High-Performance, Durable, Palladium-Alloy Membrane
forHydrogen Separation
andPurificationPresented by:Scott Hopkins
Pall CorporationMay 15, 2007
Project ID #PDP11This presentation does not contain any proprietary or confidential information
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Project Contributors
• Pall Corporation– Jim Acquaviva– Scott Hopkins
• Chevron– Karen Barnett– Babak Fayyaz-Najafi– Kevin Nguyen– Lixin You– Lyman Young
• Colorado School of Mines– Paul M. Thoen– Sabina K. Gade– J. Douglas Way
• Oak Ridge National Lab –High Temp. Materials Lab– Andrew Payzant
• DOE– Arlene Anderson– Carolyn Elam
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OverviewTimeline
• July, 2005 start date• September, 2009 end date• 30% complete
• $4 Million Project Total– $2.4M DOE share– $1.6M Contractor share
• $100K DOE funding in FY05• $175K DOE funding in FY06• $540K DOE funding in FY07** Anticipated
Budget
2010 Targets• Cost: $2.50 per GGE for H2
(delivered/untaxed)• H2 Quality: 99.95%
Partners• Chevron• Colorado School of Mines• ORNL – High Temperature
Materials Lab
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Project Objectives• Establish the technical and economic viability for use
of a palladium alloy composite membrane in a distributed hydrogen production system– Propose a process that leverages the technical
capabilities of the membrane for maximum economic benefit (reduced gallon of gas equivalent cost)
– Optimize membrane performance in terms of hydrogen throughput, purity and durability
– Minimize capital cost for the gas separation module• Pressure vessel• Internal hardware• Membrane • Substrate
Photo courtesy of Chevron
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Why Membrane ?• Capital and operating cost for a hydrogen
production system can potentially be reduced through process intensification
• Membranes that can be operated at high temperatures allow for integration with high temperature reforming processes
• Simple, compact separation systems can be designed using membranes
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1. Lee, D., Zhang, L., Oyama, S. T., Niu, S., and R. F Saraf, J. Membr. Sci., 231, 117(2004).
2. Kajiwara, M., Uemiya, S., Kojima, T., and E. Kikuchi, Catal. Today, 56, 65(2000).
3. DeVos, R. M. and H. Verweij, Science, 279, 1710(1998).
4. Hassan, M. H., J. D. Way, P. M. Thoen, and A. C. Dillon, J. Membr. Sci. , 104, 27(1995).
5. Polymer line from :Robeson, L. M., J. Membr. Sci., 62, 165(1991).
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10
100
1000
104
105
10-9 10-8 10-7 10-6 10-5 0.0001
10-9 10-8 10-7 10-6 10-5 0.0001
Polymeric Membrane MaterialsInorganic Membrane Materials
H2/N
2 Idea
l Sep
arat
ion
Fact
or
H2 Permeance (mol/m2.s.Pa)
CSM PdAu Composite #102
(1)
(2)
(3)
(4)
Why Palladium Membrane ?Project Accomplishments
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Pd alloy membrane– Functional layer provides for
gas separation– Critical features: thickness,
alloy composition and number of defects
Diffusion barrier– Enables formation of
functional layer– Critical features: surface
properties, material, gas permeability, number of defects
Components of a Composite Membrane
Porous Stainless Steel– Provides mechanical
support that can withstand the operating conditions of the process
– Critical features: permeability,weld configuration,mechanical, thermal and chemical compatibility
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The Influence of Pd Membrane Thickness on Pure H2 Flux @ 400 °C, 20 psig
0
50
100
150
200
250
300
350
400
0.00 0.20 0.40 0.60 0.80 1.00 1.20
Hyd
roge
n Fl
ux (s
cfh/
ft2 )
1/Membrane Thickness (1/microns)
3.8
5.1
7.2
Membrane Thickness (microns)
2.1
DO
E H
FI T
arge
ts
1.05.0 2.5 1.5
2005
2010
20151.3
0.93
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Technical Accomplishments/ Progress/ResultsDiffusion Barrier Properties
• Surface roughness 2005: Ra = 25 – 35 micro inch
• Surface roughness 2006: Ra = 8 – 12 micro inch
• Membrane over welds 2005: no leaks up to 20 psi
