“Laser-induced nitrogen fixation” https://www.nature.com/articles/s41467-023-41441-0
This is Open Access, and mentions how that is also a leap forward in Nitrogen fixation
“Abstract: For decarbonization of ammonia production in industry, alternative methods by exploiting renewable energy sources have recently been explored. Nonetheless, they still lack yield and efficiency to be industrially relevant. Here, we demonstrate an advanced approach of nitrogen fixation to synthesize ammonia at ambient conditions via laser–induced multiphoton dissociation of lithium oxide. Lithium oxide is dissociated under non–equilibrium multiphoton absorption and high temperatures under focused infrared light, and the generated zero–valent metal spontaneously fixes nitrogen and forms a lithium nitride, which upon subsequent hydrolysis generates ammonia. The highest ammonia yield rate of 30.9 micromoles per second per square centimeter is achieved at 25 °C and 1.0 bar nitrogen. This is two orders of magnitude higher than state–of–the–art ammonia synthesis at ambient conditions. The focused infrared light here is produced by a commercial simple CO2 laser, serving as a demonstration of potentially solar pumped lasers for nitrogen fixation and other high excitation chemistry. We anticipate such laser-involved technology will bring unprecedented opportunities to realize not only local ammonia production but also other new chemistries.”
It isn't clear to me how they're pricing the H-B process there, industrial HB uses hydrogen from hydrocarbons. An apples to apples comparison would at least add the energy you could get from burning the hydrogen instead, but arguably should compare with H-B where the hydrogen comes from electrolysis of water.
> "subsequent hydrolysis"
As far as I can tell, you just add water. zap rinse repeat. I'm a little skeptical that their yield figures were for Li2O though the repeated process has you cycling through LiOH after the first pass.
This could enable fertilizer production with no CO2 emissions. The numbers in the paper suggest that it might prove cheaper than natural gas based production which is common today. Fertilizer production is 2.1% of all CO2 emissions right now.
The abstract doesn't go into detail on energy efficiency and a comparison to the old method using gas. For instance, would this method result in less CO2 emissions using regular grid electricity, or would it need to be 100% low-carbon electricity? If, say, the electricity came from a CCGT plant, how would that compare? Etc etc
Who cares? This is about electricity to ammonia.
Given: a very efficient way to make ammonia (as an energy store) using electricity, this becomes a storage mechanism. So then, make ammonia and money whenever the grid is in a 'pay to take power' state, and (up to a point) even if you have to pay. End source is irrelevant.
Alternate process: run a solar farm, produce ammonia whenever that's cheaper than paying someone to take the power (or curtail), then sell the stored power when prices are high. Or, sell the ammonia directly.
This is not all that different from the production of hydrogen. Hydrogen is most economically produced from natural gas nowadays. You can produce it from water, with (just like here) an almost 100% current-to-hydrogen efficiency. But it's still twice as expensive, if not more.
Do we know if this process is burstable (i.e. the devices for running it are likely cheap enough compared to the energy requirement that they don't need to run 24/7, and could use excess renewable energy when available)?
1. https://nh3fuelassociation.org/2018/12/07/performance-of-amm....
This system involves ethanol as a sacrificial hydrogen donor: "The amount of ammonia produced in the 96 h experiments (3.9 ± 0.1 mmol) was around four times higher than the amount of ethanol present (1 mmol), indicating that it is not a completely sacrificial reactant but can also operate as a proton carrier."
https://www.enginelabs.com/engine-tech/engine/corrosion-of-c...
If I, the consumer, had unlimited access to cheap, unregulated liquid ammonia (as common as gasoline), how many precursor-steps am I away from having access to like... a LOT of high explosives?
-asking for your friendly neighborhood crazy person with a vendetta against... whoever.
As far as I can see, it's a very similar problem to hydrogen. It doesn't matter how safe you can make it, it matters how dangerous a random nutjob can make it.
Isn't this miniscule? Is this commercially viable?
Edit: The molecular mass of nitrogen is 28, so 1 mol is 28 grams, so 150 nmol is 28 x150 nano grams = 4.2 micro grams. How much gas is this?
It's rate of production over the area of the catalyst. Put another way, that's 1.5 ± 0.2 mmol/m²s or 25.5 ± 3.4 mg/m²s.
