CoorsTek proton ceramic membranes produce hydrogen from ammonia, natural gas or biogas
20 May 2022
A development team from CoorsTek Membrane Sciences, in collaboration with international research partners, have successfully used ceramic membrane technology to develop a scalable hydrogen generator that makes hydrogen from electricity and fuels including natural gas, biogas and ammonia with near zero energy loss. A paper on the work is published in the journal Science.
Energy efficiency is key to the future of hydrogen as a clean fuel. Our work shows that protonic membranes can make hydrogen from ammonia, natural gas and biogas so efficiently that hydrogen fuel cell cars will have lower carbon footprint than electric cars charged from the electricity grid.
—co-author Irene Yuste, chemical engineer at CoorsTek Membrane Sciences and PhD candidate at the University of Oslo
Proton ceramic membranes are electrochemical energy converters that work by first splitting hydrogen-containing molecules, such as water or methane, and then further breaking hydrogen atoms into protons and electrons. Protons are transported through the solid ceramic membrane while electrons are transported separately through a metallic conductor connected to a power source. When protons and electrons recombine on the other side of the ceramic membrane, pure hydrogen is produced as a compressed gas.
When energy is transformed from one form to another there is energy loss. With our proton ceramic membranes, we can combine otherwise distinct steps of conventional hydrogen production from fuels like natural gas and ammonia into a single stage where heat for catalytic hydrogen production is supplied by the electrochemical gas separation. The result is a thermally balanced process that makes hydrogen with near zero energy loss.
—co-author Jose Serra, professor with Instituto de Tecnología Química in Spain
Proton ceramic membranes have been under development at universities and corporate laboratories for three decades, with thousands of scientists contributing to incremental improvements. The report in Science marks the first demonstration of proton ceramic membrane technology at practical scales to make hydrogen for fuel cell cars and other clean energy deployments.
Key to the recent breakthrough in the scale-up is a novel nickel-based glass-ceramic composite interconnect material developed by CoorsTek Membrane Sciences. The composite can be shaped like a glass during fabrication, has the high-temperature robustness of a ceramic, and the electronic conductivity of a metal.
Our ceramic membrane technology is built from small cells that are joined into stacks and further combined into bigger modules. The modular nature of this technology makes it possible to start with small hydrogen generators and scale big by adding new modules as demand for hydrogen increase.
—Per Vestre, Managing Director for CoorsTek Membrane Sciences
With the ability to run on natural gas, biogas, or ammonia, the proton ceramic membranes offer a fuel-flexible and fuel-flexible hydrogen production platform. And when hydrocarbons are used as fuel, the membranes directly deliver by-product CO2 as a concentrated stream that can easily be liquified for cost-effective transport to use or storage so that no carbon is released to the atmosphere.
Authors of the report published in Science include scientists and engineers from CoorsTek Membrane Sciences, the University of Oslo and the research institute SINTEF in Norway, and the Instituto de Tecnología Química in Valencia, Spain. The work was further supported by technology experts and financial resources from leading energy companies, including Saudi Aramco, ENGIE, Equinor, ExxonMobil, Shell and TotalEnergies. A next step in the on-going development program is to install a pilot plant hydrogen generator at Saudi Aramco’s headquarter campus in Dhahran, Saudi Arabia.
Norway’s state-owned enterprise for carbon capture, storage and transport, Gassnova, through its CLIMIT program, and the Research Council of Norway, through its NANO2021 program, also contributed funding to the work.
Resources
Clark et al. (2022) “Single-step hydrogen production from NH3, CH4, and biogas in stacked proton ceramic reactors”, Science doi: 10.1126/science.abj3951
I have commented extensively on this technology here:
https://www.greencarcongress.com/2022/05/20220518-tme.html
The bottom line though is that economical, working versions of this have the potential to revolutionise energy production, not only in utilising fossil fuel resources, but by enabling renewables production where they are most plentiful and transhipment to places like Europe.
