It looks like wikipedia was already updated with this information [1]. I personally find their summary to be more informative.
“Ammonia can be manufactured from solar energy, air and water. This is an efficient way to package hydrogen into a chemical that is much cheaper to store and transport than pure hydrogen be it as gas or as liquid. In fact, per volume ammonia holds more hydrogen than does liquid hydrogen. Ammonia may be the key to overcome not only the daily but also the seasonal fluctuations of renewable energy sources.
This approach will solve many of the problems foreseen for the proposed Hydrogen economy, that instead could be replaced by an Ammonia economy, essentially still a hydrogen economy.
In early August 2018, scientists from Australia’s Commonwealth Scientific and Industrial Research Organisation (CSIRO) announced the success of developing a process to release hydrogen from ammonia and harvest that at ultra-high purity as a fuel for cars. This uses a special membrane. Two demonstration fuel cell vehicles have the technology, a Hyundai Nexo and Toyota Mirai”
It doesn't. The membrane "cracks" the ammonia into N2 and H2. The N2 is released to the atmosphere. The H2 is used in a hydrogen fuel cell to power an electrical drivetrain or in an internal combustion engine with a mechanical drivetrain.
It's highly endothermic. Replacing the hydrogen with oxygen is exothermic.
So one can create some ammonia-air fuel cell. But reducing it first to push the hydrogen into a fuel cell will almost surely net a negative amount of energy because of the losses.
(Note this is energy density by volume, which is the metric most care about. Energy density by weight of H2 gas is great, but the volume is enormous in comparison.)
Ammonia has been long recognized as a great medium for energy storage and you can generate at the site of electric generation. But the challenge has been extracting the hydrogen from the ammonia. My understanding is that hydrogen crackers exist, but have only been successful commercially at large scale. A portable cracker that you can put on a car that extracts hydrogen on demand from an ammonia storage tank is the innovation we need to see. Apparently there is work in Denmark that looks promising... (And now there is this new membrane technology from Australia.)
Personally, I am cheering for ammonia as a storage means. I am not a fan of batteries found in today's electric vehicles because there are too many conflict minerals in them. Maybe Tesla will succeed mining colbat in Colbat Ontario Canada... But until then, it is probably coming from the Congo or Bolivia.
> "The raw energy density of liquid ammonia is 11.5 MJ/L, which is about a third that of diesel."
Yes, but that's assuming you'd burn it, I suppose (not a chemist). In this case, you're extracting H atoms using a different process, and I imagine that this wouldn't utilize the full raw energy density of ammonia.
Looking at the process as a whole, it is burning - or at least oxidation. Starts with NH3 and ends up with H2O and N2 (preferably not NO2). The energy liberated from the bonds is the same. The amount of energy available at the wheels depends on a lot of fine details of how it's used.
I would expect this is due to the fact that each ammonia molecule contains three hydrogen atoms, whereas a hydrogen molecule contains only two. So liquid ammonia would be expected to contain more hydrogen per volume than liquid hydrogen.
Molecular hydrogen is unpolarized while ammonia molecules can establish hydrogen bonds, thus packing them more densely under the same conditions.
For really dense hydrogen we would need its metallic form but that requires pressures you might find in the core of jupiter. The electromagnetic force is more convenient than gravity.
Intramolecular bonds are quite a bit smaller than intermolecular distances, so if you pack atoms into longer molecules you get a denser result.
I'm guessing very long molecules become problematic (because they don't pack well), but ammonia is a small molecule so way below that.
Liquid ammonia has a density of ~690 kg/m3 and a molar mass of 17 g/mol so ~40k mol / m3, as NH3 that's ~120k atoms of hydrogen per cubic meter. Meanwhile liquid hydrogen has a density of 71g/L and a molar mass of 2.02 g/mol so a very similar ~35k mol/m3 but as H2 that's only ~70k atoms of hydrogen per cubic meter.
And liquid hydrogen aside from being extremely flammable, can't exist above 30K and degrades storage material (https://en.wikipedia.org/wiki/Hydrogen_embrittlement), ammonia is much more forgiving and liquid at ambient temperature above 1MPa (10 times atmospheric pressure), not innocuous by any means but way easier to transport and store (storage requirements are similar to propane).
Probably also because ammonia is polar, three positive protons and an electron pair in a tetrahedral arrangement. Whereas H2 is two protons hiding an electron pair in a linear arrangement.
So, does anyone have a link which describes the actual technology? The article seems to switch back and forth from talking about hydrogen to talking about ammonia as a carrier for hydrogen. Note that there's already a huge market for ammonia itself (often as a carrier for nitrogen, for agriculture)
Probably because ammonia production is using a waste product from natural gas plants (hydrogen).
