Project ID: PD012 Ravindra Datta (PI) and Yi Hua Ma (co-PI) … · 2010. 6. 24. · Ravindra Datta...

Ravindra Datta (PI) and Yi Hua Ma (co-PI)Department of Chemical Engineering

Worcester Polytechnic InstituteWorcester, MA 01609

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Project ID: PD012

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”


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!

*


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


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!


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).


Support Porous

Film MetalMolten

BarrierDiffusion Layer Oxide

M1 + M2


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


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


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


Porous Stainless Steel (PSS)/Inconel Alloying?

Porous Ceramic Wettability/Sealing/Fragility?Al2O3ZrO2TiO2SiCPorous Vycor® glass

PSS/Inconel w/Oxide Layer Best Option?

Technical Accomplishment


a) Electroless plating (Controllable/Complex)

b) Electroplating (Versatile/Simple)c) Melt imbibition (Crude but quick)

Start with M1 = Sn; No M2;Porous Support = Inconel



−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



Self-passivating Electroless Deposition

Time

Depo

sit T

hick

ness

, µm



*Solution #1; acidic


Non-porous part of membrane

Sn-Cu:

Sn-Ni:

Sn thickness remains limited!

Electroplating Apparatus 3 Sn Electrodes


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



Upon melting, Sn alloyed with Inconel to form an impermeable layer


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


dzdppBD

RTN

i

ekii

+−=µ01


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


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

Project ID: PD012 Ravindra Datta (PI) and Yi Hua Ma (co-PI) … · 2010. 6. 24. · Ravindra Datta...

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