24 hours of production over a catalyst with an area of 1000 m² would create 25 ± 3.4 t. That's about the product weight of a typical full cold / cool towed trailer tank sent to large-scale customers. A commercial ammonia refinery would need many multiples of this area to be economically viable.
https://alliancetruckandtank.com/products/transport-trailers...
> ammonia production is energy-intensive, accounting for 1% to 2% of global energy consumption, 3% of global carbon emissions,[23] and 3% to 5% of natural gas consumption
Big if we can improve this.
For more on the Haber process and its impact on the world, I highly recommend this book: "The Alchemy of Air: A Jewish Genius, a Doomed Tycoon, and the Scientific Discovery That Fed the World but Fueled the Rise of Hitler" by Thomas Hager.
"In addition to its use in the fertilizer and chemical industries, ammonia is currently seen as a potential replacement for carbon-based fuels and as a carrier for worldwide transportation of renewable energy."
Long-term grid storage?
Publication: 22 July 2022
Anyone know if maybe some pilot / small scale production facility has been set up in the mean time?
I've read about a farm that produced its own fertilizer, but dunno whether that uses this or some older / unrelated process.
Would be a huge breakthrough in any case.
They're trying to avoid using the stuff in industrial refrigeration it's so nasty, and yet here we are gleefully considering rolling down the highway with it in the cheapest vessel industry can lobby for strapped to our bum.
I guess the notion has passed so quickly we haven't had time for the media to program us with corporate agendas...
N2 + 3H2 -> 2NH3
https://about.bnef.com/blog/japans-ammonia-coal-co-firing-st...
which I just can't imagine being clean when I consider that nitrogen oxides are also a concern with combustion fuels, not to mention it being an inefficient "battery" if you're making ammonia from green hydrogen and then burning it and spinning a turbine.
Fertilizer production via this method might be a good fit for times when rates are low or even negative due to wind energy overproduction during off peak.
So I'm not exactly holding my breath. It's a big improvement over previous methods, but there's still a long way to go.
Switching to carbon free ammonia would be no great task, just a price hike and some minor retrofitting.
Could you explain exactly why you would say this?
Working past their fake news headlines like 100%. Hydrogen is almost 100% and that's not big if true.
We are decades away for renewable electricity only for our electric needs.
Then you have oil and many other things electric can replace which are worse than gas.
What about this is big? In a dream world of unlimited electricity everything is easy, like synth fuel and fertilizer and climate control. Today, burning coal to make fertilizer doesn't seem good, if this is true.
We’re decades away from 100%, but how long away are we nationally from 50%, 65%, 90%, 99%?
As solar production ramps up to higher percentages there is going to be more and more peak power in excess of demand. Industrial scale electrochemistry is going to be one of the alternatives to batteries that’s going to be developed.
Already nitrogen fixation requires a huge amount of energy, this process at scale could very well require less energy than the modern haber process.
Also, we need a fuel for long distance transport like ships when batteries won’t work. Ammonia will always be cheaper than synthetic fuel because no carbon doesn’t have to come from air, and it stores better than hydrogen.
There may be lots of surplus electricity in the future but there will also be a lot of demands for carbon capture, hydrogen, long term storage, and chemical processes.
The main challenge is building cheap electrolysers without so much regard to efficiency, in order to use all the power when available. Most commercially available electrolysers today are expensive and cannot ramp up and down quickly.
To know the energy efficiency, besides the current efficiency, which is close to 100%, we need to know how big is the overvoltage needed for electrolysis.
Yeah, someone would have to get access to the paper to see if they state the energy efficiency. I assume that b/c they don't mention it, it is abysmal. There's pressure to put good results into the abstract.
Most hydrogen produced today is consumed very close to where it is produced. Also energy storage and fuel type use cases rank very low on Michael Liebreich's hydrogen ladder. That's a nice tool that ranks different uses of hydrogen by their economic feasibility and overhead. Chemically binding it to something else to store it works of course. Ammonia (NH3) is common for this; and in fact the biggest use case for hydrogen. People have speculated about using that as a fuel. It's much easier to store and transport. And of course these chemical transformations also have an energy cost.
This always bothers me. People freak out about LiIon battery failures, or hydrogen, or ammonia, or nuclear power. But here we are with an entire economy riding on an explosive, firey, dirty fuel that is already causing global climate problems.
Safety concerns should be kept on-par with what we have today. Let’s not throw out a good solution because it can be dangerous in some cases. Any high-energy-dense thing we switch to after fossil fuels is going to release that energy if handled improperly. That concern should be quite low on the list.