It also appears to change the efficiency equations between big batteries and fuel cells.
https://www.science.org/stoken/author-tokens/ST-461/full
' ' To illustrate the practical implications of the PCER technology, comparable well-to-wheel emissions for battery electric vehicles (BEVs), internal combustion engines (ICEs) with diesel fuel, and H2 fuel-cell electric vehicles (FCEVs) are provided in figs. S22 and S23 with sensitivity to electric grid carbon intensity. In the California 2050 scenario, the emissions of FCEVs (14.6 gCO2/km) using H2 produced from CH4 with PCERs including CO2 sequestration are 90% lower than those of ICE with diesel fuel (145.4 gCO2/km) and 26% lower than FCEVs using H2 from grid-powered water electrolysis (19.8 gCO2/km). NH3-based H2 can offer reduced emissions compared with on-site electrolysis for a wide range of electric grid carbon intensities, making FCEVs fueled with NH3-based H2 directly comparable to BEVs in terms of CO2 emissions (6.3 gCO2/km, a reduction of 21% compared with BEV in the California 2050 scenario). Here, NH3 is assumed produced at off-site locations with favorable renewable energy resources and transported as a liquid to the fueling station where efficient ADH and separation to H2 takes place using the PCER technology.'
Can anyone spot any 'gotchas' though?
Posted by: Davemart | 20 May 2022 at 06:15 AM
I NEED my hydrogen car right now because it is better than a bev in canadian winters. Hurry-up. gas is 2.10$/liter actually.
Posted by: Gorr | 20 May 2022 at 02:37 PM
This could be natural gas to hydrogen at point of sale
Posted by: SJC | 20 May 2022 at 04:19 PM
Looks pretty clever to me, Davemart. I didn't see anything about energy efficiency, though. That may be because the system can operate as either a generator with low-pressure H2 production, or a load operating as an H2 compressor.
Posted by: Engineer-Poet | 21 May 2022 at 04:10 PM
Hi EP:
I am not sure I have understood your comment, but that may be due to my lack of a proper technical education.
For efficiency, I thought they were talking about nearly lossless conversion which should indicate very high efficiency?
But there is some more in the link:
https://www.science.org/stoken/author-tokens/ST-461/full
' System modeling (13) of a 1 ton/day distributed H2 production plant adopting our PCER stack (figs. S15 to S21) reveals that efficiencies of 91% for CH4 and as high as 95% for anhydrous NH3 can be achieved by virtue of microthermal integration and downstream heat recovery. '
The detailed discussion is above my head, but to the layman it sounds pretty darn good for efficiency.
Perhaps you would take a detailed look at it and tell us your take?
I might have missed critical parameters though, so am looking forward to your further comments.
Posted by: Davemart | 21 May 2022 at 04:39 PM
I'll just add that I try hard to be very clear, not about what I know, but far more importantly what I don't know.
A limited technical education means that when I come across stuff like '91% efficiency' or whatever, I am immediately cautious.
That is because to really comprehend it, you need to get very specific about what it is 91% of, and what energy state you end up with, low grade heat, electricity, or whatever.
Lower and higher heating values etc make it even trickier.
So I try to take a guess at what looks good, but am under no illusions that I need folk like EP and gryf with the requisite technical background to give a proper evaluation.
Hey, back in the day I was a cost and works guy, not an engineer, so just bright enough to work out when the engineer's fab ideas sounded expensive! ;-)
Posted by: Davemart | 21 May 2022 at 04:58 PM
I got lost in the details pretty quickly when I read the paper. The thermal integration is a stroke of genius IMHO, pairing endothermic reactions with exothermic ones to conserve both heat and energy. Hydrogen works beautifully as a heat-transfer fluid, too.
Posted by: Engineer-Poet | 21 May 2022 at 10:22 PM
Hi EP.