This just means that one of the inputs for ammonia production has esentially zero cost, on those plants. But it does not answer any of the following questions:
1) Can that scale to produce high quantities of ammonia, without having adverse effects. That is, if the goal is to reduce dependency on hydrocarbons, having more natural gas plants makes no sense.
2) Would it be cheaper to produce hydrogen (and thus ammonia) using other processes? Currently the hydrogen is free from natual gas plants, but the natural gas plant is very much non-free. If you do not want natural gas, it makes no sense.
>Would it be cheaper to produce hydrogen (and thus ammonia) using other processes?
No. The one and only thing coming close to be more economical is the nuclear sulphur-iodine process.
But by the time we get to 4G reactors, we will already be in a very different world. Bruteforce electrolysis might be something normal by then just because of its convenience.
A dark horse here is the direct production method being recently discovered in Japan.
Here is a paper created by CSIRO scientists on the round-trip conversion efficiency of the process for different routes
The paper also mentions fuel cells which was a question I wondered about:
“Ammonia at the point of end use can be converted to hydrogen for fuel cell vehicles or alternatively utilized directly in solid oxide fuel cells, in an internal combustion engine or a gas turbine. “
Petrol is safe enough that you can let untrained people pour it from one tank to another. Spill a little, no problem.
Ammonia is a gas at standard temperature, and will be transported and used as a liquid under pressure. If you expose liquid ammonia to the atmosphere, all of it boils off rapidly. The IDLH (immediate danger to life and health) limit for ammonia is 300 parts per million. If you release 15 grams of ammonia inside a typical garage, you have exceeded the IDLH threshold. If you spill just 1 gram, the smell is so strong the average person is running away in fear.
Spill some gas/petrol, wait a couple of minutes, and most of the toxicity is gone and no harm done to you except that you have increased your chance, very slightly, of getting cancer during your lifespan.
Ammonia being a gas, it's better compared to natural gas than liquid hydrocarbons.
You don't want common people handling it directly, you want safeguards every few inches on ducts that transport them and you will still have deaths caused by them every so often.
I don't think we would have to do it way before. Gasoline is toxic, and flammable. Hydrogen is flammable. Cars pump out Carbon Monoxide which is toxic.
We are well past the "safe side" currently and it seems to be going ok.
Ammonia is gaseous under normal conditions, meaning that any leak would result in presence of gaseous ammonia in air. 500 mg of ammonia per m3 of air can damages eyes, a short exposure to 3g can have overall toxic effects, at 7 g and higher it damages the skin. Gasoline, hydrogen, or monoxide don't come close to this level of toxicity.
There is an entire industrial infrastructure in many agricultural nations that manufactures, distributes, and fertilizes with liquid anhydrous ammonia. All the necessary tech to get this into a vehicle without killing anyone already exists.
And it's regulated way more than the fuel industry. In many of those developing nations, opening a gas station is as simple as burying a few containers and paying off fire-safety inspectors. I'm not at all eager to see them handling ammonia that way.
From what I've seen of "developing nations", a "gas station" is a roadside hut with a shelf of liter-size glass bottles and a skinny dude to pour the bottles into the tank of your motorcycle. Obviously no one would handle pressurized liquid ammonia in that fashion, because it isn't physically possible. One wouldn't imagine that developing nations are the target market for this anyway. The point is that lots of people know how to handle ammonia, and if the market expanded lots more people could learn. If we're serious about reducing carbon emissions (frankly that's an open question), what would be so terrible about bringing back filling station attendants?
And then there is BRICS--countries that have the means to use the modern tech, but the governments are too weak or too corrupt to enforce regulations.
This tech has its merits, if done right it can increase the overall efficiency of hydrogen tech, however carrying kgs of ammonia in consumers' cars or tons of it in local gas stations when mere grams can kill you is pushing it too far.
Can anyone confirm that this is simply a way to package hydrogen into a safe transportation medium to international markets (from Australia as an example) and then converted back to hydrogen when it reaches the target country?
Put it this way, is it converted back to hydrogen before it’s pumped into the car? I kinda like the idea of ammonia being converted into hydrogen in the car but judging from the news reports we have seen here in Australia the membrane technology looks quite large... more something one would see in a refinery than a car.
So my question is: at what stage would the ammonia be converted back to hydrogen; at a refinery, the service station or in the car itself?
Cars are far from the only potential consumer. Sure, you might also use some of the hydrogen to power cars with fuel cells. Or you use it to charge EVs. Or you use the ammonia directly for grid electricity and heating. Or industrial processes.
