September 2015 Green Ammonia Tim Hughes 1, Ian Wilkinson 1, Edman Tsang 2, Ian McPherson 2, Tim Sudmeier 2, Josh Fellowes 2 Fenglin Liao 2, Simson Wu 2,,Augustin Valera-Medina 3, Sebastian Metz 4 1 Siemens Corporate Technology, 2 University 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
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 autonomous system Decoupled generation and consumption 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 Efficiency LCC reduction Availability / reliability / security Decreasing spot market prices Subsidized economy Increasing redispatch 1) 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? 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 today s use cases are mainly niche or pilot applications 1) Corrective action to avoid bottlenecks in power grid Page 3
Large Scale storage and demand side solutions will be required Page 4
Energy storage indispensible in future ecosystem enables customers to cope with arising challenges Future power ecosystem and customer challenges and storage opportunities Renewables Generation CHP Power to heat storage Power to chemicals Power to power On off shore wind Photo-voltaics Supply side management Distributed generation <5MW Multi-fuel capability biogas, ethanol Supply side management High temperature heat pumps Demand side management Chemical feedstock Green Fuel Demand side management Batteries Fuel cells Green Fuel Supply & demand side management Page 5
I Strategic Direction II Green Ammonia Economy III Carbon Free Ammonia Synthesis IV Carbon Free Energy Conversion V Ammonia Energy Systems Page 6
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
The existing chemical industry emissions conflict with initiatives to avoid climate change Chemical Industry Emissions Climate Act Requirements 1255 MT/yr CO 1 2 è 4% world total 2 1.1TW 1 è 8.2% world total 2 UK target of 80% cut in emissions by 2050 EU wide target of 40% cut in emissions by 2030 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: 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 Page 8 1) Chemical and Petrochemical Sector IEA2009 2) Key World Energy Statistics IEA2014
Ammonia is an important chemical with a commodity market value of EUR100bn/year Ammonia 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%pa 1. 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 Page 9 Million MT 210 200 190 180 170 160 150 161.829 161.659 170.845 176.784 180.079 183.175 186.895 190.732 193.882 197.19 200.522 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
Ammonia is also a viable fuel or hydrogen carrier Page 10
With renewable energy, the ammonia cycle is carbon free N 2 from air Water Renewable Electricity + + = Electrochemically Produced Ammonia Page 11
Opportunity exists in technology for ammonia synthesis and power conversion N 2 from air Water Renewable Electricity + + Ammonia Synthesizer Technology Electrochemically Produced Ammonia Ammonia Power Conversion Technology Ammonia Storage Technology Page 12
Ammonia Innovation Landscape DISRUPTIVE ARCHITECTURAL Leverages New Business Models 2 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 4 Develops Flexible Ammonia System based on membrane technology Flexible bi-directional Ammonia Systems supply energy, fuel or chemical on demand ROUTINE RADICAL Leverages Existing Business Models 1 Develop Agile Haber Bosch based product: Electrification of thermochemical production route to service the existing fertilizer and chemical industries 3 Develops Electrochemical Ammonia product 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 Innovation Landscape Map Source: Harvard Business Review, June 2015
Green Ammonia Carbon Free Flexible Asset Distributed Chemical Industry Grid Scale Energy Storage Ammonia Synthesizer NH 3 Ammonia Synthesizer NH 3 Turbine Emission Free Transportation Ammonia Synthesizer NH 3 Page 14
Business potential for 3 markets, based on common technology platform Energy Storage at Grid level Ammonia as a Transport Fuel Chemical Industry: Ammonia as a commodity; for instance, use in fertiliser Page 15
I Strategic Direction II Green Ammonia Economy III Carbon Free Ammonia Synthesis IV Carbon Free Energy Conversion V Ammonia Energy Systems Page 16
Ammonia Production Today Typical ammonia plant today 1 Ammonia conversion and separation here! N 2 + 3H 2 à 2NH 3 Gas preparation: significant portion of plant exists to produce H2 1) Courtesy of Johnson Matthey Page 17
Ammonia Production 2020 Typical ammonia plant in near future Ammonia conversion and separation here! H 2 O Hydrogen Electrolyser H 2 air Air Separation N 2 Unit N 2 + 3H 2 à 2NH 3 Gas preparation: ultra pure Syngas from water electrolysis and air separation unit Page 18
Ammonia Production 2030 N 2 + 3H 2 O à 2NH 3 +3/2O 2 H 2 O Ammonia Electrolyser NH 3 air Air Separation Unit N 2 Direct electrochemical synthesis of Ammonia from water and nitrogen Page 19
Electrolysis of Ammonia 4 focus areas Page 20
Molten Salt Approach Stability of N 3- in metal halide salts allows direct reduction of N 2 to N 3- at ambient pressure Applied voltage causes migration of N 3- from surface of negative electrode to surface of positive electrode Facile dissociation of H 2 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
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 N 2 reduction to N 3- Excess voltage over thermodynamic value required for appreciable rates Solubility of NH 3 in molten salt/stability of LiNH 2 Page 22
Molten Salt Experimental Program Temperature and Gas Flow Control Outlet gas analysed by gas chromatography Reactor Furnace Gas supplied to porous electrodes (orange and green tubes) Page 23 100 ml molten salt held in crucible
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 Page 24
In order to be a viable product Green Ammonia must be cost effective vs Conventional Ammonia Green Ammonia Page 25
I Strategic Direction II Green Ammonia Economy III Carbon Free Ammonia Synthesis IV Carbon Free Energy Conversion V Ammonia Energy Systems Page 26
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 Page 27
There exist several routes for Ammonia as an energy vector Ammonia Ammonia Combustion Ammonia Electrochemical Ammonia Internal Combustion Ammonia Gas Turbines Ammonia PEM Fuel cell Ammonia SOFC Page 28
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
Ammonia Gas Turbine Development Evaluation of current reaction models to determine accuracy and restrictions. Generic burner, high pressure. Comparison between models and trials. Modelling of generic swirl burners through CFD studies to study combustion and emission patterns. Recommendation of first ideas for technology improvement: stratified injection. Lab combustor. Thermoacoustics. CFD model using NH 3 -CH 4 with GRI-Mech Page 30
Ammonia Gas Turbine Development A) OH* chemiluminescence, mean values out of 200 images. B) Normalized intensity of mean values using results at 0.8 E.R.-1 Bar. 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. Page 31
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. GT Cycle comparative (CH4) Thermoacoustic analysis (OSCILOS CH4) Gas turbine combustor development using 3D Printing. Page 32
I Strategic Direction II Green Ammonia Economy III Carbon Free Ammonia Synthesis IV Carbon Free Energy Conversion V Ammonia Energy Systems Page 33
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
Site layout Hydrogen electrolysis and ammonia synthesis Combustion and energy export Nitrogen generator Gas store, including ammonia tank Wind turbine and grid connection Control room Page 35
Harwell Ammonia energy storage system demonstrator NH 3 H-B Reactor (Bespoke) Page 36
System demonstrator technology development Haber-Bosch synthesis catalyst Energy management system Page 37 Ammonia combustion studies Control system
Contacts Tim Hughes timothy.hughes@siemens.com Page 38