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© 2013 Pall Corporation

Identifying Pd-Based Ternary Membranes for

Carbon and Sulfur Applications

NETL CO2 Capture Technology Meeting Pittsburgh / July 29 – August 1, 2014

Amanda Lewis, Hongbin Zhao, & Scott Hopkins

2

Outline

Project overview Palladium membrane technology background Current project progress Future plans

3

Project Overview

Funding $1,517,000 Total $1,207,000 U.S. Department of Energy $310,000 Cost Share Performance Period October 1, 2009 to September 30, 2012 (three-year project as proposed) No cost extension(s) to September 30, 2014 Participants Pall Corporation (project management, support fabrication, module

construction, mixed-gas testing) Cornell University (composition spread fabrication on silicon wafer) Georgia Institute of Technology (surface characterization of exposed wafers) Colorado School of Mines (alloy membrane fabrication and annealing)

4

Project Overview Continued

Project Objectives Develop a high temperature and pressure membrane based

system for CO2 capture and hydrogen production that resists moderate levels of contaminants, typical in gasified coal.

Identify chemically resistant palladium-based ternary alloy(s) using a high-throughput screening method.

Demonstrate lab-scale fabrication and testing reproducibility. Understand long-term effects of carbon monoxide and

hydrogen sulfide before scaling up.

5

Current Technology

Sulfur Removal

WGS Reactors Selexol Coal

Gases

Low P CO2

H2 CO2 Capture by the Conventional Technology

CO2 Capture by Pd Membrane Reactor

Advantages and Challenges Offer the potential for combined processes Reduce CO2 compression costs Severe poisoning of membrane surface by

sulfur and others

Sulfur Removal

Pd Membrane Reactor Coal

Gases

High P CO2

H2

6

Pall’s Palladium Membrane Technology

Palladium Membrane (3-5 microns thick)

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Why Palladium

Figure adapted from: 1. Robeson, L.M. Journal of Membrane Science. 62(2):(1991) p. 165-185. 2. Robeson, L.M. Journal of Membrane Science. 320(1-2):(2008) p. 390-400. 3. Lewis, A. (2012) “How Contaminants and Alloying Metals Affect Hydrogen Permeation in Pd-Based Composite Membranes” (Ph.D. Thesis) – Colorado School of Mines.

1.8E-09 1.8E-08 1.8E-07 1.8E-06 1.8E-05

1.E+00

1.E+01

1.E+02

1.E+03

1.E+04

1.E+05

1.E+00

1.E+01

1.E+02

1.E+03

1.E+04

1.E+05

1 10 100 1000 10000 100000

Hydrogen Permeance (mol/m2-s-Pa)H

ydrogen/Nitrogen SelectivityH

ydro

gen/

Nitr

ogen

Sel

ectiv

ity

Hydrogen Permeability (Barrers)

PolymersUpper BoundCSM: PdCSM: Pd-AuCSM: Pd-AgCSM: Pd-Pt

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How Palladium Membrane Works

Pd Membrane

CO2

H2O

H2O

CO CO2

H2

H2

H2

H2

H2

High Pressure

Low Pressure

Permeation 1. Dissociative Adsorption 2. Surface-to-bulk 3. Bulk Diffusion 4. Bulk-to-Surface 5. Recombinative

Desorption

Disadvantages 1. Poor chemical

resistance 2. Embrittlement

9

High Throughput Alloy Screening

0

500

1000

1500

2000

2500

3000

0 4 8 12 16Levels for Each Factor / Element

Run

s of

Scr

eeni

ng E

xper

imen

ts

Ternary Alloy System L3

Binary Alloy System L2

Conventional: One at a Time vs. Combinatorial: Hundreds at a Time

X

Y

10

Combinatorial Pd Alloy Development Workflow

Composition Spread Fabrication: 50 alloys Prof. Bruce van Dover (Cornell)

