Advanced Hydrogen Transport Membranes for Vision 21 Fossil ... · ST P) 1 4 8 14 23 34 Permeability...

ELTRON RESEARCH INC. Slide 1

ADVANCED HYDROGEN TRANSPORT MEMBRANES FOR VISION 21 FOSSIL FUEL PLANTS

Presented byAnthony F. SammellsEltron Research Inc.Boulder, CO 80301

May 24, 2005

This presentation does not contain any proprietary or confidential information. #PD11


OverviewTimeline• Project start date: October 1, 2000• Project end date: September 30, 2005• 85% percent complete

Budget• Total project funding: $2,800,000

– DOE share: $2,240,000– Contractor share: $ 560,000

• Funding received in FY04: $ 377,765• Funding for FY05: $ 736,244

Barriers Addressed• Reducing hydrogen cost• Hydrogen production from diverse

pathways• Hydrogen of sufficient purity for fuel

cells

Technical Targets• High hydrogen flux at temperatures

compatible with water-gas shift catalysis

• Compatibility with simultaneous carbon dioxide sequestration

• Stable to syngas conditions

Partners• CoorsTek• Sűd Chemie• Noram Engineering• ANL


Objectives• Identify low-cost high-performance hydrogen

transport membranes• Operate using representative synthesis

mixtures• Verify performance under high-pressure

differentials comparable with simultaneous carbon dioxide sequestration

• Address sweep gas / no sweep gas issue on membrane permeate side

• Long-term performance• Cost issues


Overall Scheme for Converting Hydrocarbon Feedstock to

Hydrogen with Simultaneous Carbon Dioxide Sequestration

OxygenTransportMembrane

Natural GasCoal

Biomass

H2 + CO2

320°C - 440°C29-35 bara

DenseHydrogenTransportMembrane 100% H2 Fuel Cells

TurbinesChemical Use

Syngas fromWater-Gas

Shift Reactor

CO2 29-35 bara

Sequestration


Integration of Water-Gas Shift Catalysts with Hydrogen Transport Membranes

for Separation of Hydrogen from Carbon Dioxide

Dense Membrane for H2 Separation

Catalysts for Re-associationand Desorption of Hydrogen

Hydrogen DissociationCatalysis

e-

H+

e-

H+

e-

H+

H+

H2

H2

H2

CO2

CO + H2 + H2O

H2

2

H+ +

2e-

(at m

embr

ane

oxid

izin

g su

rfac

e)

Wat

er-G

as-S

hift

Cat

alys

t Bed

CO

+ H

2O

CO

2 + H

2

2H+ +

2e-

H

2

(at m

embr

ane

redu

cing

sur

face

)


Eltron H2 Separation Membrane CharacteristicsMembraneCategory

TemperatureRange (°C)

MaximumPermeation Rate(mL·min-1·cm-2)

Single Phase Ceramic 700 to 950 ≈ 0.01

Thin Film Palladium on Porous Support

320 to 600 >50

Ceramic/Ceramic 700 to 950 ≈ 0.1

High-Temperature CermetWith Non H2-Permeable Metal (Ni)

700 to 950 ≈ 1

High-Temperature Cermet with H2-Permeable Metal (Pd)

400 to 800 ≈ 4

Intermediate-TemperatureComposite

320 to 440 >400


High-Pressure Differential Hydrogen Separation Units

• Tests to 69 bar (1000 psi) differential pressure at 320-440°C

• Tests with high pressure WGS mixture


Pressure Differential Hydrogen Flux Measurements under Ideal

40% H2/He Conditions as a Function of Membrane Thickness

• Bulk diffusion is rate limiting for 250 and 500 micron thick membranes.

• Flux identical for 75 and 130 micron thick membranes. Bulk diffusion is not rate limiting.

• Gas phase diffusion limited.

Comparison of Hydrogen Flux at 440°C for Various Membrane ThicknessIdeal H2/He Conditions. 75 to 500 microns thick. 16 mm diameter disks.

0

50

100

150

200

250

300

350

0 200 400 600 800 1000 1200

H2

Flux

(mL·

min

-1·c

m-2

STP)

75 micron130 micron250 micron500 micron

139631H2 Partial Pressure, Feed Side (bar)

Sieverts' LawPredictions

PH21/2(feed)-PH2

1/2(sweep) (Pa1/2)

Permeability130 = 2.4x10-7 mol·m-1 ·s-1 ·Pa-0.5


Permeability 75 = 1.3x10-7 mol·m-1 ·s-1 ·Pa-0.5


Comparison of Hydrogen Flux at 440°C for Various Membrane ThicknessIdeal H2/He Conditions. 75 to 500 microns thick. 16 mm diameter disks.