And also flammable/explosive.
And if someone really was bent on mayhem, well, anhydrous ammonia is nasty toxic stuff as is. You don’t need to do anything chemically to it to kill or injure a lot of people. On the other hand, it isn’t a chemical that sneaks up on you. If you are being exposed to dangerous levels, you’ll know it.
Or I could just purchase actual explosives at the sporting good store, like tannerite.
The negative for hydrogen is poor round trip efficiency of electricity -> hydrogen -> electricity. But for sufficiently long storage times the lower cost of storage capacity vs. batteries overwhelms that, and hydrogen becomes cheaper for grid storage.
https://phys.org/news/2021-02-plasma-technology-world.html https://portal.nifa.usda.gov/web/crisprojectpages/1025777-lo... https://pubs.acs.org/doi/10.1021/acssuschemeng.2c06357 (paywalled)
"plasma" and "NOx" seem to be the keywords here (so other process than discussed here).
Not at scale (yet), cost unclear. But the technology exists, and being improved upon.
This method of direct electroreduction should not confused with the Laser-induced method discussed elsewhere in the thread, which has abysmal numbers.
Who knows man, maybe feds caught him with some pot plants and now he's setting you up in some sort of bullshit anti-terror sting to cut a deal. Regardless of what kind of truck you have, casually buying half a ton of fertilizer for somebody else is an odd request that warrants some explaining.
When solar hits a certain ratio of production there will be a daily peak where electricity will be very cheap because there’s too much of it, regardless of what people “advocate”.
Electrochemistry things are where it’s at, metal refining specifically.
Aluminum production from ore has one step where you literally just make what is effectively an enormous battery out of aluminum ore and “charge” it, when it’s fully charged you’ve turned aluminum oxide into pure aluminum. It can even be run backwards to produce electricity because it’s literally a battery (a really shitty one). So there’s not a huge capital investment or complex process and electric input is actually a significant portion of the cost.
Other simple electrochemistry things that do have a major portion of the cost in electricity can do the same when costs get low enough. There’s a lot of recycling that becomes possible with cheap clean energy that you would never do with fossil fuel electricity.
They don’t shut down entirely because the aluminum has to stay molten at a thousand degrees, but they can scale the energy usage significantly, this is becoming more of an interest in the last decade.
https://www.greentechmedia.com/amp/article/german-firm-turns...
Not assuming it would be the same, but picturing a spill at a gas station. Spilling gas is a problem, but at least it's just sort of there. If you get an ammonia leak and it forms a vapor cloud, I don't think most people would know how to deal with that. I'll bet your spilled gas likely won't migrate into the intersection.
But on the plus side, we already see what handling/transportation of large amounts looks like for agriculture, even if rail carriers etc. dislike dealing with it.
[https://www.worksafebc.com/en/resources/health-safety/risk-a....] [https://www.osha.gov/laws-regs/standardinterpretations/1994-....]
It does have a higher ignition point than gas. But one a spark can definitely reach. It’s been a common problem in industry where ammonia gets used a lot (refrigeration in particular).
BLEVE’s are also a problem too of course. And the toxic nature of breathing it in! Haha.
Edit: Maybe methanol?
However hydrazine is liquid at room temperature and it can be converted to hydrazone (also being considered for fuel cells) which is solid at room temperature and non-reactive... until it comes into contact with water at which point it all turns back into hydrazine.
But yeah no there's really not a "nicer" fuel. Generally, if it has nitrogen in it and it isn't literally just nitrogen with itself, it's dangerous. And the more nitrogens it has the more dangerous it is.
Urea maybe? It’s almost non toxic and is 2x ammonia + a carbon monoxide molecule.
though not sure how efficient it would be to extract energy from.
Speaking of ‘extra nitrogen’s are generally bad’, a callout to the azides!
I have extinguished a fire with diesel.
It isn’t as easily flammable as gas, and doesn’t have easily autoignitable vapor like gas.
I’m guessing you dumped a lot of it on something without a lot of thermal mass?
If you did the same on a bonfire, you’d have a different story.
If you dump gasoline on a fire, it will go ‘fwoomp’ and try to climb back into whatever container you poured it out of. If it succeeds, that container may even explode. Which is bad, and why people die or get terrible burns from pouring gasoline on fires.
