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Ravindra Datta (PI) and Yi Hua Ma (co-PI)Department of Chemical Engineering
Worcester Polytechnic InstituteWorcester, MA 01609
This presentation does not contain any proprietary, confidential, or otherwise restricted information.
Project ID: PD012
2010 DOE Hydrogen Program Review
2010 DOE Hydrogen Program Review
Award No. DE-FE0001050
Timeline:Start Date: 9.30.2009End Date: 9.29.2012
Budget:Govt. Share: $996,567WPI Share: $249,857Total: $1,246,424
Funding Received:FY 09: $347,814
Project Manager: Jason C. Hissam
Technical Barriers:Non-precious metalsLow costHigh H2 flux &
selectivityCO & sulfur tolerance
Technical Targets: NETL Test Protocol: 2008/1335, October,
2008
“Supported Molten-Metal Membrane (SMMM) for Hydrogen Separation”
2010 DOE Hydrogen Program Review
Property 2010 Target 2015 TargetH2 Flux (std m3/m2.h) 60 90H2 Feed Pressure, (psia) 150 150H2 Permeate Pressure, (psia) 50 50Operating (psi) 100 100Operating Temperature, T (ºC) 300–600 250–500Pressure Tolerance, (psi) 400 800–1,000Sulfur Tolerance (ppm) 20 >100CO Tolerance Yes YesWGS Activity Yes YesH2 Purity (%) 99.5 99.99Cost ($/ft2) 500 <250
*Implies dense membrane!
*
2010 DOE Hydrogen Program Review
δ)(
)(2/1,H
2/1,H
HH22
22
pf ppQN
−=
∆+∆−==
RTHHKKcKKcS A
AtAt
oH
o
H,00,H exp)())((
−
∆−=
RTE
RTSD DD expexp
61 ‡
02
H νλ
HH2DSQ ×=
Lattice Structure Crystalline Amorphous Molten
2010 DOE Hydrogen Program Review
Enhance H diffusion via a more open lattice (M1) Enhance H dissolution via more open lattice (M1) Enhance density of surface dissociation sites (M2) Enhance H2 dissociative adsorption via catalyst (M2)
Molten metals/alloys for M1!
2010 DOE Hydrogen Program Review
Molten Ag
E. M. Sacris, and N. A. D. Parlee, “The Diffusion of Hydrogen in Liquid Ni, Cu, Ag, and Sn,” Metallurgical and Materials Transactions B, 1, 3377-3382 (1970).
Iron
Woodtli, J., and Keiselbach, R., Engng. Failure Analysis, 7, 427-450 (2000).
2010 DOE Hydrogen Program Review
Support Porous
Film MetalMolten
BarrierDiffusion Layer Oxide
M1 + M2
2010 DOE Hydrogen Program Review
Cheaper/abundant metals
Broader temperature range
Lack ofThermal mismatchSinteringHydrogen embrittlementPin holes
Improved CO toleranceImproved S tolerance
Molten Metal/Support InteractionsWettabilityAlloying with Substrate
Membrane StabilityChemicalPhysical
H2 Dissociation Activity
2010 DOE Hydrogen Program Review
PI has extensive experience in fuel cells and H2 catalysis, and has developed the technique of Supported Molten-Metal Catalysis (SMMC)Guidance in selection of molten metals/alloysGuidance in permeation modeling
Co-PI is a leading researcher in Pd/Pd-alloy membranesGuidance in selection of porous supportsGuidance in developing fabrication protocol
2010 DOE Hydrogen Program Review
1. Select molten metal (M1) and catalyst (M2) 2. Select suitable porous supports (porous
metal, with or without a diffusion barrier, or ceramic)
3. Develop membrane fabrication protocols4. Establish basic feasibility of the SMMM
2010 DOE Hydrogen Program ReviewTechnical Accomplishment
2010 DOE Hydrogen Program Review Technical Accomplishment
M2
M2
M1
2010 DOE Hydrogen Program Review Technical Accomplishment Porous Metal with Ceramic Layer
Plug side Open sidePorous part
5″ 16″6″27″
1″
Porous Metal
Porous Ceramic
2010 DOE Hydrogen Program Review
Porous Stainless Steel (PSS)/Inconel Alloying?
Porous Ceramic Wettability/Sealing/Fragility?Al2O3ZrO2TiO2SiCPorous Vycor® glass
PSS/Inconel w/Oxide Layer Best Option?
Technical Accomplishment
2010 DOE Hydrogen Program Review
a) Electroless plating (Controllable/Complex)
b) Electroplating (Versatile/Simple)c) Melt imbibition (Crude but quick)
Start with M1 = Sn; No M2;Porous Support = Inconel
Technical Accomplishment
2010 DOE Hydrogen Program Review
−22POH
−2e
−2e
−32POH
2SnCl
OH2 2HCl
PONaHSn2HCl OHPONaHSn(Cl) :
1 2eH2POHNa OHPOHNa :
1 HCl2Sn 2eH2Sn(Cl) :
Reaction, Electrode
320
2222
32
Pd
222
02
++++
++++
++++
−+−+−+
−+
Overall
Anode
Cathode
s ρρ σ
Technical Accomplishment
2010 DOE Hydrogen Program Review
Self-passivating Electroless Deposition
Time
Depo
sit T
hick
ness
, µm
Technical Accomplishment
2010 DOE Hydrogen Program Review
*Solution #1; acidic
Technical Accomplishment
Non-porous part of membrane
Sn-Cu:
Sn-Ni:
Sn thickness remains limited!
Electroplating Apparatus 3 Sn Electrodes
2010 DOE Hydrogen Program Review
Whiskers
2424
mA/cm 25
SOH M 0.3 ,SnSO M 0.2 :SolutionL) 5.7" OD, (1" m 0.1Support Inconel Porous
=i
µ
Technical Accomplishment
2010 DOE Hydrogen Program Review Technical Accomplishment
Upon melting, Sn alloyed with Inconel to form an impermeable layer
2010 DOE Hydrogen Program Review Technical Accomplishment
2010 DOE Hydrogen Program Review Technical Accomplishment
2010 DOE Hydrogen Program Review Technical Accomplishment
0
10
20
30
40
50
60
70
80 85 90 95 100 105 110 115
Elapsed Time [hr]
Flux
[m3 /m
2 -h]
0
50
100
150
200
250
300
Tem
pera
ture
[o C]
He
H2
H2
2010 DOE Hydrogen Program Review Technical Accomplishment
2010 DOE Hydrogen Program Review Technical Accomplishment
dzdppBD
RTN
i
ekii
+−=µ01
2010 DOE Hydrogen Program Review
1. Alternate Supportsa. Porous Stainless Steel with Oxide Layerb. Other Porous Ceramic Supports
2. Alternate Molten Metalsa. M1: In, Ga, Bib. M2: Ni, Cu, Co, Ag, W, Mo, Nb
3. SMMM Feasibility and Permeation Studies
2010 DOE Hydrogen Program Review
1. Steady progress made toward goals of Phase I2. Identified candidates for molten metals/supports3. Developed electroless/electroplating methodologies
for SMMM fabrication4. Porous metal supports likely not suitable due to
alloying with molten metals5. Sealing and fragility an issue with ceramic supports6. Work planned to Fabricate SMMM on PSS with Oxide Layer Establish feasibility Study Performance characteristics Incorporate M2 to enhance SMMM permeability