0

50

100

150

200

250

300

350

0 200 400 600 800 1000 1200

H2

Flux

(mL·

min

-1·c

m-2

STP)

75 micron130 micron250 micron500 micron

139631H2 Partial Pressure, Feed Side (bar)

Sieverts' LawPredictions

PH21/2(feed)-PH2

1/2(sweep) (Pa1/2)










Hydrogen Flux at High Pressure Differential

Hydrogen Partial Pressure at Feed Side (bar)

0

100

200

300

400

500

0 500 1000 1500 2000

pf1/2-ps

1/2(Pa1/2)

H2 P

erm

eatio

n (m

L·m

in-1

·cm

-2ST

P)

342314841

Permeability = 2.3 x10-7 mol·m-1·s-1·Pa-0.5

H2 Flux up to 423 mL·min-1·cm-2

• Permeability of 2.3x10-7 mol·m-1·s-1·Pa-0.5 and hydrogen flux of 423 mL·min-1·cm-2 (STP) achieved at 440°C (713K) under ideal hydrogen-helium mixture up to 33 bar (476 psi) differential pressure and partial pressure of hydrogen of 34 bar (488 psi).


Long-Term Ambient Pressure Performance

Performance of Hydrogen Transport Membrane(80% H2 / 20% He Feed at 320°C)

0

2

4

6

8

10

12

14

16

18

20

0 2 4 6 8

Months

H2 P

erm

eatio

n (m

L· m

in-1

· cm

-2 ST

P)

Regeneration Step

• No guard bed used to adsorb impurities.


Long-Term Results

Long-term test @ 340 oC with a feed containing 41.4%H2, 37.3%H2O, 3.3%CO and 17.8% CO2 and a Cu/ZnO guard bed

0

2

4

6

8

10

12

14

16

18

20

0 400 800 1200 1600 2000 2400 2800Time (Hours)

H2 F

lux

(mL·

min

-1·c

m-2

STP

)

0.0E+00

2.0E-08

4.0E-08

6.0E-08

8.0E-08

1.0E-07

1.2E-07

1.4E-07

1.6E-07

1.8E-07

2.0E-07

Perm

eabi

lity

(mol

·s-1

·m-1

·Pa-0

.5)

H2 Flux

Permeability


Membrane Performance upon Going from Ideal to Syngas Conditions

0

50

100

150

200

250

300

0 200 400 600 800 1000

Pf1/2 - Ps

1/2 (Pa1/2)

H2 f

lux

(mL·

min

-1·c

m-2

STP

)

40%H2 and 60%He

39%H2 and 59%H2O

41%H2, 18%CO2, and 37%H2O

41%H2, 3.3%CO, 17.8%CO2 and 37%H2O


Dependency of Membrane Performance on Carbon Monoxide Fraction

CO Dependency at 420oC and 200 psig

0.0E+00

4.0E-08

8.0E-08

1.2E-07

1.6E-07

2.0E-07

2.4E-07

2.8E-07

3.2E-07

3.6E-07

4.0E-07

0 0.5 1 1.5 2 2.5 3 3.5 4

CO Concentration (vol%)

H P

erm

eabi

lity

(mol

·m-1

·s-1

·Pa-0

.5)

41% H2, 17.8% CO2, 37.3%H2O,3.5% (He+CO)


Performance of a 250-Micron Hydrogen Transport Membrane up to 1000 psi

Pressure Differential at 420°C

0

20

40

60

80

100

120

0 200 400 600 800 1000 1200 1400 1600 1800 2000 2200

p f1/2-p s

1/2(Pa1/2)

H2 F

lux

(mL·

min

-1·c

m-2

) STP

Permeation = 102 mL•min-1•cm-2 STP


Membrane Performance under Pressure (300 psig); 40% Hydrogen; No Sweep Gas. Hydrogen Pressure

on Permeate Side 15 psia.

0

20

40

60

80

100

120

140

160

0 20 40 60 80 100

Time (Hours)

Perm

eatio

n (m

L•m

in-1

•cm

-2) S

TP


Cross-Sectional Schematic of Stacked Hydrogen Separation Membrane Unit

Membrane

Valve

H2 + CO2 + CO + N2

2048clh.dsf

Water-GasShift

Reactor

SweepStream

SweepStream

Seal

Membrane

H2O + CO2 +

CO + H2 + N2

SweepStream

+ H2

Steam

ExhaustH2O + CO2 Syngas

(H2 + CO2 + CO + N2)

SweepStream

+ H2

CatalystGuard Bed

Seal


Performance of Two Membrane Stack at Ambient Pressure

0

50

100

150

200

250

0 0.5 1 1.5 2 2.5 3 3.5 4 4.5

Time (hour)

H2 F

lux

(mL·

min

-1) S

TP

Membrane #1Membrane #2Total


Relative Costs of H2 Production Using Membrane Technologies

• H2 separation membranes could reduce purification cost by ~30% relative to Pressure Swing Absorption (PSA). (S. Lasher et al., Hydrogen Technical Analysis, Proc. 2002 DOE Hydrogen Program Review)

• Eltron H2 separation membranes are ~200 times cheaper than analogous Pd membranes and permeate 10x faster.