Since there are already hydrogen fuel cars available from reputable manufacturers who (I assume) would be hesitant to add a fairly complicated component into their production vehicles, it might be easiest to transport liquid ammonia to car fill stations at which point it would be converted to hydrogen before going into the cars.
The arid locations mentioned in the article are lacking one of the feedstocks for this reaction -- water. I am not an Aussie, so what I know may be wrong, but doesn't Australia already have a water shortage inland?
You probably need relatively little water compared to other processes that evaporate/drain it (agriculture) or use it for run-through cooling (power plants). Even an ocean tanker full of water wouldn't make much of a dent into the flow rates of a river.
Other articles talking about this technology mention the possibility of using clean energy (solar/wind) to desalinate water to facilitate the production of ammonia.
Ammonia is also key to modern agriculture; it would be fantastic news if it became economical to create it from air and water using wind or solar power.
When it is, we need to cover Australia, North Africa and the Southern United States with sun panels and start piping/shipping it to the places it can be used.
Australia does not have huge deposits of hydrogen they're just sitting around trying to find uses for. So the input for this technology is imaginary.
Making ammonia out of hydrogen, which is so useful that half your food comes from it, is called the Haber-Bosch process (https://en.wikipedia.org/wiki/Haber_process), and has been around for about a century.
Ammonia is a pretty crappy way to move things around too. Not as bad as hydrogen, but if you have ammonia, reacting it with some CO2 to make urea is how the professionals do it. Ammonia is still a dangerous gas or liquid. Urea is inoffensive little white pellets. You can already buy urea at American truck stops as "DEF" or diesel exhaust fluid.
Finally, unless they've miniaturized their technology to where you can pump ammonia into your car to run it on hydrogen instead of filling it directly with hydrogen, you're still limited by hydrogen's crappy storage density where it's needed most- in the car.
So let's take two flows and compare them to this technology's flows:
NG -> pipeline -> CNG -> CNG Engine (simple, if not all that widespread)
e- -> grid -> EV charger -> battery -> EV motor (same)
vs.
Aussie coal -> CO2 + H2 -> NH3 -> H2 -> H2 tank -> Fuel Cell -> EV motor
or
Aussie PV -> H2 -> NH3 -> H2 -> H2 tank -> Fuel Cell -> EV motor
I wish I could educate newspeople on how to distinguish real breakthroughs from university-sponsored snake oil like this.
You seem to be dismissively implying that because scientists are experts that they have obviously considered this. Which isn't true at all. Scientists are typically much more motivated by the pursuit of knowledge than strict commercial value.
I checked out the Toyota Mirai - it does indeed use hydrogen gas cylinders from what I can tell. So this research is targeting simply the ability to transport hydrogen.
Ironically, the ships that carry all that ammonia to Asia almost certainly used fossil fuels and who knows what the carbon footprint around building the membranes for the hydrogen transfer is like
And shipping is the most egregiously polluting transportation in existence. Something like 10 to 30% of emissions come from 6000 ships in service. Folks claim its ok because it settles into the ocean quickly - ok for everybody but the ocean.
> Something like 10 to 30% of emissions come from 6000 ships in service.
Some 10% to 30% of sulfur emissions come from those ships. They do that because they move in the open ocean where nobody cares about a short lived pollutant.
Sulfur moves quickly into the ocean where it not only non-toxic, but also beneficial to life. (Sulfates - what it will settle down into - is widely used as fertilizer on land.)
Well, there is certainly some amount where the wrong kind of life takes over. It is way over what cargo ships throw around, but people have been polluting some parts of the ocean with too much sulfates.
this is from some horribly irresponsible clickbait newsy reporting a couple of years ago. It's only a very specific subtype of emissions, not 'emissions' in general.
Nitrogen oxides and sulfur oxides. How is that irresponsible? The conversation has turned to CO2 because of global warming, but these are still damaging. And CO2 isn't strictly a pollutant at all. I stand by those statistics.
Here's a fun little exercise with the Toyota Mirai.
Read the spec sheet, and read the wikipedia article. They claim the thing can hold 5 kg of H2, at 10,000 psi.
Look into how big the tanks are.
The math will show that at that pressure, taking up that much space, you can fit no more than about 3.7 kg of H2 in there.
The difference between the diesel emissions and mileage scandal and the Mirai is that they actually made the math work with the former, as well as large enough scale for people to care.
density of hydrogen at 87.5MPa equals 45.96 g/L [3]
122.4L at 45.96 g/L equals equals 5.63kg [4]
So the amount is somewhere between 4.5kg and 5.63kg, depending upon the final pressure after filling. Which seems to line up squarely with "Approx. 5.0kg".