If you pour diesel on a fire, the fire will get bigger and none of those things will happen. Unless, apparently, like the poster above, you pour so much on it so fast it drowns it before the diesel can get up to temp. Apparently. I’ve personally never tried that.
Diesel is basically cooking oil in many ways, and you can do the same thing with cooking oil too if you want.
This is well known by every redneck I’ve ever met, and I’ve personally done it numerous times.
P.S. also, putting gasoline on cold fuel in warm climates makes a pretty cool fireball due to said flashpoint. Just, you know, don’t light it from close up. Cold climates? No problem.
Ammonia is easier to liquify than hydrogen, and is in many respects easier to handle. However, it's definitely not something you want to have a spill of at a gas station or in your garage, and for that reason, it probably won't have "consumer" uses.
As far as industrial gasses go, it's certainly nowhere near the worst, and there's plenty of ammonia tankers on the roads today, but large spills do kill people every now and then.
I was once in a presentation which claimed formic acid to be a better alternative, but I'm not an expert in that field, so I can't comment on its merits.
Or maybe a regional factory with short pipelines.
As for the idea itself. Ammonia as fuel fails the first principle of safe design. It’s a poisonous gas. Using it as a fuel is a willingness to trade the safety of people for a cheaper fuel.
Being near either one as it explodes would be bad, but I wonder which one looks more impressive movie-effects-wise? :)
If there were an oxidizer in the mix somehow, it would be rather more explosive.
Add the issues with hydrogen embrittlement and Ammonia starts to look trivial by comparison. People deal with industrial quantities of Ammonia on a regular basis without significant issues. Hell even gasoline and diesel are toxic and can be quite dangerous
This is not to mention everything else. The immense death toll directly (crashes) and indirectly (pollution, particulates, etc). The waste of space in cities. The waste of time in traffic that is unfixable if everyone is driving in an individual car. Etc etc. I wish people would stop trying to save the auto industry and start looking at the root of the problem.
Result, reduces carbon footprint of travel - land shipping - ability to build out modern towns - etc
Toss in a bill to require all train lines to also install national fiber. You now have enabled the revitalization of large swaths of the county.
Well its not like you can put any petrochemical fuels in you coffee
No, they have significant issues on a regular basis still.
And plenty of more recent examples: https://www.fox29.com/news/tanker-truck-fire-closes-stretch-...
Ammonia is one of the most common chemicals manufactured and transported around the world and has plenty of accidents but hydrocarbon accidents get into the hundreds of deaths: 150 dead https://en.wikipedia.org/wiki/Tacoa_disaster 500-600 dead 5000–7000 suffering severe burns https://en.wikipedia.org/wiki/San_Juanico_disaster 167 dead https://en.wikipedia.org/wiki/Piper_Alpha
People even hook up to natural gas lines after events big and small like: 300 dead https://en.wikipedia.org/wiki/New_London_School_explosion or here’s a recent event which destroyed 60-100 homes https://en.wikipedia.org/wiki/Merrimack_Valley_gas_explosion...
Ammonia is probably too unsafe for cars and boats. But anything filled by professionals like trains or ships would work. But might work to have tank exchange system like with propane.
https://spectrum.ieee.org/why-the-shipping-industry-is-betti...
https://www.wartsila.com/media/news/30-06-2020-world-s-first...
https://www.lr.org/en/about-us/press-listing/press-release/i...
https://www.ammoniaenergy.org/articles/maritime-fuel-mix-cou...
But the main concern is that ammonia burns slowly. It might work in power plants but not in EVs
The lower explosive limit of hydrogen is ~4%. By comparison the 300 ppm immediate danger to life and health threshold of ammonia is .03%.
It is intrinsically dangerous, i.e. without a source of ignition, at concentrations 2 orders of magnitude lower than the LEL of hydrogen.
Not every hydrogen leak is a concern, but just about every ammonia leak is.
The established OSHA 15 minute exposure limit for ammonia is 35 ppm, 8 hours is 25 ppm.
https://about.bnef.com/blog/japans-ammonia-coal-co-firing-st...
“willingness to trade the safety of people for a cheaper X” is exactly what we should expect car companies (and companies in general) to do, because that’s what they’ve done so often though history.
[1] https://youtube.com/watch?v=jN7mSXMruEo “These stupid trucks are literally killing us” -NotJustBikes
Gasoline fumes don’t typically auto-ignite either. And that is all flash point is about.