Fabrication and Testing: 6 alloys Prof. Doug Way (CSM) and Pall

Heater

Heater

Conditioning Gas

Vent

Discs

SS Process Tube with Quartz Liner

Corrosion Assessment: Prof. Meilin Liu (Georgia Tech)

Syngas Exposure: Pall Corporation

L M

Pd

L M

Pd

11

Sputtered Wafers After Syngas Exposure

A B

Pd

A B

Pd

C D

Pd

C D

Pd

E F

Pd

E F

Pd

H I

Pd

H I

Pd

J K

Pd

J K

Pd

L M

Pd

L M

Pd

N O

Pd

N O

Pd

N O

Pd

P Q

Pd

P Q

Pd

R S

Pd

R S

Pd

12

Pure-gas Testing Summary at 500oC

0

0.2

0.4

0.6

0.8

1

1.2

1.4

1.6

Pd-A-B Pd-C-D Pd-E-F Pd-H-I Pd-J-K Pd-N-O

Hyd

roge

n Pe

rmea

bilit

y x

108

(mol

-m/m

2 /s/P

a0.5 )

13

Pd Alloy Simulated Syngas Testing

Testing Conditions Feed Pressure ~160 psig Temperature 400 / 500oC Testing Sequence 24 hours in 36 v% H2,

3 v% H2O, balance N2

24 hours in syngas 24 hours in syngas + 20

ppm H2S 24 hours in syngas

Syngas (air blown coal gasifier) H2 = 36 v% CO2 = 11 v% CO = 1.3 v% H2O = 3 v% N2 = 49 v%

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Sample Test Sequence

0.0E+00

2.0E-04

4.0E-04

6.0E-04

8.0E-04

1.0E-03

1.2E-03

0 20 40 60 80 100

Hyd

roge

n Pe

rmea

nce

(mol

H2/m

2 /s/P

a0.5 )

Time (hours)

No Carbon AverageSyngas No Sulfur AverageSyngas With Sulfur Average

Syngasno sulfurNo Carbon

Syngaswith sulfur

Syngasno sulfur

T = 500°C

1.

2.

1. Carbon Resistance2. Sulfur Resistance

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Testing Results at 500oC, Pfeed = 160 psig

*Note: membranes without the “no carbon” data were tested before the current testing plan was in place.

0.0E+00

2.0E-04

4.0E-04

6.0E-04

8.0E-04

1.0E-03

1.2E-03

1.4E-03

1.6E-03

Pd-A-B* Pd-C-D Pd-E-F Pd-H-I Pd-J-K Pd-N-O*

Hydr

ogen

Per

mea

nce

(mol

H2/

m2 /

s/Pa

0.5 )

Effect of Carbon and Sulfur on Hydrogen Permeance

No Carbon Syngas no H2S Syngas with H2S

16

Testing Results at 400oC, Pfeed = 160 psig

*Note: membranes without the “no carbon” data were tested before the current testing plan was in place.

0.E+00

2.E-04

4.E-04

6.E-04

8.E-04

1.E-03

Pd-A-B* Pd-C-D Pd-E-F Pd-H-I Pd-J-K Pd-N-O*

Hydr

ogen

Per

mea

nce

(mol

H2/

m2 /

s/Pa

0.5 )

Effect of Carbon and Sulfur on Hydrogen Permeance

No Carbon Syngas no H2S Syngas with H2S

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Project Schedule & Milestones

Completed Ongoing #Will not complete

#Tasks 5, 6, and 7 were changed to A and B due to time constraints.

*Task 4 was delayed, due to 1) negotiation of subcontract with Cornell University, 2) change of subcontractor from Cornell University to Colorado School of Mines to acquire technical capability of alloy membrane deposition on tubular substrate.