I am highly skeptical of using Wolfram Alpha like this. It steadfastly refuses to explain how it got its answer or what sources it used. These are high pressures and large densities. Are these results of an ideal gas law calculation? Are they results from the van der Waals equation? Are they extrapolated from actual experimental data? If so, what experiment? What are the error bars? Are they talking about pure Hydrogen-1 or are they talking about the isotopic mix found in sea water? (The latter is a small correction, but it’s still something that they should explain on the site.)
I.e. these are standard reference curves at a fixed temperature.
If you click the link on "Hydrogen" you get a page for molecular hydrogen, H2, so not an isotopic mix. Whether that's the right input for this calculation is beyond my technical knowledge, but Wolfram is displaying its parameters quite straightforwardly.
To my reading it looks like a quite well-explained calculation, though I can see why you might think otherwise if you hadn't spotted the somewhat-hidden "sources" link.
Surely van der Waals should provide a better model here, as we're having pretty dense gas which is far from ideal. So I'd assume it should be van der Waals model; not sure what Wolfram Alpha actually does.
The data I found for the internal volume of the tanks says they're about 122 litres.
When I do the math with that volume, 10.000 psi, and 25 degrees, I get about 3400 moles, which is actually over 5 kg. But certainly 25 is an ideal temperature, so claiming 5 kg seems reasonable.
They proposed one use, which would be to use it as storage for solar/wind power. Perhaps their plan is that when there's excess output from renewables, they'll use electrolysis to generate hydrogen gas from water?
That is exactly the plan. With renewables you have to deploy far more than you need due to capacity factor, so to average 100kW on solar you need to deploy between 300kW and 400kW of capacity. So during the course of the day you will be generating significantly more or significantly less power than required.
Batteries and hydro will help for short term storage of excess power (ie: overnight, during cloud passage) but for long term storage (eg for transport by sea) you need something with higher energy density. For export especially you need high energy density since shipping charged batteries across the planet is going to be extremely inefficient.
The breakthrough this membrane represents is an increase in the “well to wheels” efficiency of the hydrogen economy (which is lower overall than the “pure electric” economy involving BEVs). Having said that, the “well to wheels” efficiency of H2 using Ammonia as a transport medium is under 20%, so it’s really only useful when there is plentiful cheap energy which nobody else has a better use for.
Other uses for plentiful cheap electricity could be (for example) chilling or heating large volumes of water or other thermal mass for air conditioning and industrial processes. If you have large tanks of water you can spend energy chilling (or heating) them when electricity is cheap, then use the chilled water to cool whatever it is you have that is getting too hot (and vice versa for hot water storage).
But if people are willing to pay enough for hydrogen at point of use, there will be an economic case for producing ammonia in Australia to be converted to hydrogen in Japan resulting in 1kWh in Japan costing about the same as 4kWh in Australia.
On my memory, there were countless claims of "direct" ammonia production, and all came to be uneconomical or being outright scams. But in last few years, there were numerous works on catalytic production with some merit to them.
The comparative advantage nations have over each other in energy in a post-fossil fuel world will be much reduced. That is, Saudi Arabia has a huge advantage over Japan in terms of cheap fossil fuel energy, so Japan imports a lot from them. Though Saudi Arabia likely has an advantage over Japan in renewable resources, its not as dramatic as their fossil fuel advantage, so Japan would invest in their own energy resources and import less of them.
Because of this there will likely be much less international energy traded in general.
It's coming out of the CSIRO, which while not the greatest at commercialisation, have a pretty solid track record of not spinning bullshit. The car spinning looks like it's coming from auto industry wingnuts.
”Australia does not have huge deposits of hydrogen”
Australia has plenty of sunlight, though, much more than they need. In the long term, if/when we live of renewables, they hope to export the energy in it.
The traditional solution is a cable, but Australia is fairly distant from the possible export markets.
That, I think, is where this comes in.
Australia has access to oceans that have the hydrogen, and air contains the necessary nitrogen.
I would think they envision producing ammonia at scale, shipping it in tankers to a densely populated country or a country that has less sunlight, converting it back to electricity in a power station there, and feeding the result into the grid.
Doable? Yes. Economically viable? Who knows. That doesn’t only depend on this process, but also on the question how easily other countries can get their power cheaper.
It might help to note that in 2009, Australia imported 900,000 tonnes of urea. Gonna take a long time before they meet that demand.
Australia's an energy importer, big time. Sure, bargeloads of coal go out to places like Saudi Arabia, but tankerloads of oil and LNG come in.
If you want to export your energy cheaply, look at Aluminum (sorry Aussies, Aluminium to you) instead. It's safe, made from local ingredients, and stable. That's why gulf petrostates are putting huge aluminum smelters in- much cheaper to make the aluminum with their natural gas than compress and store the stuff.
