Effect of CO2 Permeance on Cost of Electricity Increase

0

5

10

15

20

25

30

35

14

15

16

17

18

19

50 100 150 200 250 300 350 400 450 500

Mem

bra

ne a

rea (

×10

4m

2)

CO

E in

cre

ase (

%)

CO2 permeance (GPU)

COE increase

Membrane area

COE increase

of BP1Q1COE increase

of BP1Q2

COE increase

of BP1Q3

14

Membranes Synthesized with Tuned H2S/CO2 Selectivities

0

3

6

9

0 1 2 3 4 5 6 7 8 9 10 11 12 13

H2S

/CO

2s

ele

cti

vit

y

Feed CO2 partial pressure (bar)

Membrane M6

Membrane BP1Q3

15

Effect of H2S/CO2 Selectivity on H2S Concentration in H2 Product

16

0.1

1

10

100

1000

10000

1 2 3 4 5 6

Sw

eet

syn

gas H

2S

(p

pm

v)

H2S/CO2 selectivity

< 6 ppm H2S

for BP1Q3

Plans for Future Testing/Development

17

• Remaining BP1– Increase CO2 Sorption at High Pressure

– Enhance Membrane Mechanical Properties

– Preliminary Techno-Economic Analysis

• BP2– Membrane Scale-up and Characterization

+ Continuous roll-to-roll fabrication (14″ wide by 20′ long)

– Prototype SW Module Fabrication

+ Fabricate 9 prototype SW modules (800 cm2 each)

+ 200-h stability test with simulated syngas

– Final Techno-Economic Analysis

18

Acknowledgments

David Lang & José Figueroa, DOE/NETL

Financial Support

DOE/NETLDE-FE0031635

– Federal funding for membrane development