Task# Project Milestone Description Q3 Q4 Q1 Q2 Q3 Q4 Q1 Q2 Q3 Q4 Q1 Q2 Q3 Q4 Q1 Q2 Q3 Q4 Q1 Q2 Q3 Q4

1 Project management and planning

2 Literature and patent searchMilestone 1 Report demonstrating understanding of previous work

3Design and modeling of binary and ternary Pd alloysMilestone 2 Report on use of combinatorial method

4Construct and test 15 cm2 active membrane area prototypesMilestone 3 Report on testing of small scale membranes

5 Confirmation and long-term (100-500) testingMilestone 4 Report on testing of scaled-up membranes

6

Construct and test a working membrane module with best performing alloy from Task 5Milestone 5 Report on long-term performance of membranes

7

Provide complete analysis of relevant data sufficient of permit economic evaluatoin of the processMilestone 6 Report on advancement necessary to commercialize membrane process

AConfirmation and short-term repeat testing - top two performers

B Long-term (100-500) testingMilestone 4 Report on repeat testing: reproducibility and durability

20132009 2010 2011 2012 2014

No Cost Time Extension*

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Progress and Current Status

Task A Fabricate, anneal, and pure-gas test a minimum of three

confirmation membranes of top two performing alloys.

Completion: 100%

Task B Repeat mixed-gas testing procedure to confirm initial testing

results of at least three membranes.

Completion: 67% (two of each membrane have been mixed-gas tested, with one currently being tested)

Understand long-term (100+ continuous hours in simulated syngas) effects of carbon monoxide and hydrogen sulfide before scaling up.

Completion: 0%

19

Current Work: Repeat Testing of Pd-A-B

Demonstrates the sensitivity of permeability to composition Permeability data taken at 500oC

0

0.2

0.4

0.6

0.8

1

1.2

1.4

1.6

1.8

A-B-1 A-B-2 A-B-3 A-B-4 A-B-5 A-B-6

Hyd

roge

n Pe

rmea

bilit

y x

108

(mol

-m/m

2 /s/P

a0.5 )

20

Current Work: Repeat Testing of Pd-A-B

Demonstrates the testing reproducibility (data is taken at 500oC)

*Changed feed gas composition to be DOE test protocol for H2 separating membranes (test condition 2B, but with 20 ppm H2S instead of 30)

Syngas (Test 2B) H2 36% 33% CO2 11% 40% CO 1.3% = 1.3% H2O 3% 25% N2 49% 0%

0.00E+00

2.00E-04

4.00E-04

6.00E-04

8.00E-04

1.00E-03

1.20E-03

1.40E-03

Pd-A-B-1 Pd-A-B-2 Pd-A-B-2 Pd-A-B-3

Hyd

roge

n Pe

rmea

nce

(mol

/m2 /s

/Pa0.

5 )

Syngas no H2S Syngas with H2S

50% Drop

24% Drop*

23% Drop*

47% Drop

21

Current Work: Repeat Testing of Pd-J-K

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

J-K-1 J-K-2 J-K-3

Hyd

roge

n Pe

rmea

bilit

y x

108

(mol

-m/m

2 /s/P

a0.5 )

Demonstrates the sensitivity of permeability to composition Permeability data taken at 500oC

22

Current Work: Repeat Testing of Pd-J-K

J K

Pd

J K

Pd

Two repeat membranes have been tested in mixed-gas Both failed upon the introduction of H2S Current hypothesis is that the two repeat membranes are

on the edge of what can resist carbon and sulfur species ICP-MS analysis is being used to prove (or disprove) this

hypothesis

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Plan for Completion

Understand fabrication reproducibility Have completed two repeat tests of each

leading candidate with one remaining of Pd-J-K Use analysis (ICP-MS) to help explain

differences

Conduct long-term (100+) hour performance test to gain insight to membrane durability of each composition

24

Acknowledgements

U.S. DOE National Energy Technology Laboratory - Jason Hissam

Pall Corporation - Bill Hogan, Matthew Keeling

Colorado School of Mines - Douglas Way, Colin Wolden, Dan Cooney