I live 20min from the largest aluminium smelter in Oz. :) It's the largest energy consumer in the state and every time there's fears about electricity blackouts they make the news because of the worry about their potlines getting killed.
We're also a bit LNG exporter... so I'm curious, as what you're saying they're doing in the gulf should apply here too. When they use LNG for smelting, are they using it to generate electricity or burning it direct for heating?
What I never understood was why they didn't tap into Portland's geothermals for a ready source of steam to run a local electricity generating turbine.
These days they would have to be worried about a bushfire hitting Loy Yang. It was a close call in 2009 when they could have lost the mine and plant.
There's a gas powerstation at Mortlake and talks of building another for Alcoa as it could feed straight off the Otway Basin gas fields.
I see a few wind farms have popped up, no doubt due to the areas reputation for being constantly windy.
Lithium, cobalt and Metal hydride are messy and Lithium, since it is so cheap, it is not recycled for reuse. Though hydrogen is leaky, clunky and expensive to get from source to engine, it will be a better investment in reduced CO2 emission, a reduced need for lithium salt "flats" and cobalt mines. (Ever seen a cobalt mine?) scorching the earth surface.
"...Recycled lithium is as much as five times the cost of lithium produced from the least costly brine based process. It is not competitive for recycling companies to extract lithium from slag, or competitive for the OEMs to buy at higher price points from recycling companies. "
> Dr Dolan said the cost for the fuel would be around $15 a kilogram, with an average car holding five kilos of pure hydrogen in a tank. "But the efficiency of the car is twice as good as current gasoline cars, so you can actually drive twice as far on a tank," he said.
So AUD $75 for 800 kms? My Prius gets 600 kms on the highway on a CAD $40 tank of gasoline.
Perhaps a hydrogen/electric hybrid would be better.
It is a watershed moment for australian economy.New areas opportunites will boost the income and generate jobs on a large scale for job aspirants and will have a cascading effect on the economy
92 comments
[ 3.5 ms ] story [ 150 ms ] thread“Ammonia can be manufactured from solar energy, air and water. This is an efficient way to package hydrogen into a chemical that is much cheaper to store and transport than pure hydrogen be it as gas or as liquid. In fact, per volume ammonia holds more hydrogen than does liquid hydrogen. Ammonia may be the key to overcome not only the daily but also the seasonal fluctuations of renewable energy sources.
This approach will solve many of the problems foreseen for the proposed Hydrogen economy, that instead could be replaced by an Ammonia economy, essentially still a hydrogen economy.
In early August 2018, scientists from Australia’s Commonwealth Scientific and Industrial Research Organisation (CSIRO) announced the success of developing a process to release hydrogen from ammonia and harvest that at ultra-high purity as a fuel for cars. This uses a special membrane. Two demonstration fuel cell vehicles have the technology, a Hyundai Nexo and Toyota Mirai”
[1] https://en.m.wikipedia.org/wiki/Ammonia#Energy_carrier
Also what does the chemical reaction look like when harvesting hydrogen from ammonia?
Reverse Haber process maybe?
2NH3 -> N2 + 3H2
So one can create some ammonia-air fuel cell. But reducing it first to push the hydrogen into a fuel cell will almost surely net a negative amount of energy because of the losses.
https://en.wikipedia.org/wiki/Ammonia#As_a_fuel
(Note this is energy density by volume, which is the metric most care about. Energy density by weight of H2 gas is great, but the volume is enormous in comparison.)
https://en.wikipedia.org/wiki/Hydrogen_storage
Ammonia has been long recognized as a great medium for energy storage and you can generate at the site of electric generation. But the challenge has been extracting the hydrogen from the ammonia. My understanding is that hydrogen crackers exist, but have only been successful commercially at large scale. A portable cracker that you can put on a car that extracts hydrogen on demand from an ammonia storage tank is the innovation we need to see. Apparently there is work in Denmark that looks promising... (And now there is this new membrane technology from Australia.)
https://www.mvsengg.com/products/hydrogen/ammonia-cracker/
http://www.ammoniaenergy.org/ammonia-cracking-to-high-purity...
Personally, I am cheering for ammonia as a storage means. I am not a fan of batteries found in today's electric vehicles because there are too many conflict minerals in them. Maybe Tesla will succeed mining colbat in Colbat Ontario Canada... But until then, it is probably coming from the Congo or Bolivia.
https://www.washingtonpost.com/graphics/business/batteries/c...
https://www.bloomberg.com/news/features/2017-10-31/the-canad...
