Hydrogen Separation: Membranes, Processes and

Engineering

T. F. Barton Principal Engineer

Energy Production and Generation

Western Research Institute, 365 North 9th Street, Laramie, WY, 82072 tbarton@uwyo.edu

What is Hydrogen For?

• Ten years ago when the latest “Hydrogen Economy” buzz was developing momentum, emphasis on hydrogen production was placed on 99%+ hydrogen suitable for PEM fuel cells and hydrogen storage. – Hydrogen based cars – Distributed hydrogen based power

• The best materials for producing pure hydrogen from fossil

energy were dense membranes of palladium alloys, vanadium alloys, and Perovskites. Few were tested at larger than bench scale.

So Where is Pure Hydrogen Technology?

• After about ten years of supporting bench scale research in hydrogen membranes, DOE recently published an RFP to complete the engineering for producing pure hydrogen from syngas at 4 ton per day scale.

• DOE has also funded research into non-noble metal dense membranes at bench scale. – Vanadium (niobium, tantalum) – Amorphous metals

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V-9Pd Alloy (AHE-61)

Sophisticated Alloys, Inc. V-9Pd alloy measured oxygen level of 767 ppmw, carbon at 381 ppmw, nitrogen at 151 ppmw, and sulfur at 18 ppmw.

Ames Lab arc melted button cold fabricated to 0.008" thickness. Measured oxygen level of 397 ppmw

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Task 2 Scale Up Integrated Device #1

This integrated device has eight 4.5” diameter vanadium alloy membranes sandwiched with honeycomb ceramic supported WGS catalyst to provide sufficient working area to produce 10,000 l/day hydrogen.

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Chart Three Module Membrane - WGS Reactor

Membrane Scale-Up Detail

Planar membranes can be assembled into dual faced modules and stacked for producing a large surface area in a small volume

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10,000 cm2 Membrane – WGS Reactor The WGS reaction takes place in annular space of a 12” diameter pipe, and hydrogen is collected through a manifold system. Modules are 15 cm x 15 cm with vanadium alloy membranes on both sides; configuration will meet target of 10,000 square cm of surface area. Overall length of the vessel is 90 inches.

Synkera Technologies Membranes

Synkera Membranes(patent pending)

AAO membrane Pd nanoplug

Al rim

Synkera Technologies’ membranes are based on anodic alumina sheets filled with alloys with hydrogen transport properties

Amorphous Metal Alloys

• WRI is working with Southwest Research Institute and Georgia Tech to investigate amorphous metal alloys such as NiZr for their hydrogen transport properties.

• The thin foils are produced by SWRI using their magnetron sputtering system in coatings as thin as 3 microns on porous substrates. Georgia Tech is conducting modeling studies to anticipate the affects of alloy components on hydrogen transport. WRI is testing the thermal stability and hydrogen flux of the materials.

Is 99%+ Hydrogen Necessary?

• Hydrogen cars and distributed power are not around the corner, PEM fuels cells are limited in scope. – National Hydrogen Association reports that 98% of hydrogen used in

the US is for petroleum refining and chemical production.

• In the design of IGCC power plants, the majority of hydrogen separated from CO2 would be burned in a gas turbine.

• Maybe the purity of hydrogen is less important than the supply pressure.

Thermal Cycle Absorption for H2 Separation

Sweep Inlet Syngas Inlet

Syngas OutletSweep/Hydrogen Outlet

ExternalHeating

Thermal Cycle Absorption is a process in which beds of ceramic material are used to absorb hydrogen from syngas, then are alternately swept with steam. The thermal cycle and partial pressure differentials are used to produce high pressure hydrogen. The steam is condensed to remove it as a sweep. Syngas at 600 psig could produce 200 psig hydrogen, though not at 99% purity.

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Polymer Membranes

• WRI is a partner of a team with INL and GE to investigate high temperature polymer materials as hydrogen selective membranes.

• At temperatures up to 250 ̊C, the polyimide based membranes cast on a structural porous substrate are selective for hydrogen over carbon dioxide with a factor up to 10.

• WRI will test polymer film stability in syngas at temperature and membrane

performance of tubular components under gasifier conditions.

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WRI’s Research Scale Coal Gasifier

10 Ton per Day Gasifier at WRI site

Gasifier Arriving at WRI 6-9-10

Hydrogen Test Facility

As part of WRI’s existing US DOE Cooperative Agreement, WRI is building a new hydrogen test facility which will include the separation equipment including flow, pressure and temperature control for various membrane formats and scales.

WRI’s Hydrogen Separation Support

[1] Integration of a Structural water Gas Shift Catalyst with a Vanadium Alloy Hydrogen Transport Device, DOE DE-FC26-05NT-42454

[2] Water Gas Shift Membrane Reactor for High Pressure Hydrogen

Production, DOE AARA Code 200432 Agreement 18989 [3] Amorphous Alloy Membranes for High Temperature Hydrogen Separation,

DOE DE-FE-0001057 [4] Hydrogen Separation, DOE DE-FC26-08NT-43293 [5] Hydrogen Separation for Clean Coal Applications, Wyoming Clean Coal

Technologies Research Program 2009