September 2015

Green Ammonia
Tim Hughes1, Ian Wilkinson1, Edman Tsang2, Ian McPherson2, Tim Sudmeier2, Josh Fellowes 2
Fenglin Liao2, Simson Wu2, ,Augustin Valera-Medina3, Sebastian Metz4
1 Siemens Corporate Technology, 2University of Oxford, 3 University of Cardiff ,4 STFC

.
 I Strategic Direction

II Green Ammonia Economy

III Carbon Free Ammonia Synthesis

IV Carbon Free Energy Conversion

V Ammonia Energy Systems

Page 2 March 2016

 The changing Energy Landscape
Different solutions for different market stages

Energiewende 2.0

<10% 20+% 40+% 60+% 80+%

Traditional mix System integration Market integration Regional Decoupled generation

autonomous system and consumption
Fossil (coal, gas, oil) Fossil (coal, gas, oil) Capacity markets etc. Predictable regional area Interaction of all energy
Nuclear Renewables (wind, PV, generation (topological carriers
Renewables (mainly hydro) hydro) plants)

Efficiency Decreasing spot market Power2Heat, CHP Regional plants, cellular Complete integration of
LCC reduction prices increasing grids decentralized power
Availability / reliability / Subsidized economy Demand side HVDC overlay and generation
security Increasing redispatch1) management meshed AC/DC systems Storage systems/
operation First storage solutions Power2Chem / Return of gas power
HVDC/AC overlay Stability challenge plants?
Past Today Mid-term Long-term

Fierce competition in traditional businesses, need to set benchmark in new or changed markets
Profitable business for new technologies cannot be shown yet todays use cases are mainly niche or pilot applications

1) Corrective action to avoid bottlenecks in power grid

Page 3 March 2016

Large Scale storage and demand side solutions will
be required

Page 4 March 2016

Energy storage indispensible in future ecosystem
enables customers to cope with arising challenges

Future power ecosystem and customer challenges and storage opportunities

Renewables Power to heat Power to

CHP Power to power
Generation storage chemicals
On off shore wind Distributed generation High temperature heat Chemical feedstock Batteries
Photo-voltaics <5MW pumps Green Fuel Fuel cells
Multi-fuel capability Green Fuel
biogas, ethanol Demand side
Supply side Demand side Supply & demand
management
management Supply side management side management
management

Page 5 March 2016

 I Strategic Direction

II Green Ammonia Economy

III Carbon Free Ammonia Synthesis

IV Carbon Free Energy Conversion

V Ammonia Energy Systems

Page 6 March 2016

The chemical industry faces significant challenges

The chemicals industry is a vital part of modern life

e.g. Fertilisers for food, steel processing, plastics and so on.

It is dependent on hydrocarbons for raw materials and energy for production.

The chemical industry therefore faces significant challenges:

Growing carbon emissions
Finite resources
Security of supply for both energy and raw materials

These large challenges represent an opportunity through

electrification of the chemical industry.

Page 7 March 2016

The existing chemical industry emissions conflict
with initiatives to avoid climate change

Chemical Industry Emissions Climate Act Requirements

1255 MT/yr CO21

UK target of 80% cut in

4% world total2 emissions by 2050

1.1TW 1 EU wide target of 40% cut in

emissions by 2030
8.2% world total2

Opportunity: carbon free synthesis of chemicals powered by renewable

energy

Ammonia: 1.8% of the world consumption of fossil energy goes into the
production of ammonia. 90% of ammonia production is based on natural gas.
Top 10 Chemicals / Processes: 4) Methanol 8) Butadiene (C4 sep.)
1) Steam cracking 5) Butylene 9) Soda ash
2) Ammonia 6) Propylene FCC 10) Carbon black
3) Aromatics extraction 7) Ethanol

1) Chemical and Petrochemical Sector IEA2009 2) Key World Energy Statistics IEA2014
Page 8 March 2016
Ammonia is an important chemical with a commodity
market value of EUR100bn/year

A gas, produced by the chemical industry. Over 80% of ammonia is

used in the fertiliser industry.
Demand for fertiliser, as shown in the graph (including projected
growth to 2018), is growing at +3%pa1.
Ammonia Current production levels of Ammonia are about 180m t/year. The
commodity value is 600-700/t, leading to a commodity market value
of over 100bn/year
Production today uses the Haber-Bosch process and relies on natural
gas as a feedstock.