Yes, but that's assuming you'd burn it, I suppose (not a chemist). In this case, you're extracting H atoms using a different process, and I imagine that this wouldn't utilize the full raw energy density of ammonia.
How is this possible? Suspect the answer would be way over my head!
Molecular hydrogen is unpolarized while ammonia molecules can establish hydrogen bonds, thus packing them more densely under the same conditions.
For really dense hydrogen we would need its metallic form but that requires pressures you might find in the core of jupiter. The electromagnetic force is more convenient than gravity.
I'm guessing very long molecules become problematic (because they don't pack well), but ammonia is a small molecule so way below that.
Liquid ammonia has a density of ~690 kg/m3 and a molar mass of 17 g/mol so ~40k mol / m3, as NH3 that's ~120k atoms of hydrogen per cubic meter. Meanwhile liquid hydrogen has a density of 71g/L and a molar mass of 2.02 g/mol so a very similar ~35k mol/m3 but as H2 that's only ~70k atoms of hydrogen per cubic meter.
And liquid hydrogen aside from being extremely flammable, can't exist above 30K and degrades storage material (https://en.wikipedia.org/wiki/Hydrogen_embrittlement), ammonia is much more forgiving and liquid at ambient temperature above 1MPa (10 times atmospheric pressure), not innocuous by any means but way easier to transport and store (storage requirements are similar to propane).
http://www.siemens.co.uk/en/insights/potential-of-green-ammo...
Edit: this seems to be more detailed http://www.sciencemag.org/news/2018/07/ammonia-renewable-fue...
To begin with, a lot of ammonia production is usually colocated with natural gas plants for a ready supply of hydrogen.
This just means that one of the inputs for ammonia production has esentially zero cost, on those plants. But it does not answer any of the following questions:
1) Can that scale to produce high quantities of ammonia, without having adverse effects. That is, if the goal is to reduce dependency on hydrocarbons, having more natural gas plants makes no sense.
2) Would it be cheaper to produce hydrogen (and thus ammonia) using other processes? Currently the hydrogen is free from natual gas plants, but the natural gas plant is very much non-free. If you do not want natural gas, it makes no sense.
No. The one and only thing coming close to be more economical is the nuclear sulphur-iodine process.
But by the time we get to 4G reactors, we will already be in a very different world. Bruteforce electrolysis might be something normal by then just because of its convenience.
A dark horse here is the direct production method being recently discovered in Japan.
https://phys.org/news/2017-06-ammonia-on-demand-alternative-... - looks almost too good to be true
Corrosive reagants at 1000C? Great.
The company was originally Brin's Oxygen Company, Ltd. started by French Brothers.
https://en.m.wikipedia.org/wiki/The_BOC_Group
The paper also mentions fuel cells which was a question I wondered about:
“Ammonia at the point of end use can be converted to hydrogen for fuel cell vehicles or alternatively utilized directly in solid oxide fuel cells, in an internal combustion engine or a gas turbine. “
https://pubs.acs.org/doi/10.1021/acssuschemeng.7b02219
Ammonia is a gas at standard temperature, and will be transported and used as a liquid under pressure. If you expose liquid ammonia to the atmosphere, all of it boils off rapidly. The IDLH (immediate danger to life and health) limit for ammonia is 300 parts per million. If you release 15 grams of ammonia inside a typical garage, you have exceeded the IDLH threshold. If you spill just 1 gram, the smell is so strong the average person is running away in fear.
That's a safety feature.
Spill ammonia?
https://www.vyperlook.com/extreme-things/policeman-killed-in...
You don't want common people handling it directly, you want safeguards every few inches on ducts that transport them and you will still have deaths caused by them every so often.
We are well past the "safe side" currently and it seems to be going ok.
This tech has its merits, if done right it can increase the overall efficiency of hydrogen tech, however carrying kgs of ammonia in consumers' cars or tons of it in local gas stations when mere grams can kill you is pushing it too far.
I have this inkling that developing this for cars isn't the best use, as battery EV looks set to best Hydrogen fuel-cells in that market.
Instead, I think pursuing it for shipping, aviation and utility-scale energy storage is a much better idea.
Put it this way, is it converted back to hydrogen before it’s pumped into the car? I kinda like the idea of ammonia being converted into hydrogen in the car but judging from the news reports we have seen here in Australia the membrane technology looks quite large... more something one would see in a refinery than a car.
So my question is: at what stage would the ammonia be converted back to hydrogen; at a refinery, the service station or in the car itself?
[1] https://en.wikipedia.org/wiki/Hydrogen_embrittlement
When it is, we need to cover Australia, North Africa and the Southern United States with sun panels and start piping/shipping it to the places it can be used.
