Curtin Energy Corporation

TECHNICAL MEMO
To: Manager, Process Technologies
From: Brendan Jones
Date: 20th September 2018
Re: Preliminary Assessment of Green Ammonia for Energy Storage

1 The Green Ammonia Process

1.1 Overview

The German industrial manufacturing and energy company, SIEMENS, has launched a demonstration
project in the UK to showcase the potential of using “Green Ammonia” for energy storage [1]. The
project, costing approximately AUD$2.7m (US$2m), has been constructed at the Harwell Science and
Innovation Campus in partnership with the University of Cardiff and Oxford University.

The project has been outlined to demonstrate that renewable energies can be utilised to separate
water molecules to produce hydrogen, to, in turn, produce ammonia when combined with nitrogen
extracted from the atmosphere [1]. Anhydrous ammonia is then stored and transported in high
pressure containers, for future use as fuel or to reform hydrogen in the case of hydrogen fuel cells.
This is designed to reduce the effect of intermittency that renewable energy is known for. The
production of ammonia in this manner avoids carbon dioxide emissions and the need for natural gas
(methane) as a source of energy and resource to obtain hydrogen gas. Additionally, the combustion
of ammonia for fuel produces nitrogen and water with zero carbon emission, however small
amounts of nitric acid or nitrous oxide can form if the conditions are not ideal.

1.2 Synthesis Process

A pressure swing absorption air separation (PSAAS) unit is utilised to produce nitrogen from air
whilst water is split to produce hydrogen using a technique called polymer electrolyte membrane
(PEM) electrolysis. Using PEM electrolysis reduces operational costs as it can operate at high current
densities, utilising renewable energies such as solar and wind more effectively – capturing spikes in
energy input that would otherwise be lost [2]. The nitrogen and hydrogen gas streams are fed into a
reactor which carries out the Haber-Bosch process (on a fixed bed reactor) producing ammonia (1)
and then onto a pressurised tank where liquid ammonia is stored. Unreacted hydrogen and nitrogen
are recycled back, while the ammonia flows into the storage tank, via a separation vessel.

𝑁2 (𝑔) + 3𝐻2 (𝑔) ⇌ 2𝑁𝐻3 (𝑔) Δ𝐻 = −92 𝑘𝐽 𝑚𝑜𝑙 −1 (1)

The production of ammonia is an exothermic reaction - in general, optimum conditions for this
reaction to proceed in the forward direction is a temperature of about 400-450°C and pressure of
200 atm [3]. At these conditions a single pass results in a conversion of approximately 15% (varying
largely by different conditions), however by continually recycling the unreacted nitrogen and
hydrogen (as demonstrated in the BFD in fig. 1), the overall conversion is about 98%.

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Currently the bespoke reactor designed for the demonstration produces approximately 30 kg/d of
ammonia. The ammonia is combusted with the electrical energy fed back into the grid via a three-
cylinder spark ignition 30 kW electric generator.

2 Block Flow Diagram of Green Ammonia Process

Figure 1. BFD of ammonia synthesis

3 Preliminary Selection of Materials for Construction

For preliminary selection of materials, it is imperative that corrosion is one of the largest
contributing factors as to what materials are considered in construction.

Table 1. Material selection for equipment and related chemicals [4]

Equipment Chemical Material Selection Comment
PSAAS Oxygen Stainless Steel 304 Limited oxidation up to
Nitrogen 816°C (max temp. 450°C)
PEM Electrolyser Water (liquid) Ruthenium species with Rate of ammonia synthesis
Hydrogen graphite catalyst bed for is approximately 50%
Oxygen ammonia synthesis3. higher when compared to
Membrane: Nafion 117 other catalysts.
Cathode: Pt or Pt/C
Anode: Ir, Ru, Pt (oxide
based)
Gas Holder Nitrogen Carbon Steel ASTM A 387 Hydrogen can lead to
Hydrogen Grade 22 blistering and
embrittlement of steel.
Additionally, it readily
combines with other
elements to form
corrosive compounds.

