green ammonia siemens oxford cardiff
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Green Ammonia September 2015
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
March 2016 Page 2
I Strategic Direction
II Green Ammonia Economy
III Carbon Free Ammonia Synthesis
IV Carbon Free Energy Conversion
V Ammonia Energy Systems
March 2016 Page 3
The changing Energy Landscape Different solutions for different market stages
Past Today Mid-term Long-term
<10% 20+% 40+% 60+% 80+%
– Efficiency – LCC reduction – Availability / reliability /
security
– Decreasing spot market prices
– Subsidized economy – Increasing redispatch1)
operation
– Power2Heat, CHP increasing
– Demand side management
– First storage solutions – HVDC/AC overlay
– Regional plants, cellular grids
– HVDC overlay and meshed AC/DC systems
– Power2Chem / – Stability challenge
– Complete integration of decentralized power generation
– Storage systems/ – Return of gas power
plants?
– Fossil (coal, gas, oil) – Nuclear – Renewables (mainly hydro)
– Fossil (coal, gas, oil) – Renewables (wind, PV,
hydro)
– Capacity markets etc. – Predictable regional “area generation” (topological plants)
– Interaction of all energy carriers
Traditional mix System integration Market integration Regional autonomous system
Decoupled generation and consumption
Fierce competition in traditional businesses, need to set benchmark in new or changed markets Profitable business for new technologies cannot be shown yet – today’s use cases are mainly niche or pilot applications
Energiewende 2.0
1) Corrective action to avoid bottlenecks in power grid
March 2016 Page 4
Large Scale storage and demand side solutions will be required
March 2016 Page 5
Energy storage indispensible in future ecosystem – enables customers to cope with arising challenges
Future power ecosystem and customer challenges and storage opportunities
Supply side management
• On – off shore wind • Photo-voltaics
Renewables Generation
Supply side management
• Distributed generation <5MW
• Multi-fuel capability – biogas, ethanol
CHP
Demand side management
• High temperature heat pumps
Power – to – heat storage
Demand side management
• Chemical feedstock • Green Fuel
Power – to – chemicals Power – to – power
Supply & demand side management
• Batteries • Fuel cells • Green Fuel
March 2016 Page 6
I Strategic Direction
II Green Ammonia Economy
III Carbon Free Ammonia Synthesis
IV Carbon Free Energy Conversion
V Ammonia Energy Systems
March 2016 Page 7
The chemical industry faces significant challenges
§ Growing carbon emissions
§ Finite resources
§ Security of supply for both energy and raw materials
The chemical industry therefore faces significant challenges:
These large challenges represent an opportunity through electrification of the chemical industry.
It is dependent on hydrocarbons for raw materials and energy for production.
The chemicals industry is a vital part of modern life – e.g. Fertilisers for food, steel processing, plastics and so on.
March 2016 Page 8
The existing chemical industry emissions conflict with initiatives to avoid climate change
1) Chemical and Petrochemical Sector – IEA2009 2) Key World Energy Statistics – IEA2014
Chemical Industry Emissions
1255 MT/yr CO21
è 4% world total2
1.1TW 1
è 8.2% world total2
UK target of 80% cut in emissions by 2050
EU wide target of 40% cut in emissions by 2030
Climate Act Requirements
≠
Top 10 Chemicals / Processes: 1) Steam cracking 2) Ammonia 3) Aromatics extraction
4) Methanol 5) Butylene 6) Propylene FCC 7) Ethanol
8) Butadiene (C4 sep.) 9) Soda ash 10) Carbon black
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.
Opportunity: carbon – free synthesis of chemicals powered by renewable energy
March 2016 Page 9
Ammonia is an important chemical with a commodity market value of EUR100bn/year
Source: World Fertilizer Trends and Outlook to 2018, Food and Agriculture Organization of the United Nations
Global fertilizer nutrient consumption
161.829
161.659
170.845
176.784
180.079
183.175
186.895
190.732
193.882
197.19
200.522
150 160 170 180 190 200 210
2008 2009 2010 2011 2012 2013 2014 2015 2016 2017 2018
Mill
ion
MT
§ 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.
§ 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.
Ammonia
March 2016 Page 10
Ammonia is also a viable fuel – or hydrogen carrier
March 2016 Page 11
With renewable energy, the ammonia cycle is carbon free
Electrochemically Produced Ammonia
+ + Water N2 from air Renewable Electricity
=
March 2016 Page 12
Opportunity exists in technology for ammonia synthesis and power conversion
Ammonia Synthesizer Technology
Ammonia Power
Conversion Technology
Ammonia Storage Technology
Electrochemically Produced Ammonia
+ + Water N2 from air Renewable Electricity
March 2016 Page 13
Ammonia Innovation Landscape
Innovation Landscape Map Source: Harvard Business Review, June 2015
Leverages Existing Technologies Requires New Technologies
Leve
rage
s Ex
istin
g B
usin
ess
Mod
els
Leve
rage
s N
ew
Bus
ines
s M
odel
s
DISRUPTIVE
ROUTINE RADICAL
ARCHITECTURAL
Develops Flexible Ammonia System based on membrane technology
Flexible bi-directional Ammonia Systems supply energy, fuel or chemical on demand
Develops Electrochemical Ammonia product
All electric membrane based electrochemical technology for the direct production of ammonia for the existing fertilizer and
chemical industries
Develops Ammonia Energy System based on gas turbines
Ammonia used as an energy storage medium for grid scale chemical energy storage over long time
periods
Ammonia used as a fuel for Mobility
Develop Agile Haber Bosch
based product: Electrification of thermochemical production
route to service the existing fertilizer and chemical industries
1
2
3
4
March 2016 Page 14
Green Ammonia – Carbon Free Flexible Asset
Ammonia Synthesizer NH3
Distributed Chemical Industry
Grid Scale Energy Storage
Ammonia Synthesizer NH3
Emission Free Transportation
Ammonia Synthesizer NH3
Turbine
March 2016 Page 15
Chemical Industry: Ammonia as a commodity; for
instance, use in fertiliser
Energy Storage at Grid level
Ammonia as a Transport Fuel
Business potential for 3 markets, based on common technology platform
March 2016 Page 16
I Strategic Direction
II Green Ammonia Economy
III Carbon Free Ammonia Synthesis
IV Carbon Free Energy Conversion
V Ammonia Energy Systems
March 2016 Page 17
Typical ammonia plant today1
Ammonia Production Today
Ammonia conversion and separation here!
