New ceramic membrane generates compressed H2 from methane and electricity with near-zero energy loss
20 November 2017
A team of scientists from CoorsTek Membrane Sciences, the University of Oslo (Norway) and the Instituto de Tecnología Química (Spain) have successfully completed laboratory testing of a ceramic membrane that generates compressed hydrogen from natural gas and electricity in a one-step process with near-zero energy loss.
The research, reported in the journal Nature Energy, builds on 20 years of experience in the development and manufacturing of ceramic membranes at CoorsTek. The membrane—a “protonic membrane reformer” (PMR)—is made from oxides of abundant materials (including barium, zirconia, and yttrium), forming a solid ceramic electrolyte that can transport hydrogen in the form of protons at temperatures from 400 to 900 °C. By applying an electric potential over the ceramic cell, hydrogen is not only separated from other gases but also electrochemically compressed.
The researchers achieved full methane conversion at 800 ˚C by removing 99% of the formed hydrogen, which is simultaneously compressed electrochemically up to 50 bar. A thermally balanced operation regime is achieved by coupling several thermochemical processes.
Herein, we report an electrochemically driven PMR that realizes four process steps simultaneously within a 400μm length scale. First, it extracts hydrogen from the reforming side and shifts a thermodynamically limited reaction sequence towards full conversion of methane; second, it delivers heat to the strongly endothermic reaction through the electrical operation of the membrane—acting as a separator and a compressor; third, it compresses hydrogen directly at the sweep side of the membrane; and last, it produces high-purity hydrogen. The combination of these functions in a single spatially integrated stage confers high overall energy efficiency, process simplicity and compactness.
—Malerød-Fjeld et al.
The membrane reformer in the study is a tubular cell, 10 mm O.D., composed of a dense 30-μm-thick BaZr0.8-x-yCexYyO3-δ (BZCY) proton-conducting electrolyte sandwiched between two porous electrodes of BZCY and Ni. At 800 °C and a steam pressure of 1 bar, BZCY exhibits pure proton (H+) conductivity of 10 mS cm−1. By applying a voltage and hence current across the electrolyte, hydrogen is selectively extracted from the inner steam methane reforming chamber, reaching hydrogen production rates of 25 Nml min−1 cm−2 at 4 A cm−2, operating essentially at the theoretical Faradaic limit and with an area specific resistance of 0.4Ωcm2.
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| Protonic membrane reformer for production of compressed hydrogen. Methane is steam-reformed to CO and H2 over Ni particles inside the ceramic tube. Hydrogen is transported as protons to the outer side, while CO is converted to CO2 by WGS reaction. Outlet composition is mainly CO2 and steam. The hydrogen produced is of high purity and compressed in situ. The net endothermic chemical reaction is balanced with the heat evolved from the galvanic operation of the electrochemical cell. Red, white and grey atoms represent O, H and C, respectively. Top scanning electron micrograph insets correspond to the cathode/electrolyte/anode structure (left), composite reforming anode (center) and composite cathode (right), including chemical and electrochemical reactions, depicted schematically. Malerød-Fjeld et al. Click to enlarge. |
Our breakthrough ceramic membrane technology makes it possible for hydrogen-fueled vehicles to have superior energy efficiency with lower greenhouse gas emissions compared to a battery electric vehicle charged with electricity from the grid. The potential for this technology also goes well beyond lowering the cost and environmental impact of fueling motor vehicles. With high-volume CoorsTek engineered ceramic manufacturing capabilities, we can make ceramic membranes cost-competitive with traditional energy conversion technology for both industrial-scale and smaller-scale hydrogen production.
—Per Vestre, Managing Director at CoorsTek Membrane Sciences
Although use of hydrogen as an energy carrier for next-generation fuel cell electric vehicles is still limited, hydrogen is already an important molecule for a range of industrial processes from food processing to manufacturing of glass and semiconductors, with ammonia-based fertilizers as the single largest application for hydrogen today.
While a fuel cell electric vehicle might only need about 0.4 kg of hydrogen per day for typical family use, a world-scale ammonia plant needs a million times more, from 200 to 600 tons of hydrogen per day.