• Estimated H2 cost using combined oxygen and hydrogen transport membrane technologies is $4/MMBtu or $0.55/kg. (Hydrogen Production Facilities: Plant Performance and Cost Comparison, Final Report for Contract No. DE-AM26-99FT40465, Parsons)


Membranes for Hydrogen Supply

O2CMR

H2CMR

Air CO + 2H2 H2

Natural GasPetroleumBiomassor Coal

CO2 Sequestration

N2

Wat

er-G

as S

h ift

CO2 + 3H2

H2O

FuelCell

H2O- +

H2O + N2

Com

bust

ion

Air


Concept for Emission-Free Electric Utility

CO2Capture

CO2 in Saline Formation

Methane Displacement from Coal Using CO2

CO2 in Exhausted Oil Reservoir

CO2 for Enhanced Oil Recovery

O2CMR

H2CMR

H2

H2O

CO2

CombustionAir

H2O+N2

Electric Utility

Wat

er-G

a s S

hift


Future Work

• Remainder of FY 2005– Complete build and performance verification of

1.3 lb/day membrane separation unit• FY 2006

– Build and test 5 lb/day PDU– Integrate with coal gasifier slip stream

Participants:Eltron Research Inc.CoorsTekEmery EnergyNoram Engineering and ConstructorsPraxair


Hardware for Performance Testing of1.3 lb/day Hydrogen Separation Unit


Acknowledgements

• DOE Vision 21 Contract DE-FC26-00NT40762

• Arun Bose

• Gary Stiegel


ELTRON RESEARCH INC.AN ELECTROCHEMICAL, ENVIRONMENTAL AND CATALYSIS RESEARCH COMPANY

4600 Nautilus Court SouthBoulder, CO 80301-3241

(303) 530-0263www.eltronresearch.com


Publications and Presentations• Hydrogen and Oxygen

Transport Membranes for Spontaneous Conversion of Coal to Hydrogen

• Simultaneous Hydrocarbon Reforming, Carbon Dioxide Sequestration and Hydrogen Separation Using Dense Inorganic Membranes

• Oxygen and Hydrogen Transport Membranes for Combined Hydrocarbon Reforming and Hydrogen Separation

29th International Conference on Coal Utilization and Fuel Systems, Clearwater, FL, April 2004

Annual Carbon Capture and Sequestration Conference, Alexandria, VA, May 2004

8th International Conference on Inorganic Membranes, Cincinnati, OH, July 2004

A.F. SammellsM.V. MundschauS.E. RoarkT.F. Barton

M.V. Mundschau X. XieC.R. EvensonA.F. Sammells

A.F. Sammells M.V. Mundschau X. Xie


Publications and Presentations (cont.)7th International Conference on Greenhouse Gas Control Technology, Vancouver, BC, Sept. 2004

21st Annual International Pittsburgh Coal Conference, Osaka, Japan, Sept. 2004

30th International Technical Conference on Coal Utilization & Fuel Systems, Clearwater, FL, April 2005

M.V. Mundschau X. XieA.F. Sammells

A.F. Sammells M.V. Mundschau X. Xie C.R. Evenson

M.V. Mundschau X. Xie A.F. Sammells

• Dense Membranes for Separation of H2 from CO2in High-Pressure Water-Gas Shift Reactors

• Advanced Membranes for the Spontaneous Conversion of Coal to Hydrogen

• Advances in Hydrogen Separation Membrane Technology for the Separation of CO2 and the Purification of Hydrogen Produced from Coal


Hydrogen Safety

The most significant hydrogen hazards associated with this project are:

• Carbon monoxide poisoning

• Hydrogen leakage

• Hydrogen feed explosion


Hydrogen Safety

Our approach to dealing with these hazards is:• Continuous monitoring for reducing gases

• Operation of hydrogen separation units in contained, well-ventilated conditions

• Hydrogen membrane hardware has incorporated rupture disks vented to the outside

Advanced Hydrogen Transport Membranes for Vision 21 Fossil ... · ST P) 1 4 8 14 23 34 Permeability...

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