Yep, in my view 21st century engineering is all about integrating systems instead of 20th century stuff of focussing on one output and chucking the rest away.
I got interested in what the energy efficiency of hydrogen was coming up for 20 years ago now, when those pushing batteries as 'the solution' were coming up with figures like 4 times the energy efficiency as against a hydrogen cycle.
At the time it was clear that using batteries was more energy efficient by a considerable margin, but that they were making worst case assumptions for hydrogen, ignoring synergies, and best case assumptions for batteries and ignoring intermittency, resource constraints and so on.
If you are going to have a lot of renewables in the grid, you either chuck loads of it away, or use it, likely in some sort of hydrogen cycle.
So the inefficiency is against what would otherwise be a 100% loss.
And since like you I have long been an advocate of nuclear power, I am very attracted to the great economics of producing hydrogen instead of throttling down a plant, where the overwhelming cost is fixed, not marginal, against the extra power.
Upping the temperature of electrolysis by utilising waste heat from nuclear instead of venting it as waste is remarkably energy effective.
I have somewhat moderated what I think is the optimum contribution of nuclear to the grid, in view of the remarkable falls in cost of renewables, but they remain very space intensive for a start, and should there, say, be a large volcanic eruption dimming the amount of solar then having a nuclear leg greatly enhances system stability.
Technically, things look good for low carbon power, one way or another, which is more hopeful than is the case with our present political situation.......
Posted by: Davemart | 22 May 2022 at 03:47 AM
Things happen to fast in fuel cell and hydrogen tech for me to be anywhere near catching up.
Here is another tech using LOHC (liquid organic hydrogen carriers) to deliver hydrogen in a liquid and release it where needed, 99% of the hydrogen makes it out, with the energy coming from solar, and a much reduced use of rhodium in the electrolyser.
https://fuelcellsworks.com/news/new-tech-aims-to-drive-down-costs-of-hydrogen-fuel/
At least within Europe my guess is that we will simply pipe hydrogen around in converted NG pipes, which are being tested and validated for different percentages of hydrogen.
Ammonia and LOHC's being mainly used for transport from major renewable production centres, like Saudi etc.
But that is just a guess, we will have to see how it all plays out, but the costs and the the various competing techs look good, which is the main thing.
Posted by: Davemart | 23 May 2022 at 11:11 AM
"..achieves complete conversion of methane with more than 99%
recovery to pressurized hydrogen.."
https://www.science.org/doi/10.1126/science.abj3951
Posted by: SJC | 23 May 2022 at 11:32 AM
"Modelling of a small-scale (10 kg H2 day−1) hydrogen plant reveals
an overall energy efficiency of >87%."
https://www.nature.com/articles/s41560-017-0029-4
Posted by: SJC | 23 May 2022 at 11:40 AM
@Davemart,
"Can anyone spot any 'gotchas' though?"
So far so good with this impressive technology to generate H2 from established carrier molecules.
The gotchas that I can spot are that:
1.. NH3 ammonia is very toxic and lethal if released quickly during rupture of a container, while H2 is far safer,
2.. CH4 methane and NH3 take considerable amount of energy and expense to produce, so, even if the conversion process back to H2 is 91% efficient, the round-trip efficiency won't be that good.
3.. What the cost of producing this ceramic membrane with built-in catalysts? may not be that cheap!
So, this will be rather a niche application where H2 pipeline won't be available. Otherwise, H2 would best be transported via pipelines just like Natural Gas is transported right now, just replacing one gas for another.
LOHC (Liquid Organic H2 Carrier) would be more practical bulk H2 carrier since it is in liquid form, non-toxic and non-flammable.
It would be
Posted by: Roger Pham | 23 May 2022 at 11:52 AM
I disagree, point of sale hydrogen from natural gas
is better than an expensive hydrogen pipeline
Posted by: SJC | 23 May 2022 at 12:42 PM
Here in Europe we have not authorised fracking, and have not got plentiful, at least non-Russian, gas.