Modeling of a small-scale (10 kg H2 day−1) hydrogen plant suggested an overall energy efficiency of >87%. The researchers suggested that future declining electricity prices could make PMRs a competitive alternative for industrial-scale hydrogen plants integrating CO2 capture. CoorsTek Membrane Sciences research suggests that the ceramic membranes can be a competitive technology for hydrogen production with integrated carbon capture, even at a scale required for cost-effective ammonia production.
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| Sankey energy diagram for a 10 kg day−1 hydrogen production facility based on system modeling, closing the energy input (electricity and natural gas) and output (thermal losses, utility losses and hydrogen) in the overall energy balance. The heat recovery and microthermal integration are the specific properties of PMR resulting in the overall high energy efficiency. Malerød-Fjeld et al. Click to enlarge. |
By combining an endothermic chemical reaction with an electrically operated gas separation membrane, we can create energy conversions with near zero energy loss. When you have the technology to convert energy from one form to another with almost no loss of energy, this opens up new ways to think about energy systems. For example, we can use the ceramic membrane technology to produce hydrogen from water. This will require more electric power than reforming of methane, but if electricity is available from renewable sources we can make hydrogen without CO2 emissions.
You can also think one step further and design energy systems that are not only low carbon or zero carbon, but even have negative carbon emissions. This will be the case if you use renewable electricity to reform biogas to hydrogen, and store the produced carbon from the biogas underground. In this way, hydrogen can one day become a negative emission energy carrier.
—Dr. Jose Serra, Professor with Instituto de Tecnología Química (ITQ) and a co-author
Resources
Harald Malerød-Fjeld, Daniel Clark, Irene Yuste-Tirados, Raquel Zanón, David Catalán-Martinez, Dustin Beeaff, Selene H. Morejudo, Per K. Vestre, Truls Norby, Reidar Haugsrud, José M. Serra & Christian Kjølseth (2017) “Thermo-electrochemical production of compressed hydrogen from methane with near-zero energy loss” Nature Energy doi: 10.1038/s41560-017-0029-4
When fined tuned and mass produced, this smart membrane could make clean H2 a negative emission energy carrier?
Secondly, it could reduce the total cost of REs by using excess/surplus energy instead of letting solar and wind plants run idle.
Thirdly, it will bring plentiful distributed H2 cost down to average electricity and fossil/bio fuel price.
H2FC heavy vehicles such as (trucks, buses, trains and ships) and airplanes will become realities.
Posted by: HarveyD | 20 November 2017 at 09:35 AM
Many thanks for a great write up which highlights some of the features.
I had mentioned the technology before on another thread, but this casts more light on this exciting technology.
I will leave it to those better qualified than I to comment of the tech, but I did do a quick check on Coorstek, and they are no underfunded venture capital start up, but a very serious player in their field.
It is still early days, and we await the move from the lab to the far more demanding prototype stage, but fingers crossed!
Posted by: Davemart | 20 November 2017 at 09:35 AM
The reference in the previous thread didn't note that this scheme is basically enhanced SMR. There's never any solid carbon in the process, and any that is formed would gasify to CO + H2 in the presence of steam anyway; CO + H2O then reacts to CO2 + H2. Pumping out the H2 drives the equilibrium toward CO2 + H2O as the product gas. Pushing the reaction to completion and incorporating the separation eliminates the need for a recycle gas stream or using a partially-reacted off-gas in some other process.
Very clever IMO, but it still leaves the natural gas (oil) companies in the driver's seat. I think that's a mistake.
Posted by: Engineer-Poet | 20 November 2017 at 09:28 PM
Ehh, Engineer-poet,
It could also be a good thing. They have the capital to invest now in oil legacy projects, like H2.
We will need oil, indefinitely, we might not burn it in our cars thirty years from now, but we will need oil for nearly everything we do.
The Saudis are doing interesting things. Most companies are getting ready for the end of the ICE in one form or another.
As renewables sources of hydrogen come about, we can transition just the same. We shouldn't limit ourselves to much in the near term to step away from ICE vehicles.