Making ammonia out of hydrogen, which is so useful that half your food comes from it, is called the Haber-Bosch process (https://en.wikipedia.org/wiki/Haber_process), and has been around for about a century.
Ammonia is a pretty crappy way to move things around too. Not as bad as hydrogen, but if you have ammonia, reacting it with some CO2 to make urea is how the professionals do it. Ammonia is still a dangerous gas or liquid. Urea is inoffensive little white pellets. You can already buy urea at American truck stops as "DEF" or diesel exhaust fluid.
Finally, unless they've miniaturized their technology to where you can pump ammonia into your car to run it on hydrogen instead of filling it directly with hydrogen, you're still limited by hydrogen's crappy storage density where it's needed most- in the car.
So let's take two flows and compare them to this technology's flows:
NG -> pipeline -> CNG -> CNG Engine (simple, if not all that widespread)
e- -> grid -> EV charger -> battery -> EV motor (same)
vs.
Aussie coal -> CO2 + H2 -> NH3 -> H2 -> H2 tank -> Fuel Cell -> EV motor
or
Aussie PV -> H2 -> NH3 -> H2 -> H2 tank -> Fuel Cell -> EV motor
I wish I could educate newspeople on how to distinguish real breakthroughs from university-sponsored snake oil like this.
Ironically, the ships that carry all that ammonia to Asia almost certainly used fossil fuels and who knows what the carbon footprint around building the membranes for the hydrogen transfer is like
Some 10% to 30% of sulfur emissions come from those ships. They do that because they move in the open ocean where nobody cares about a short lived pollutant.
Sulfur moves quickly into the ocean where it not only non-toxic, but also beneficial to life. (Sulfates - what it will settle down into - is widely used as fertilizer on land.)
Read the spec sheet, and read the wikipedia article. They claim the thing can hold 5 kg of H2, at 10,000 psi.
Look into how big the tanks are.
The math will show that at that pressure, taking up that much space, you can fit no more than about 3.7 kg of H2 in there.
The difference between the diesel emissions and mileage scandal and the Mirai is that they actually made the math work with the former, as well as large enough scale for people to care.
Hydrogen storage is "Approx. 5.0 kg"
122.4L of volume (60L front, 62.4L rear)
pressure is between 70 MPa and 87.5MPa
Doing the math shows:
density of hydrogen at 70MPa equals 36.69 g/L [1]
122.4L at 36.69 g/L equals 4.49kg [2]
density of hydrogen at 87.5MPa equals 45.96 g/L [3]
122.4L at 45.96 g/L equals equals 5.63kg [4]
So the amount is somewhere between 4.5kg and 5.63kg, depending upon the final pressure after filling. Which seems to line up squarely with "Approx. 5.0kg".
[0] - https://pressroom.toyota.com/releases/2016+toyota+mirai+fuel...
[1] - http://www.wolframalpha.com/input/?i=density+of+hydrogen+at+...
[2] - http://www.wolframalpha.com/input/?i=122.4L+at+36.69+grams%2...
[3] - http://www.wolframalpha.com/input/?i=density+of+hydrogen+at+...
[4] - http://www.wolframalpha.com/input/?i=122.4L+at+45.96+g%2FL
National Institute of Standards and Technology, NIST Reference Fluid Thermodynamic and Transport Properties Database (REFPROP)
https://www.nist.gov/srd/refprop
I.e. these are standard reference curves at a fixed temperature.
If you click the link on "Hydrogen" you get a page for molecular hydrogen, H2, so not an isotopic mix. Whether that's the right input for this calculation is beyond my technical knowledge, but Wolfram is displaying its parameters quite straightforwardly.
To my reading it looks like a quite well-explained calculation, though I can see why you might think otherwise if you hadn't spotted the somewhat-hidden "sources" link.
Surely van der Waals should provide a better model here, as we're having pretty dense gas which is far from ideal. So I'd assume it should be van der Waals model; not sure what Wolfram Alpha actually does.
When I do the math with that volume, 10.000 psi, and 25 degrees, I get about 3400 moles, which is actually over 5 kg. But certainly 25 is an ideal temperature, so claiming 5 kg seems reasonable.
Except it became one of the most controlled substances around out of a sudden.
They proposed one use, which would be to use it as storage for solar/wind power. Perhaps their plan is that when there's excess output from renewables, they'll use electrolysis to generate hydrogen gas from water?
Batteries and hydro will help for short term storage of excess power (ie: overnight, during cloud passage) but for long term storage (eg for transport by sea) you need something with higher energy density. For export especially you need high energy density since shipping charged batteries across the planet is going to be extremely inefficient.