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 Haber-Bosch Nitrogen (gas) AISI 321 Stainless Steel Stabilised by Titanium and
Reactor1, 2 Hydrogen (gas) Internal lining of Inconel is resistant to carbide
Ammonia (gas) 600 precipitation – causing
embrittlement of
materials.
Inconel 600 is not
susceptible to nitriding
(formation of nitride layer)
and provides protection
against high temperature
hydrogen attacks.
Pipework1 Nitrogen AISI 430 Stainless Steel Less prone to leaking.
Oxygen
Hydrogen
Water (liquid)
Ammonia (gas,
liquid)
Ammonia Storage Ammonia AISI 316 Stainless Steel Condensed ammonia in an
Tank1 (liquid) anhydrous state can cause
stress-corrosion cracking
of stressed carbon steels
or high-strength, low-alloy
steels.
Not corrosive to 304L or
316 SS.
Notes:

1. Non-corrosive storage containers – anhydrous ammonia will corrode copper, zinc, aluminium
and tin and any alloys which contain these metals. Zinc is generally used to galvanise steel and as
such, galvanised steel containers and pipes cannot be used. Materials of construction for
ammonia are usually dependent on operating temperatures. In this case stainless steel was the
material chosen for sections involving ammonia. It is important to note that impurities such as
air or carbon dioxide in liquid ammonia can cause stress corrosion or cracking of mild steel.
2. At high temperatures ammonia a high potential for nitriding metals and at high pressures form
corrosive ammonium carbamate. Medium and high strength steels are prone to cracking at low
or moderate temperatures in the presences of hydrogen.
3. The catalyst is designed by using sub-nano Ruthenium (Ru) particles on high surface area
graphite (HSAG) [5]. Ru3(CO)12 is adsorbed onto the surface of HSAG via CO groups in the
Ruthenium molecule and oxygen at the surface groups on HSAG.

4 Other Energy Storage Options

4.1 Lithium Ion Batteries

As shown in fig. 1, at the end of the BFD the ammonia is burnt in an electric generator and therefore
instead of sending the electricity back into the grid it could be stored in rechargeable lithium-ion
batteries or cells. This would allow the energy to be stored and transported with ease and
introduced into systems which do not requires large amounts of non-renewable energies to operate
(e.g. coal, oil, LNG, etc.).

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4.2 Hydrogen Fuel Cells

Hydrogen, in its elemental state, is difficult to store and transport and as such ammonia is often
referred to as “other hydrogen” due to its triple hydrogens and single nitrogen and relative ease to
store and transport, in comparison [6]. Hydrogen fuel cells are designed to take in hydrogen and
oxygen to produce energy and water vapour, however, even with hydrogens high energy density by
weight, large amounts are required to power systems such as a motor vehicle.

At low pressures ammonia gas becomes a liquid and becomes a good “carrier” of hydrogen.
Compressed hydrogen or liquid hydrogen contains less hydrogen by volume than liquid ammonia –
which is approximately 50% more energy dense per unit volume than liquid hydrogen. Therefore,
liquid ammonia can be stored and distributed easier than elemental hydrogen, hence fuel stations
are will become much easier to convert to dispensing ammonia than hydrogen [6]. Additionally,
ammonia can be readily stored onboard a vehicle in which the hydrogen and nitrogen are separated
just before the hydrogen is fed into the fuel cell – expelling nitrogen gas into the atmosphere and
producing water from hydrogen combustion.

There are several fuel cells designed to use ammonia directly, in addition to hydrogen fuel cells. This
would eliminate the need to separate the ammonia into its hydrogen and nitrogen elements before
it is used in the fuel cell, in which the conversion of ammonia to electric power enables high
efficiency.

4.3 Other uses of Ammonia

The combustion of ammonia produces nitrogen and water vapour (2), which provides cleaner
alternative to petroleum and diesel internal combustion engines.