This new technology claims to be very cost effective and efficient, it's not as green as it can be, but it is a great step forward to what we have now, and as you point out, it's dangerously better than current offerings, and could lead to existing monopolies keeping the status quo.
Posted by: CheeseEater88 | 21 November 2017 at 07:07 PM
The handicap of the electric car has always been the short range and time required to charge the battery. In every other way it has always been superior.
Now we have Li-ion coming with silicon anodes which allow charging to 80% capacity in 5 minutes, which puts charging in the same class as refueling an ICEV. Plus, you can deliver electrons to a car in motion. 5-minute charging without stopping gives you a car that NEVER has to stop until it reaches its destination. That is superior to the ICEV, and will kill it without any further developments.
We will use oil for lubricants, plastics and such, but it's a dead fuel walking right now.
Posted by: Engineer-Poet | 22 November 2017 at 06:35 AM
Batteries and very quick charge facilities is still a problem to be fully solved. Adequate units may not be fully available before 2030+.
Batteries current low performances (large volume and weight per kWh) is also another problem to be solved and may not be solved before the 2030s.
Batteries current high cost has not yet been solved. More automation and lower cost materials may not solve this difficult problem before 2030/2035.
Much lower cost distributed clean H2 may be a reality by 2025/2030.
Competitive mass produced extended range all weather FCEVs may be a reality by 2025 or so.
Posted by: HarveyD | 22 November 2017 at 09:16 AM
Envia silicon-anode batteries supposedly solve the battery problem today.
Acela locomotives handle 5.2 MW of power through a pantograph connection at over 100 MPH today. That problem was solved years ago.
tl;dr Harvey is so enamored with a gas that he can't think.
Solved by using a 100-mile battery and charging it in motion every 50 miles. But you're breathing so much hydrogen your brain is hypoxic.
Posted by: Engineer-Poet | 22 November 2017 at 05:01 PM
Can you imagine the total cost of (charging in motion) global systems?
USA/Canada can't even afford limited overhead electric facilities for their rail systems and continue to use polluting diesel-electric locomotives like in India, Africa, So-America and many other countries?
Most nations, including USA, are moving to REs at a fast rate. REs account for 30% to 50% of e-energy produced in many places.
Combined generation from CPPs, NGPPs, NPPs and Oil PPs is going down in favour of REs
REs production (except Hydro with reservoirs) do not always match requirements, daily excess/surplus hours are common place. Lower cost excess/surplus energy from REs will be available to generate H2. Clean competitive lower price H2 can be distributed and/or stored for FCEVs
Posted by: HarveyD | 23 November 2017 at 02:05 PM
Figure $100/foot or $528k/mile for a single lane of through-slot conductive charging guardrail. That's $1.056 million/mile for both directions.
Figure charging at 45 MPH for 5 minutes, 3.75 miles is sufficient to top off the battery. Now put this every 50 miles on every interstate; it covers 7.5% of the total length.
The US Interstate system has 47,856 miles of road. Covering 7.5% of it at $1.056 million/mile would cost $3.79 billion. That's chump change, Harvey.
The entire National Highway System includes 160,995 miles of roads. Covering all of it would cost $12.75 billion. Still chump change. You'd make that back in 1 year of petroleum saved.
USA rail operators are private businesses and have to pay property taxes on infrastructure. Burning off-road diesel costs less than the taxes on new overhead wires.
NG generation up steeply YoY since 2014. NG was up far more than wind from 2015-2016; it was up almost as much as wind and solar combined.
This will only be done as a publicity stunt/greenwashing.And here we get back to the motivation for your motivated reasoning: you want the FCVs to artificially create the H2 demand so you can use H2 as a sink for REs.
What you don't realize is that such sinks play to base-load nuclear, not flaky wind and PV. If H2 generation eliminated negative pricing, nuclear could expand to serve the mid-load and get far better utilization out of the H2 generators than REs.
Batteries are a far more efficient sink for excess generation. Completely electrifying the US ground transport system would take OTOO 180 GW average, which comes to almost the US average grid load if it's all used between 6 PM and 6 AM. It's a natural match, and hydrogen has no place in it.
