
Hydrogen derived from ammonia could open up new export market for Australia - boyter
http://www.abc.net.au/news/2018-08-08/hydrogen-fuel-breakthrough-csiro-game-changer-export-potential/10082514
======
mchannon
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](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.

~~~
yomly
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

~~~
mchannon
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.

~~~
dsp1234
The spec sheet at [0] claims:

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...](https://pressroom.toyota.com/releases/2016+toyota+mirai+fuel+cell+product.download)

[1] -
[http://www.wolframalpha.com/input/?i=density+of+hydrogen+at+...](http://www.wolframalpha.com/input/?i=density+of+hydrogen+at+70MPa)

[2] -
[http://www.wolframalpha.com/input/?i=122.4L+at+36.69+grams%2...](http://www.wolframalpha.com/input/?i=122.4L+at+36.69+grams%2Fliter)

[3] -
[http://www.wolframalpha.com/input/?i=density+of+hydrogen+at+...](http://www.wolframalpha.com/input/?i=density+of+hydrogen+at+87.5MPa)

[4] -
[http://www.wolframalpha.com/input/?i=122.4L+at+45.96+g%2FL](http://www.wolframalpha.com/input/?i=122.4L+at+45.96+g%2FL)

~~~
amluto
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.)

~~~
theptip
If you hover over the "Variation with temperature at constant pressure" chart
you get a "sources" link, which references

National Institute of Standards and Technology, NIST Reference Fluid
Thermodynamic and Transport Properties Database (REFPROP)

[https://www.nist.gov/srd/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.

------
credit_guy
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”

[1]
[https://en.m.wikipedia.org/wiki/Ammonia#Energy_carrier](https://en.m.wikipedia.org/wiki/Ammonia#Energy_carrier)

~~~
growlist
> per volume ammonia holds more hydrogen than does liquid hydrogen

How is this possible? Suspect the answer would be way over my head!

~~~
masklinn
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](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).

~~~
meta_AU
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.

~~~
falsedan
spot on

------
mjsweet
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. “

[https://pubs.acs.org/doi/10.1021/acssuschemeng.7b02219](https://pubs.acs.org/doi/10.1021/acssuschemeng.7b02219)

------
mjsweet
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?

~~~
tk75x
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.

------
pjc50
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)

[http://www.siemens.co.uk/en/insights/potential-of-green-
ammo...](http://www.siemens.co.uk/en/insights/potential-of-green-ammonia-as-
fertiliser-and-electricity-storage.htm)

Edit: this seems to be more detailed
[http://www.sciencemag.org/news/2018/07/ammonia-renewable-
fue...](http://www.sciencemag.org/news/2018/07/ammonia-renewable-fuel-made-
sun-air-and-water-could-power-globe-without-carbon)

------
radicalbyte
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.

------
maga
Ammonia is toxic, though, we will have to convert it back to hydrogen way
before it reaches the car or most gas stations, just to be on a safe side.

~~~
_Codemonkeyism
Petrol is also toxic, that said I have no clue about the relative toxicity.

~~~
semi-extrinsic
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.

~~~
Dylan16807
> If you spill just 1 gram, the smell is so strong the average person is
> running away in fear.

That's a safety feature.

~~~
marcosdumay
Yes. With natural gas we have to add it, in ammonia it's there for free.

------
nicktelford
Does anyone know what the potential as a utility-scale energy storage medium
is?

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.

------
timbit42
> 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.

------
black6
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?

~~~
Shoh3pif
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.

------
acd
Other ammonia based car projects

[http://www.nh3car.com/](http://www.nh3car.com/)
[https://nh3fuelassociation.org/2013/06/20/the-amveh-an-
ammon...](https://nh3fuelassociation.org/2013/06/20/the-amveh-an-ammonia-
fueled-car-from-south-korea/)

[https://en.wikipedia.org/wiki/Energy_density](https://en.wikipedia.org/wiki/Energy_density)

------
tigerlily
CSIRO is partnering with the British Oxygen Company (BOC) on this tech.

~~~
TheSpiceIsLife
BOC hasn’t stood for British Oxygen Company since 1978.

The company was originally Brin's Oxygen Company, Ltd. started by French
Brothers.

[https://en.m.wikipedia.org/wiki/The_BOC_Group](https://en.m.wikipedia.org/wiki/The_BOC_Group)

------
SCAQTony
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.

Lithium to cheap to recycle: [https://waste-management-world.com/a/1-the-
lithium-battery-r...](https://waste-management-world.com/a/1-the-lithium-
battery-recycling-challenge)

"...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...](https://www.washingtonpost.com/news/in-
sight/wp/2018/02/28/the-cost-of-cobalt/?utm_term=.11e1d3b1c0dc)

Goro Nickel Mine image: [http://www.sulphuric-acid.com/sulphuric-acid-on-the-
web/acid...](http://www.sulphuric-acid.com/sulphuric-acid-on-the-
web/acid%20plants/Goro%20Nickel%201.jpg)

------
krishnamohan291
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

------
baybal2
>"Today is the very first time in the world that hydrogen cars have been
fuelled with a fuel derived from ammonia — carbon-free fuel."

To begin with, a lot of ammonia production is usually colocated with natural
gas plants for a ready supply of hydrogen.

~~~
gonvaled
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.

~~~
baybal2
>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.

[https://phys.org/news/2017-06-ammonia-on-demand-
alternative-...](https://phys.org/news/2017-06-ammonia-on-demand-alternative-
production-method.html) \- looks almost too good to be true

~~~
pjc50
> nuclear sulphur-iodine process.

Corrosive reagants at 1000C? Great.

~~~
baybal2
This is the least nasty process of all other know alternatives

