Renewable NH3 and Direct NH3 Fuel Cells: Canadian R&D for Clean Distributed Electricity Generation Presented at 9 th Annual NH3 Fuel Conference San Antonio, TX Andrew McFarlan, Ph.D. October 1 2012
CanmetENERGY is the R&D branch of Natural Resources Canada, with headquarters and labs in Ottawa ON, and labs in Varennes QC and Devon AB Varennes, QC Devon, AB Ottawa, ON
Introduction Anhydrous ammonia (NH3), the chemical building block for nitrogen fertilizers, is also a carbon-free fuel. Considerable infrastructure is in place to transport and store NH3 due to its extensive use in agriculture. Direct NH3 fuel cells can potentially produce electric power and high grade heat (CHP) efficiently and with zero emissions Like hydrogen, NH3 can be produced from non-fossil renewable electricity sources (hydro, wind). NH3 production from renewable electricity, and NH3 as a renewable fuel is gaining attention worldwide, particularly in the Corn Belt of US Midwest.
Topics: Conventional NH3 production energy requirements and GHG emissions Direct NH3 fuel cell development at CanmetENERGY Direct fuelling of conventional SOFC s with NH3 NH3 as a carbon-free renewable fuel R&D needs and opportunities
Conventional (Fossil) NH3 Production ~200 million tonnes global capacity annually Production: 67% natural gas-based, 27% coal-based Use: >80% NH3 is used for fertilizer manufacture US imports >50% of its NH3 Canada exports ~50% of its NG to US Also, NH3 Production from NG or coal produces pure CO2 byproduct which lowers cost of large scale CCS and can be used for enhanced recovery of oil or coal-bed methane (NH3 from coal with CCS practiced commercially in Beulah N.Dakota since 2000) 5
NH3 Production from Natural Gas Reforming Energy input: 30 million scf NG per tonne NH3 (30 GJ/tonne NH3) CO2 Emissions: 1.8 tonnes CO2 per tonne NH3
Overall Efficiency and CO 2 Emissions During Production and Distribution of Hydrogen Energy Carriers (H. Anderson, World Hydrogen Energy Conference, Montreal, 2002) Conclusions drawn from studies done by Norsk Hydro: CO 2 capture and sequestration contributes only slightly to the losses in the full hydrogen value chain Central hydrogen and ammonia production seem to be the most efficient way to produce CO2-free energy carriers Ammonia infrastructure development is easier because truck transport is possible supply and demand will be in balance through time On site natural gas reforming and methanol steam reforming have highest CO 2 emissions
Direct NH3 Fuel Cells: Development of Proton- Conducting Ceramic FC Materials at CanmetENERGY
Direct NH3 Fuel Cells: What is the concept? Ammonia is catalytically decomposed to N 2 + H 2 at anode high temperature, low pressure favors equilibrium limited decomposition Protons transport across a solid proton conducting electrolyte. Removal of hydrogen at the anode drives decomposition reaction to completion. H 2 /air oxidation at the cathode provides chemical driving force for the fuel cell AND provides the heat of reaction for ammonia decomposition. Products of the fuel cell are nitrogen, water, electric power and heat. Fuel 2NH 3 N 2 + 3H 2 3H 2 6H + + 6e - N 2 Electrolyte H + H + H + H + Anode Load 6e - Overall: 2NH 3 + 3/2O 2 Air/Oxygen 3/2 O 2 3/2 O 3O 2-2 + 6e - 6H + + 3O 2-3H 2 O Cathode H 2 O N 2 + 3H 2 O
Direct NH3 Fuel Cells: Pt/BCGP/Pt Ammonia Single Cell Fuel Cell 90 Cell performance as a function of Pr concentration (700 C). Optimization at approximately Pr 0.05 (BaCe 0.8 Gd 0.15 Pr 0.05 ). Related to increased material density and decrease of cell unit volume. Optimal Power Density (mw/cm 2 ) 80 70 60 50 40 30 20 10 BCG First BCGP Optimal Pr Hydrogen Ammonia 0 0.00 0.02 0.04 0.06 0.08 0.10 0.12 Pr content Fuel Cells, volume 7, issue 4 (2007) 323.