Posted by: Engineer-Poet | 23 November 2017 at 02:57 PM
When most countries cannot afford to install relative low cost over head power lines on their railroads, they will not/never find the funds to electrify all their 2 to 6 lanes roads and highways.
In road (in all lanes) wireless charging systems could be an (extremely costly) solution for hot weather areas but could be a real challenge in areas with lots of snow, ice and cold weather.
The 100+ trolley buses we used in the 60s were sold/given to Vancouver after a few years because of frequent icing problems on over head cables.
In 13 to 20 years, if 4X to 5X lower cost mass produced Solid States quick charge batteries are available, affordable extended range BEVs will (positively) compete against extended range small FCEVs.
Users living in cold areas, heavy long range buses, trucks, trains, ships, power grids and e-planes may prefer FCs + super capacitors and/or a few batteries.
Posted by: HarveyD | 24 November 2017 at 03:37 PM
Harvey you 1d10t, almost all of Europe's RRs are electrified. So's the trans-Siberian, IIUC. US RRs aren't because of peculiar tax issues.
Harvey you 1d10t, only about 7.5% of the total length needs to be electrified and on just one lane.
Harvey you 1d10t, wireless charging is not proposed here. It's all conductive charging.
That's because your 1d10t Canadian engineers couldn't figure out how to circulate enough current through the overhead lines to keep them heated to above freezing during precipitation conditions. This is literally an undergrad electrical engineering problem.
FWIW I saw Montreal's ex-trolley buses running in Vancouver. I saw some rail trolleys running in Toronto, which has similar weather to Montreal. Those people understand things you do not. You should be ashamed.
Do you have these phrases bound to hot-keys? You use them often enough. You certainly can't think beyond them. I'm beginning to wonder if you're a basic chat-bot operating as a troll-bot.
Posted by: Engineer-Poet | 26 November 2017 at 09:50 PM
It is well known that a few countries in EU have built/installed a few lines with high speed electric passenger trains over the last 30+ years. The latest champion is China with 110,000+ Km. USA and Canada have NONE, with the exception of a few short low speed suburb lines. The same can be said for India, So-America, Africa and 120+ other countries.
Germany will get the first FC passenger e-trains in about 18 months. It may become a valuable solution for USA and Canada (for passenger e-trains) to avoid the installation of costly over head power cables. Shared H2 stations (with trains,trucks and cars) would be an added advantage.
Over head cables for e-cars/trucks would not longer be accepted and many places. All electric/comm cables and subways in our area are underground and that's the way we want it. The new Hydro high voltage lines to Vermont will be under ground on both sides of the border. Chicago style cables and overhead rails are not acceptable.
The majority is more environment oriented. What was acceptable in the last century is questioned.
Posted by: HarveyD | 27 November 2017 at 01:50 PM
I said till a year to commercialize a bi-fuel gas-hydrogen ice car, Is it clear now or you wuill still flare away 35% of the natural gas that is coming out of petroleum extraction.
Some day i was hoping that trump and pruitt will erase all the energy catastrophies happening everywhere. these incompetant bureaucrats are really starving the entire planet but till than journalists and most bloggers are cashing good money been paid to cover the scene.
Posted by: And Bri | 27 November 2017 at 01:56 PM
Harvey you 1d10t, Acela averages 82 MPH and reaches 150 MPH. Just because it has engineering problems doesn't mean it doesn't exist.
The problem in the US is that pesky thing, property rights. China can expropriate whom they wish and build new grade-separated rail lines. Acela has to share rails with freight trains and had to be built to withstand collisions with cars and trucks because the government can't just tear up people's property to build a new train system. I prefer the USA to China for just that reason.
A charging system built into a freeway guard rail is NOT overhead. A system that only needs to cover a 4-mile stretch every 50 miles can be sited where nobody minds.
You are either not reading or are unable to understand what you read. Whether the stupid is real or an act, just cut it out. Don't comment on things if you can't be on-topic and insightful.
Honestly, you're descending to the level of gorr.