4𝑁𝐻3 (𝑔) + 3𝑂2 (𝑔) → 2𝑁2 (𝑔) + 6𝐻2 𝑂(𝑔) (2)

Ammonia can be used in converted internal combustion engines as is already has a high-octane
rating of about 120 compared to petrol at 91-95 [6]. Therefore, an octane enhancer is not required,
and it can be used in high compression engines. Complimentary to hydrogen, ammonia is the only
fuel that has zero carbon emissions when combusted as it doesn’t contain carbon, however
compared to petrol, ammonia has relatively low energy density per unit volume (approximately half
that of petroleum) [6].

5 Improvements for Commerciality

Capital equipment such as the Haber-Bosch process should be able to run 24 hours, 365 days of the
year continuously, as stated in the article. Having electrolysers sitting around waiting for "negative
load" would be expensive. Additionally, the hydrogen could be stored and size the ammonia plant
for continual operation. Eliminating the intermittent energy of which renewable energies provide,
particularly in this process. Improving the process so it runs continually, whether that is through the
form of stored renewable energy reserves or more forms of renewable energy contributing to the
energy input.

Ammonia is perhaps the best choice for a synthetic fuel, particularly since it is also used for
agriculture, in homes as a zero-carbon emission fuel, and as a feedstock in the chemical industry.
The sulphur-iodine cycle may be a better way to liberate hydrogen for ammonia production.

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Typically, it is an iron catalyst used in the PEM electrolyser, however (as mentioned earlier)
Ruthenium species with graphite catalyst bed for ammonia synthesis is looking to be a more
promising catalyst – in conjunction with both magnesium and aluminium oxide. However, under
laboratory conditions the synthesisation of ammonia best occurs via the hydrolysis of a metal nitride
(3), e.g. Magnesium Nitride:

4𝑀𝑔3 𝑁2 + 6𝐻2 𝑂 → 2𝑁𝐻3 + 3𝑀𝑔(𝑂𝐻)2 (3)

6 Summary

 Clean (renewable energy) is used to run the PEM electrolyser and possibly the PSAAS too.
 Intermittent renewable energy is the bottleneck for continuous operation of the Haber-
Bosch process. Ideas of hydrogen fuel cells or stored energy could be methods to combat
this issue.
 For most of the materials suggested in the construction of the green ammonia process, they
are largely corrosive resistant including carbon steel, and stainless steel 304/316/321. These
materials are for the construction of the PSAAS, gas holder, reactor, ammonia storage tanks
and piping.
 Hydrogen fuel cells and ammonia as a synthetic fuel are two key avenues of technology
which needs to be explored as the technology for green ammonia is developed further.
 A major point to improve commercialising the process is to use the Ruthenium species with
graphite catalyst bed for ammonia synthesis, in the PEM electrolyser.

7 References

[1] Duckett, A., Green ammonia project launched, in The Chemical Engineer. 2018. p. 12.
[2] Carmo, M., et al., A comprehensive review on PEM water electrolysis. International Journal of
Hydrogen Energy, 2013. 38(12): p. 4901-4934. DOI: 10.1016/j.ijhydene.2013.01.151
[3] Clark, J. The Haber Process. 2013; Available from:
https://www.chemguide.co.uk/physical/equilibria/haber.html
[4] Kobrin, G., Stainless Steels in Ammonia Production, A.I.a.S. Institute, Editor. 1978.
[5] Wenfeng, H., Strong Interaction of Ruthenium Species with Graphite Structure for the Self-
Dispersion of Ru under Solvent-Free Conditions. ACS Sustainable Chemistry & Engineering,
2017. 5(8): p. 7195-7202. DOI: 10.1021/acssuschemeng.7b01413
[6] Hofstrand, D. Ammonia as a Transportation Fuel. 2009; Available from:
https://www.agmrc.org

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