Gas preparation: significant portion of plant exists to produce H2
1) Courtesy of Johnson Matthey
N2 + 3H2 à 2NH3
March 2016 Page 18
Typical ammonia plant in near future
Ammonia Production 2020
Ammonia conversion and separation here!
Gas preparation: ultra pure Syngas from water electrolysis and air separation unit
Hydrogen
Electrolyser
Air Separation
Unit
H2O H2
air N2
N2 + 3H2 à 2NH3
March 2016 Page 19
Ammonia Production 2030
Direct electrochemical synthesis of Ammonia from water and nitrogen
Ammonia
Electrolyser
Air Separation
Unit
H2O NH3
air
N2
N2 + 3H2O à 2NH3+3/2O2
March 2016 Page 20
Electrolysis of Ammonia – 4 focus areas
March 2016 Page 21
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
March 2016 Page 22
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
March 2016 Page 23
Molten Salt Experimental Program Temperature and Gas Flow Control
Furnace
Outlet gas analysed by gas chromatography
Reactor
Gas supplied to porous electrodes (orange and green tubes) 100 mL molten salt
held in crucible
March 2016 Page 24
Solid Electrolyte Ammonia Electrolysis
Anode • Oxidation of hydrogen • Electrically conducting • Proton conducting
Electrolyte ◦ Proton conducting ◦ Electrically insulating
Cathode ◦ Reduction of nitrogen ◦ Formation of ammonia ◦ Electrically conducting ◦ Proton conducting
March 2016 Page 25
In order to be a viable product – Green Ammonia must be cost effective vs Conventional Ammonia
Green Ammonia
March 2016 Page 26
I Strategic Direction
II Green Ammonia Economy
III Carbon Free Ammonia Synthesis
IV Carbon Free Energy Conversion
V Ammonia Energy Systems
March 2016 Page 27
Ammonia as a fuel possible due to key properties of energy density and logistics
Ammonia has a power density similar to fossil fuels, with zero carbon in it.
NH3 can be transported easily at low pressures.
Ammonia is a good energy vector
March 2016 Page 28
There exist several routes for Ammonia as an energy vector
Ammonia
Ammonia
Combustion
Ammonia
SOFC
Ammonia
Electrochemical
Ammonia
PEM Fuel cell
Ammonia
Internal Combustion
Ammonia
Gas Turbines
March 2016 Page 29
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.
March 2016 Page 30
• Evaluation of current reaction models to determine accuracy and restrictions.
• Modelling of generic swirl burners through CFD studies to study combustion and emission patterns.
• Recommendation of first ideas for technology improvement: stratified injection.
Comparison between models and trials. Generic burner, high pressure.
Ammonia Gas Turbine Development
Lab combustor. Thermoacoustics. CFD model using NH3-CH4 with GRI-Mech
March 2016 Page 31
• 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 conditions. A)OH*chemiluminescence,meanvaluesoutof200images.
B)Normalizedintensityofmeanvaluesusingresultsat0.8E.R.-1Bar.
Ammonia Gas Turbine Development
March 2016 Page 32
• 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 using 3D Printing. GT Cycle comparative (CH4)
Ammonia Gas Turbine Development – Future Work
Thermoacoustic analysis (OSCILOS –CH4)
March 2016 Page 33
I Strategic Direction
II Green Ammonia Economy
III Carbon Free Ammonia Synthesis
IV Carbon Free Energy Conversion
V Ammonia Energy Systems
March 2016 Page 34
• Being built at Rutherford Appleton Laboratory, near Oxford, UK.
• Project 50% supported by Innovate UK (UK government funding agency).
Decoupling Green Energy: “green” ammonia synthesis and energy storage system demonstrator
• Evaluation of all-electric synthesis and energy storage demonstration system by Dec 2017.
March 2016 Page 35
Site layout
Nitrogen generator
Hydrogen electrolysis and ammonia synthesis
Combustion and energy export
Gas store, including ammonia tank
Control room Wind turbine and grid connection
March 2016 Page 36
Harwell Ammonia energy storage system demonstrator
NH3 H-B Reactor
(Bespoke)
March 2016 Page 37
System demonstrator technology development
Ammonia combustion studies Haber-Bosch synthesis catalyst
Energy management system
Control system