Posted by: Engineer-Poet | 28 November 2017 at 08:42 AM
As usual, the Poet is not very tolerant and will never accept that HE may be wrong, much the same as DT does.
Posted by: HarveyD | 01 December 2017 at 03:50 PM
The Acela's moderate/high speed e-trains, part of a $2.5B project (Boston to Washington via NY and Penn) will eventually have 28 trains. Prototype due in late 2019. In service/revenue units due in 2021/2022. Essential upgrades to number of trains, tracks and over head cables will probably drive the final cost close to or over $4B.
Even at $4+B, it is a good (relative low cost) first try for USA.
Posted by: HarveyD | 01 December 2017 at 06:13 PM
Harvey is indignant at being shown to be totally ignorant of basic facts of these matters. He should be grateful at being given information he did not know, so he could correct his erroneous views. He is not.
Posted by: Engineer-Poet | 02 December 2017 at 07:54 PM
Can you imagine the energy required to recharge extended range EVs travelling at 80+ miles/hour on 8 to 10 lanes on Interstate 95 and the energy required from microwave TXs?
More poems are required.
Posted by: HarveyD | 03 December 2017 at 08:46 AM
If you weren't a poseur you wouldn't even try to imagine it, you'd just get down and calculate it.
You have never run a calculation to test an assumption in all the time I've been reading your comments here, Harvey. Not. Even. Once.
Posted by: Engineer-Poet | 03 December 2017 at 12:12 PM
EP, I think you grossly underestimate the cost to implement charging on the go.
The cost for the test mile of over head charging lines in California was much much higher $13,500,000 for one mile, where the centerlanes were electrified, not the right lanes.
That's the cost today, maybe not in the future, but you were off by $100,000,000,000
Also, one thing i don't think you factored in is the load at which some of these highways would see. There would need to be new substations, perhaps high tension lines brought in along the highway, lots of infrastructure would need to change.
On top of that, highway maintenance and repair costs would go up.
Each mile electrified would be an ordeal, each mile would be different and have its own challenges.
I'm not saying it can't be done, but i am saying there might be a better way that doesn't involve the sort of long term commitment our current highway system cannot support.
We are better off spending those billions, tapping that caldera, and making geothermic electricity for as much as we can. We can probably install a huge gigawatt facility, or even terrawatt with that sort of money, thus displacing most of our electric base load dependent on coal and natural gas. We could tie in with hightension dc lines to the east coast as well.
Posted by: CheeseEater88 | 05 December 2017 at 03:45 PM
Okay maybe not a terrawatt, but a gigawatt or a few is more than doable with a few billion dollars.
Your original estimate of 12billion, would net a 3.5 gigawatt geothermal plant, perhaps even more with economies of scale. With 90% uptime it can rival nuclear for a base load.
Also, your five minute top off wouldn't likely be a five minute top off. I'd plan for 75mph traffic, and I'd plan for 5miles increments. Also youd need about 150kw available for each vehicle on that five mile stretch. In a rush hour situation that could get interesting.
Posted by: CheeseEater88 | 05 December 2017 at 04:06 PM
I took my numbers from published figures for the cost of guardrail. They were in the range of $20-$60 per foot. I bumped that up to $100 per foot for the added elements; the structural details wouldn't change greatly.
So you're taking the figures for
- a first-of-a-kind system,
- of a completely different design,
- with inherently higher costs due to no local supply chain or reusable existing elements,
and attributing them to my proposal. Bad form.They'd have to be brought in to feed charging stations, so what's the big deal? I'll let you gather the numbers on traffic in vehicles/hour and energy/mile to compute instantaneous power demand.
Everything has costs. Elements of conductive charging systems are going to be subject to wear. What matters is that it's likely the cheapest way of cleaning up our transport system.
If you don't understand that geothermal power is inherently difficult and costly except where nature has provided favorable conditions, and that you have gone off into completely unrelated territory here, your thinking is too uninformed and disordered to contribute in any worthwhile fashion.
Posted by: Engineer-Poet | 06 December 2017 at 06:58 AM