Anhydrous ammonia’s ‘flash point’ (producing flammable/explosive vapors) is well below room temperature at STP? It boils at -28F. That’s why it is so commonly used for refrigeration.
It does have a specific LEL and UEL that makes it less dangerous than gasoline. It also has a much higher auto ignition temp.
Yeah, anhydrous ammonia is less dangerous than gasoline (1 instead of 4) on the fire diamond due to it being less easy to ignite.
But flash point doesn’t help you here?
electrical sparks or open flame can still definitely do it. And have, multiple times.
Some pretty amazing clips in industrial accident videos from it, actually. My favorite part is when the chunk of roof almost makes it to the highway.
The Toyota Mirai, a production hydrogen car, uses a type IV carbon fiber pressure vessel rated for 70 MPa / 10,000 psi.
Type V are rated for 15,000 psi.
It is not necessary to liquefy hydrogen for adequate range in ground transport applications: The Mirai yields a 402 mile EPA rated range on gaseous hydrogen.
The tanks weigh 93kg filled with 5.65kg hydrogen, yielding an approximately 190 kWh of stored energy.
All without corroding flesh in trace concentrations.
By comparison the Tesla Roadster's 450kg battery pack yields a 200 kWh capacity.
Ammonia is and would likely continue to be stored in metal pressure vessels as an obvious cost optimization and thus would compare unfavorably to hydrogen pressure vessels' effective energy density where that area of the performance versus cost optimization space is not available due to embrittlement.
I suppose it's worth noting in your second link, the fatalities were from the kinetics of the impact, which is a hazard that belongs to "things with velocity" rather than "things containing fuels".
We can assume that uncontained fire and explosion are categorical hazards with fuels.
Ammonia has significant risks that few other proposed fuels present and I believe it's worth considering whether this is something we want moving outside of hazmat routes between industrial zones.
Major spills of either are dangerous but rare compared to how much is being created and transported. We’re only ~5x as much gasoline vs Ammonia today. Considering most cars would be EV’s I suspect the total amount of Ammonia produced even with widespread adoption isn’t going to change by that much. Say Long haul trucks, heavy equipment, aircraft etc.
PS: Which isn’t to say Ammonia is actually a good fuel, the only thing I can think that actually used the stuff was the X-15. So it would need significant economic advantages to end up adopted.
Enough hydrogen to power humanity by fusion is readily available anywhere :)
That video took place in an engine room, so any combination of heat, flame, or spark is possible.
If ammonia is boiling (and producing a fog) of concentrated vapor which then burns/explodes in exposure to an open flame, which it will definitely do at even OF, that is an entirely academic point no?
It still has the same effect.
I once got to watch some moderately crazy students fill an ordinary party balloon with a stoichiometric mix of hydrogen and oxygen at ambient temperature and pressure. When it was ignited, the result was extremely impressive. No one was injured (because we were all warned to protect our ears and open our mouths and balloons don’t produce significant shrapnel), but the shock wave was not at all subtle.
We ran into two problems. First, a number of the flames blew out on their way up. No fireball.
Second, we ran out of balloons pretty fast. So he cast around for ideas, and decided to fall back on a box of condoms. They held a lot more hydrogen than the balloons.
They were also equally likely to go out before blowing up. I always imagined them coming down on someone's lawn, causing no end of confusion.
[DO NOT TRY THIS AT HOME! And if you're tempted, there's one thing I left out that's necessary for it to work properly, and the only thing I'll say about it is this warning: https://sciencenotes.org/add-acid-to-water-or-water-to-acid/ ]
The stoichiometric premixed balloon is only 2/3 H2 by volume, so it releases 1/3 less energy, but it’s a whole different experience when the energy is released essentially all at once. Interestingly, there was no noticeable fireball from the premixed balloon.
A premixed H2+air balloon probably makes a fine explosion, too :)
Oh, I'm quite aware. The other fun game we played was with his acetylene welding torch and balloons. It has separately controlled tanks of acetylene and oxygen. Acetylene only = nice big fireball. Acetylene + oxygen = no fireball at all, instead a very loud boom + a bit of a shockwave.
But H2 takes up most of the space in the balloon, and acetylene is nice and compact, so considerably more total energy should be available with acetylene!
I don’t know whether oxyacetylene will detonate nicely, though, or whether a balloon-sized oxyacetylene mix will merely combust subsonically.