So the plan is to use renewables to generate hydrogen, as well as importing it, perhaps as ammonia.
Maybe some of the point of use conversion idea will be most economical, but if not, then the economics of converting the present NG network with some limited additions seems reasonable.
Most of the present detailed costings have been done for less than 100% hydrogen, , but in any case should pipelines and storage as hydrogen work out cheapest, it seems practical enough.
Here is a UK white paper:
https://phys.org/news/2017-07-uk-gas-grid-green-white.html
After all, in my childhood we used town gas, before North Sea natural gas was exploited, and that was 50% hydrogen, so the technology is hardly entirely unknown, even with pre 1960's technology, in fact we managed town gas since around 1800.
Posted by: Davemart | 23 May 2022 at 01:36 PM
You could replace a lot of natural gas with nuclear-heated hot water (a la Pevek and Haiyang) and a great deal of the rest with nuclear hydrogen. The sulfur-iodine cycle requires high temperatures but is otherwise well-suited, does not require finicky electrolyzers which don't like to be switched on and off, and recycles all its reagents... and a nuclear heat source can be operated 24/7/365 to provide an energy buffer for peak demand times.
https://www.hydrogen.energy.gov/pdfs/review05/pd27_pickard.pdf
Posted by: Engineer-Poet | 23 May 2022 at 07:33 PM
@EP
One of the many reasons that I am keen on SMRs is that it would enable efficient district heating without pumping water for long distances.
My attitude to technologies is usually: 'All of the above' rather than seeking to prematurely rule out options.
Posted by: Davemart | 24 May 2022 at 01:25 AM
Roger:
Ammonia seems to have considerable favour as a carrier, especially for places like Saudi where desalination to provide the water would only use a minor amount of the power.
And some of the reasons for that favour are that we have a lot of experience of bulk shipment of ammonia for the fertiliser industry.
That is a different matter to transporting it around the country on trucks, but of course that tech is also pretty familiar.
The likes of Topsoe Haldor also get good efficiency in solar/wind to ammonia.
I've lost the run of the comparative studies of energy carriers I had bookmarked, but here is a brief look at why the interest in ammonia:
https://www.ammoniaenergy.org/articles/round-trip-efficiency-of-ammonia-as-a-renewable-energy-transportation-media/
' Liquid hydrogen and methanol, despite also being alternative energy vectors, have lower RTE values [than ammonia] as estimated in previous studies. Further, the infrastructure required for liquid hydrogen transport is almost nonexistent and methanol is an emission producing fuel at the point of use; make these alternatives less attractive at this stage. Ammonia therefore provides an attractive option in terms of RTE, as well as being an emission-less energy carrier.'
Posted by: Davemart | 24 May 2022 at 01:42 AM
I started reading the paper, and immediately got my senses jarred. "Media" is plural; they meant "medium".
Posted by: Engineer-Poet | 24 May 2022 at 03:20 AM
EP:
The ectoplasm misbehaved! ;-)
It is probably those darn Germans or Chinese being less than perfectly fluent in God's own language?
Posted by: Davemart | 24 May 2022 at 11:34 AM
Without disrespect to Sanscrit and Hebrew! :-0
Posted by: Davemart | 24 May 2022 at 12:49 PM
What happens to the Carbon from using CH4 with this process? CO2 sequestration will have a big cost burden.
Ideally direct Carbon conversion to Carbon products like carbon fiber... would be a huge value added byproduct.
Until FCEV's systems can be designed to use as little space as BEV's and cost compete against a 1st mover huge advantage, BEV's will still dominate.
FCEV's will have niches like long haul trucking, ships, trains, long range aircraft...
The Russian gas problem is temporary until political change from Ruzzain to an enlightened and educated Russian society. Huge investments in Russian fossil fuels are a great incentive to reform.
Posted by: GdB | 26 May 2022 at 02:36 PM