Global fertilizer nutrient consumption

210 200.522
200 193.882
186.895
190 180.079
Million MT

197.19
180 170.845 190.732
170 161.829 183.175
176.784
160
150 161.659
2008 2009 2010 2011 2012 2013 2014 2015 2016 2017 2018
Source: World Fertilizer Trends and Outlook to 2018, Food and Agriculture Organization
of the United Nations
Page 9 March 2016
Ammonia is also a viable fuel or hydrogen carrier

Page 10 March 2016

With renewable energy, the ammonia cycle is carbon
free

N2 from air Water Renewable Electricity

+ +

Electrochemically
Produced Ammonia

Page 11 March 2016

Opportunity exists in technology for ammonia
synthesis and power conversion

N2 from air Water Renewable Electricity

+ +

Ammonia
Ammonia
Power
Synthesizer Electrochemically Conversion
Technology Produced Ammonia Technology

Ammonia Storage
Technology

Page 12 March 2016

 Ammonia Innovation Landscape

DISRUPTIVE ARCHITECTURAL
Business Models
Leverages New

Develops Ammonia Energy System

based on gas turbines Develops Flexible Ammonia System

2 4
Ammonia used as an energy storage medium for based on membrane technology
grid scale chemical energy storage over long time Flexible bi-directional Ammonia Systems
periods supply energy, fuel or chemical on demand
Ammonia used as a fuel for Mobility

ROUTINE RADICAL
Leverages Existing
Business Models

Develop Develops Electrochemical Ammonia

Agile Haber Bosch product

1 3
based product:
Electrification of thermochemical production
route to service the existing fertilizer and
chemical industries
All electric membrane based electrochemical
technology for the direct production of
ammonia for the existing fertilizer and
chemical industries

Leverages Existing Technologies Requires New Technologies

Page 13 March 2016

Innovation Landscape Map Source: Harvard Business Review, June 2015
Green Ammonia Carbon Free Flexible Asset

Distributed Chemical Grid Scale Energy Storage

Industry

Ammonia Ammonia
Synthesizer NH3 Synthesizer NH3
Turbine

Emission Free Transportation

Ammonia
Synthesizer NH3

Page 14 March 2016

Business potential for 3 markets, based on common
technology platform

Ammonia as a
Energy Storage at Grid Transport Fuel
level

Chemical Industry:
Ammonia as a commodity; for
instance, use in fertiliser

Page 15 March 2016

 I Strategic Direction

II Green Ammonia Economy

III Carbon Free Ammonia Synthesis

IV Carbon Free Energy Conversion

V Ammonia Energy Systems

Page 16 March 2016

Ammonia Production Today

Typical ammonia plant today1

Ammonia conversion
and separation here!

N2 + 3H2 2NH3
Gas preparation: significant portion
of plant exists to produce H2
1) Courtesy of Johnson Matthey
Page 17 March 2016
Ammonia Production 2020

Typical ammonia plant in near future

Ammonia conversion
and separation here!

Hydrogen H2
H 2O
Electrolyser

air Air Separation N2

Unit

N2 + 3H2 2NH3
Gas preparation: ultra pure Syngas
from water electrolysis and air
separation unit
Page 18 March 2016
Ammonia Production 2030

N2 + 3H2O 2NH3+3/2O2

Ammonia NH3
H 2O
Electrolyser

air Air Separation

Unit
N2
Direct electrochemical synthesis of
Ammonia from water and nitrogen

Page 19 March 2016

Electrolysis of Ammonia 4 focus areas

Page 20 March 2016

 Molten Salt Approach

Stability of N3- in metal halide salts allows

direct reduction of N2 to N3- at ambient
pressure

Applied voltage causes migration of N3- from

surface of negative electrode to surface of
positive electrode

Facile dissociation of H2 occurs on positive

electrode to generate surface H
Surface N and H combine to produce
ammonia

Equivalent to high pressures used in thermal

route

Page 21 March 2016

 Challenges for molten salt approach

Providing correct ratio of N and H at the surface of the positive electrode to ensure:

N,H combination outcompetes N,N recombination

Formation rate is not slowed down waiting for H

High energy barrier for N2 reduction to N3-

Excess voltage over thermodynamic value required for appreciable rates

Solubility of NH3 in molten salt/stability of LiNH2

Page 22 March 2016

 Molten Salt Experimental Program
Temperature and
Gas Flow Control

Reactor
Outlet gas analysed
by gas
chromatography

Furnace

Gas supplied to
porous electrodes
(orange and green
tubes) 100 mL molten salt
held in crucible