The breakthrough this membrane represents is an increase in the “well to wheels” efficiency of the hydrogen economy (which is lower overall than the “pure electric” economy involving BEVs). Having said that, the “well to wheels” efficiency of H2 using Ammonia as a transport medium is under 20%, so it’s really only useful when there is plentiful cheap energy which nobody else has a better use for.
Other uses for plentiful cheap electricity could be (for example) chilling or heating large volumes of water or other thermal mass for air conditioning and industrial processes. If you have large tanks of water you can spend energy chilling (or heating) them when electricity is cheap, then use the chilled water to cool whatever it is you have that is getting too hot (and vice versa for hot water storage).
But if people are willing to pay enough for hydrogen at point of use, there will be an economic case for producing ammonia in Australia to be converted to hydrogen in Japan resulting in 1kWh in Japan costing about the same as 4kWh in Australia.
>NG -> pipeline -> CNG -> CNG Engine (simple, if not all that widespread)
>e- -> grid -> EV charger -> battery -> EV motor (same)
>vs.
>Aussie coal -> CO2 + H2 -> NH3 -> H2 -> H2 tank -> Fuel Cell -> EV motor
>or
>Aussie PV -> H2 -> NH3 -> H2 -> H2 tank -> Fuel Cell -> EV motor
There is still one dark horse in the competition:
https://phys.org/news/2017-06-ammonia-on-demand-alternative-...
On my memory, there were countless claims of "direct" ammonia production, and all came to be uneconomical or being outright scams. But in last few years, there were numerous works on catalytic production with some merit to them.
The comparative advantage nations have over each other in energy in a post-fossil fuel world will be much reduced. That is, Saudi Arabia has a huge advantage over Japan in terms of cheap fossil fuel energy, so Japan imports a lot from them. Though Saudi Arabia likely has an advantage over Japan in renewable resources, its not as dramatic as their fossil fuel advantage, so Japan would invest in their own energy resources and import less of them.
Because of this there will likely be much less international energy traded in general.
It's coming out of the CSIRO, which while not the greatest at commercialisation, have a pretty solid track record of not spinning bullshit. The car spinning looks like it's coming from auto industry wingnuts.
Australia has plenty of sunlight, though, much more than they need. In the long term, if/when we live of renewables, they hope to export the energy in it.
The traditional solution is a cable, but Australia is fairly distant from the possible export markets.
That, I think, is where this comes in. Australia has access to oceans that have the hydrogen, and air contains the necessary nitrogen.
I would think they envision producing ammonia at scale, shipping it in tankers to a densely populated country or a country that has less sunlight, converting it back to electricity in a power station there, and feeding the result into the grid.
Doable? Yes. Economically viable? Who knows. That doesn’t only depend on this process, but also on the question how easily other countries can get their power cheaper.
Australia's an energy importer, big time. Sure, bargeloads of coal go out to places like Saudi Arabia, but tankerloads of oil and LNG come in.
If you want to export your energy cheaply, look at Aluminum (sorry Aussies, Aluminium to you) instead. It's safe, made from local ingredients, and stable. That's why gulf petrostates are putting huge aluminum smelters in- much cheaper to make the aluminum with their natural gas than compress and store the stuff.
We're also a bit LNG exporter... so I'm curious, as what you're saying they're doing in the gulf should apply here too. When they use LNG for smelting, are they using it to generate electricity or burning it direct for heating?
These days they would have to be worried about a bushfire hitting Loy Yang. It was a close call in 2009 when they could have lost the mine and plant.
There's a gas powerstation at Mortlake and talks of building another for Alcoa as it could feed straight off the Otway Basin gas fields. I see a few wind farms have popped up, no doubt due to the areas reputation for being constantly windy.
There's an equivalent amount of electrical energy to make an aluminum can as a gallon of gasoline (err.. 4L of petrol?).
http://www.nh3car.com/ https://nh3fuelassociation.org/2013/06/20/the-amveh-an-ammon...
https://en.wikipedia.org/wiki/Energy_density
Lithium to cheap to recycle: https://waste-management-world.com/a/1-the-lithium-battery-r...
"...Recycled lithium is as much as five times the cost of lithium produced from the least costly brine based process. It is not competitive for recycling companies to extract lithium from slag, or competitive for the OEMs to buy at higher price points from recycling companies. "
Cobalt Mines and their problems: https://www.washingtonpost.com/news/in-sight/wp/2018/02/28/t...
Goro Nickel Mine image: http://www.sulphuric-acid.com/sulphuric-acid-on-the-web/acid...
So AUD $75 for 800 kms? My Prius gets 600 kms on the highway on a CAD $40 tank of gasoline.
Perhaps a hydrogen/electric hybrid would be better.