• Membrane over welds 2006: no leaks up to 40 psi
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Support tubes – as welded
Support tubes ZrO2 coated
Porous Stainless Steel
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Components of a Gas/Gas Separation ModulePressure vessel with fittings
Internal hardware
Non-porous end fitting
Porous substrate
Weld
Membrane tube sub-assembly*
* Pd alloy membrane not shown, typically on the OD of the tube
Welds
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Research Development
Scalability of Metal Tube Technology
Commercialization
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Guidelines for Membrane Performance2010 DOE / EERE Targets for Dense Metallic Membrane*
– Flux: 250scfh/ft2 @20 psi & 400oC
– Module Cost: $1,000/ft2
– Durability: 3 years
– Operating pressure: 400 PSI
– H2 Recovery: > 80%
– H2 quality: 99.99 %
* As per the Multi-Year RD&D Plan Updated 11/14/06 http://www1.eere.energy.gov/hydrogenandfuelcells/mypp/pdfs/production.pdf
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Technical Accomplishments/ Progress/Results
0
50
100
150
200
250
300
0.0
0.0050
0.010
0.015
0.020
0.025
0.030
0 50 100 150
H2and N
2 Flux for PdAu Membrane, CSM-Pall-102,
at 20 psi Transmembrane Pressure and 400 oC.
H2 Flux
N2 Flux
H2 Fl
ux (S
CFH
/ft2)N
2 Flux (SFC
H/ft2)
Time (hrs)
2 minair
1 minair
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Automated Gas/Gas Separation Test Stand
Photos courtesy of Chevron
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CSM Test Data Confirmed at Pall Corp and Chevron
0
50
100
150
200
250
300
350
400
0 5 10 15 20 25 30 35
CSM ResultsPall ResultsChevron Results
H2 F
lux
(SC
FH/ft
2 )
H2 Transmembrane Pressure (psi)
Test Location
Ideal H2/N2
*
CSM 90,000
Pall ∞Chevron ∞
* Ideal H2/N2 selectivity at 20 psi
Note: Same membrane sample tested at all three locations
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Future Work• Optimize substrate and alloy properties
to meet or exceed membrane targets• Test membrane in synthetic reformate
streams to establish conditions for >80% hydrogen recovery
• Establish long term durability testing at temperature
• Use membrane properties for economic analysis of advanced process design to achieve targeted H2 production costs
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Proposed Use of Pd Alloy Membrane in a Hydrogen Production System
DesulfurizationUnit
Natural gas (reactant)
Natural gas (fuel)
Water
H2
Storage
PEM
Retentate Side (Fuel Optional)
Condensor
Pd-alloy membrane
Modified CVX Adv. SMR
Multi stage compressor
Modified Chevron Adv . SMR Integrated with Pd -alloy Membrane
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Economic Analysis Strategy
Economic Model
Membrane Model Energy Model
H2 Cost($/gge)
Process D
ata
Adv. SMR ProcessModel
Compression
Cost
Hydrogen Permeate Flow
Surface AreaMembrane Pilot Plant
Performance Measurements
Adv. SMR
CompressorOPEX & CAPEX
MembraneOPEX & CAPEX
PSAOPEX & CAPEX
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Summary• Developed porous stainless steel substrate and
diffusion barrier that enables formation of high flux Pd alloy membranes
• Produced Pd alloy membranes that exceed the 2010 target for H2 flux and purity
• Analyzed membrane and module manufacturing costs to confirm the current cost basis ($1,500 ft2)
• Completed fabrication of an automated test stand for long term testing with synthetic reformate
• Established membrane, process and energy models that will be used to determine overall economics for H2 production
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The most significant hydrogen hazards associated with this project are:A test system that leaks hydrogen while at
temperature. Plumbing is tested for leaks prior to installation in the furnaceMixing hydrogen with air while system is at temperature. An argon or nitrogen purge is used to evacuate the system of residual air after an air purge cycle, prior to introducing hydrogen to the system.
Hydrogen Safety