Page 23 March 2016

 Solid Electrolyte Ammonia Electrolysis

Electrolyte Cathode
Anode
Proton conducting Reduction of nitrogen
Oxidation of hydrogen
Electrically insulating Formation of ammonia
Electrically conducting
Proton conducting Electrically conducting
Proton conducting

Page 24 March 2016

In order to be a viable product Green Ammonia
must be cost effective vs Conventional Ammonia

Green
Ammonia

Page 25 March 2016

 I Strategic Direction

II Green Ammonia Economy

III Carbon Free Ammonia Synthesis

IV Carbon Free Energy Conversion

V Ammonia Energy Systems

Page 26 March 2016

Ammonia as a fuel possible due to key properties of
energy density and logistics

Ammonia has a power density similar to NH3 can be transported easily at low
fossil fuels, with zero carbon in it. pressures.

Ammonia is a good energy vector

Page 27 March 2016

There exist several routes for Ammonia as an energy
vector

Ammonia

Ammonia
Ammonia
Combustion
Electrochemical

Ammonia
Ammonia Ammonia Ammonia
Internal
Combustion Gas Turbines PEM Fuel cell SOFC

Page 28 March 2016

Ammonia as a Fuel

Ammonia combustion has the following challenges

Slow chemical kinetics

Unstable regimes when burned

High NOx emissions

High toxicity for humans and living organisms

A new program of research has been started to use ammonia as fuel for
power generation at large scale. The aim is to develop a highly efficient ultra
low emissions gas turbine combustor fuelled by ammonia.

Page 29 March 2016

 Ammonia Gas Turbine Development

Evaluation of current reaction

models to determine accuracy
and restrictions.

Modelling of generic swirl

burners through CFD studies to
Comparison between models
study combustion and emission
Generic burner, high pressure.
and trials. patterns.

Recommendation of first ideas

for technology improvement:
stratified injection.

Lab combustor. Thermoacoustics. CFD model using NH3-CH4

with GRI-Mech
Page 30 March 2016
Ammonia Gas Turbine Development

Retrofitting of gas turbine

combustion facilities for
ammonia tests.
Experimental evaluation of
methane-ammonia blends
to understand NH3
injection challenges.
Recognition of unstable
combustion with ammonia
blends.
Recognition of low NOx
emissions from high
equivalence ratio
A) OH* chemiluminescence, mean values out of 200 images. conditions.
B) Normalized intensity of mean values using results at 0.8
E.R.-1 Bar.

Page 31 March 2016

Ammonia Gas Turbine Development Future Work

Development of new stratified

injection techniques for H2-NH3
injection.

Development of new reaction

models for H2-NH3 blends at high
temperature/high pressure.

Thermoacoustic studies for flame

stability (OSCILOS FFT).

Thermodynamic characterisation of
GT cycle using H2-NH3 blends.

Gas turbine combustor development

Thermoacoustic analysis using 3D Printing.
GT Cycle comparative (CH4) (OSCILOS CH4)

Page 32 March 2016

 I Strategic Direction

II Green Ammonia Economy

III Carbon Free Ammonia Synthesis

IV Carbon Free Energy Conversion

V Ammonia Energy Systems

Page 33 March 2016

Decoupling Green Energy: green ammonia
synthesis and energy storage system demonstrator

Being built at Rutherford Appleton

Laboratory, near Oxford, UK.
Project 50% supported by Innovate UK
(UK government funding agency).

Evaluation of all-electric
synthesis and energy
storage demonstration
system by Dec 2017.

Page 34 March 2016

 Site layout

Combustion
Hydrogen electrolysis and energy
and ammonia synthesis export

Nitrogen
generator

Gas store, including

ammonia tank

Wind turbine and Control room

grid connection

Page 35 March 2016

Harwell Ammonia energy storage
system demonstrator

NH3 H-B
Reactor
(Bespoke)

Page 36 March 2016

 System demonstrator technology development

Haber-Bosch synthesis catalyst Ammonia combustion studies

Energy management
Control system
system

Page 37 March 2016

Contacts

Tim Hughes
timothy.hughes@siemens.com

Page 38 March 2016