Today, palladium-based membranes are used at commercial scale to provide pure hydrogen for semiconductor manufacturing, food processing, and fertilizer production, among other applications in which the membranes operate at modest temperatures. If palladium membranes get much hotter than around 800 kelvins, they can break down.
Now, MIT engineers have developed a new palladium membrane that remains resilient at much higher temperatures. Rather than being made as a continuous film, as most membranes are, the new design is made from palladium that is deposited as "plugs" into the pores of an underlying supporting material. At high temperatures, the snug-fitting plugs remain stable and continue separating out hydrogen, rather than degrading as a surface film would.
The thermally stable design opens opportunities for membranes to be used in hydrogen-fuel-generating technologies such as compact steam methane reforming and ammonia cracking - technologies that are designed to operate at much higher temperatures to produce hydrogen for zero-carbon-emitting fuel and electricity.
"With further work on scaling and validating performance under realistic industrial feeds, the design could represent a promising route toward practical membranes for high-temperature hydrogen production," says Lohyun Kim PhD '24, a former graduate student in MIT's Department of Mechanical Engineering.
Kim and his colleagues report details of the new membrane in a study appearing in the journal Advanced Functional Materials. The study's co-authors are Randall Field, director of research at the MIT Energy Initiative (MITEI); former MIT chemical engineering graduate student Chun Man Chow PhD '23; Rohit Karnik, the Jameel Professor in the Department of Mechanical Engineering at MIT and the director of the Abdul Latif Jameel Water and Food Systems Lab (J-WAFS); and Aaron Persad, a former MIT research scientist in mechanical engineering who is now an assistant professor at the University of Maryland Eastern Shore.
Similar issues arise in a number of other processes for producing hydrogen, where gases must be separated and recirculated back into a reactor. Concepts for such recirculating systems would require first cooling down the gas before it can pass through hydrogen-separating membranes - an expensive and energy-intensive step that would involve additional machinery and hardware.
"One of the questions we were thinking about is: Can we develop membranes which could be as close to the reactor as possible, and operate at higher temperatures, so we don't have to pull out the gas and cool it down first?" Karnik says. "It would enable more energy-efficient, and therefore cheaper and compact, fusion systems."
The researchers looked for ways to improve the temperature resistance of palladium membranes. Palladium is the most effective metal used today to separate hydrogen from a variety of gas mixtures. It naturally attracts hydrogen molecules (H2) to its surface, where the metal's electrons interact with and weaken the molecule's bonds, causing H2 to temporarily break apart into its respective atoms. The individual atoms then diffuse through the metal and join back up on the other side as pure hydrogen.
Palladium is highly effective at permeating hydrogen, and only hydrogen, from streams of various gases. But conventional membranes typically can operate at temperatures of up to 800 kelvins before the film starts to form holes or clumps up into droplets, allowing other gases to flow through.
This gave the team an idea: If a supporting material's pores could be "plugged" with deposits of palladium - essentially already forming a droplet with the lowest surface energy - the tight quarters might substantially increase palladium's heat tolerance while preserving the membrane's selectivity for hydrogen.
To test this idea, they fabricated small chip-sized samples of membrane using a porous silica supporting layer (each pore measuring about half a micron wide), onto which they deposited a very thin layer of palladium. They applied techniques to essentially grow the palladium into the pores, and polished down the surface to remove the palladium layer and leave palladium only inside the pores.
They then placed samples in a custom-built apparatus in which they flowed hydrogen-containing gas of various mixtures and temperatures to test its separation performance. The membranes remained stable and continued to separate hydrogen from other gases even after experiencing temperatures of up to 1,000 kelvins for over 100 hours - a significant improvement over conventional film-based membranes.
"The use of palladium film membranes are generally limited to below around 800 kelvins, at which point they degrade," Kim says. "Our plug design therefore extends palladium's effective heat resilience by roughly at least 200 kelvins and maintains integrity far longer under extreme conditions."
These conditions are within the range of hydrogen-generating technologies such as steam methane reforming and ammonia cracking.
Steam methane reforming is an established process that has required complex, energy-intensive systems to preprocess methane to a form where pure hydrogen can be extracted. Such preprocessing steps could be replaced with a compact "membrane reactor," through which a methane gas would directly flow, and the membrane inside would filter out pure hydrogen. Such reactors would significantly cut down the size, complexity, and cost of producing hydrogen from steam methane reforming, and Kim estimates a membrane would have to work reliably in temperatures of up to nearly 1,000 kelvins. The team's new membrane could work well within such conditions.
Ammonia cracking is another way to produce hydrogen, by "cracking" or breaking apart ammonia. As ammonia is very stable in liquid form, scientists envision that it could be used as a carrier for hydrogen and be safely transported to a hydrogen fuel station, where ammonia could be fed into a membrane reactor that again pulls out hydrogen and pumps it directly into a fuel cell vehicle. Ammonia cracking is still largely in pilot and demonstration stages, and Kim says any membrane in an ammonia cracking reactor would likely operate at temperatures of around 800 kelvins - within the range of the group's new plug-based design.
Karnik emphasizes that their results are just a start. Adopting the membrane into working reactors will require further development and testing to ensure it remains reliable over much longer periods of time.
"We showed that instead of making a film, if you make discretized nanostructures you can get much more thermally stable membranes," Karnik says. "It provides a pathway for designing membranes for extreme temperatures, with the added possibility of using smaller amounts of expensive palladium, toward making hydrogen production more efficient and affordable. There is potential there."
Research Report:"Nanostructured Hydrogen-Selective Palladium 'Plug' Membranes Capable of Withstanding High Temperatures"
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