Direct NH3 Fuel Cells: Power Density (mw/cm 2 ) Mixed ionic and electronic conducting anode 35 30 25 20 15 10 5 0 Pt anode NiO-BCE anode 0 20 40 60 80 100 120 140 Current Density (ma/cm 2 ) Cell was stable for over 500 h on ammonia fuel with very little degradation in performance. Voltage (V) 1.0 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0 NiO-BCE anode outperformed Pt anode in a BCGP electrolyte supported fuel cell at 600 C in NH 3 Single cell operating at: 100 ma and 46 mw 0 100 200 300 400 500 600 Time on stream (h)
Direct NH3 Fuel Cells In-house development of advanced proton conducting ceramic fuel cell electrode/electrolyte materials: Proton conducting ceramics allow lower operating temperatures in H2 and NH3 They are thermodynamically more efficient than oxygen ion conducting ceramics X-section of Samarium doped barium cerate (BCS) under scanning electron microscope shows a uniform and dense ~25 micron thickness electrolyte layer, supported by a porous 1 mm thickness anode composed of NiO-BCS cermet This single fuel cell exhibits correct material properties needed for producing a fuel cell stack.
Direct NH3 Fuel Cells: Testing NH3 on Conventional Precommercial SOFC Stacks at Acumentrics Canada
Acumentrics Canadian Division was established in 2007 at the Fuel Cell Research Centre in Kingston ON. CanmetENERGY partnered with them to do field testing of their stack using direct NH3 fuel. RP-20 500W SOFC systems at a well head in Texas (2012) Source: www.acumentrics.com
Direct NH3 Fuel Cells: Acumentrics SOFC Direct NH3 Field Test Objectives: Assess the technical feasibility of using ammonia as a direct fuel source in a SOFC micro CHP generator. Measure the long term stability and performance of the SOFC to see if the stack materials are degraded by direct NH3 fuel. Measure level of emissions, especially NOx in the stack effluent gas Determine the modifications required to a natural gas based system to allow it to operate on ammonia Acumentrics SOFC stack: 9x5 array of extruded tubes NiO/YSZ anode support YSZ electrolyte shell (air) side cathode nominal 1 kw output
Direct NH3 Fuel Cells: Acumentrics Custom SOFC Test Stand Startup Burner Fuel Cell Module Recuperator Stack/Hot Box Stack Anode Inlet Thermocouple/ Voltage Sense Leads Power Leads Test Stand
Direct NH3 Fuel Cells: Acumentrics SOFC Stack Under Test CPOX Polarization Data Current and Stack Temps During Test Average Stack Temp = 785 deg C 860 30 840 25 820 Temperature C Stack Current 800 780 760 20 15 10 Stack Current (Amps) 9 T206 Stack Bottom A 10 T207 Stack Bottom B 11 T208 Stack Bottom C 12 T209 Stack Middle A 13 T210 Stack Middle B 16 T213 Stack Top B 17 T214 Stack Top C Avg. Stack Temp Stack Amps 740 5 720 700 0 10/12/2008 14:09 10/12/2008 14:12 10/12/2008 14:15 10/12/2008 14:18 10/12/2008 14:21 10/12/2008 14:24 10/12/2008 14:26 10/12/2008 14:29 Date/Time Temperature profile for CPOX Polarization Curve
Direct NH3 Fuel Cells: Acumentrics SOFC Stack Under Test NH3 Polarization Data Current and Temperatures During Test Average Stack Temp = 835 deg C 860 30 840 25 820 Stack Temperatures (deg C) 800 780 760 20 15 10 9 T206 Stack Bottom A 10 T207 Stack Bottom B 11 T208 Stack Bottom C 12 T209 Stack Middle A 13 T210 Stack Middle B 16 T213 Stack Top B 17 T214 Stack Top C Avg Stack Temp Stack Amps 740 5 720 700 0 08/01/2009 13:13 08/01/2009 13:14 08/01/2009 13:16 08/01/2009 13:17 08/01/2009 13:19 08/01/2009 13:20 08/01/2009 13:22 Date/Time Temperature profile for NH3 Polarization Curve
Direct NH3 Fuel Cells: Acumentrics SOFC Stack Under Test 1 0.95 0.9 0.85 Volts/Cell (VDC) 0.8 0.75 0.7 y = -0.00145x + 1.01483 R 2 = 0.99876 V1 V2 V3 V4 V5 Vavg Linear (Vavg) 0.65 0.6 0.55 0.5 0 20 40 60 80 100 120 140 160 180 200 Current Density (ma/cm^2) NH3 Polarization Curve
Direct NH3 Fuel Cells: Acumentrics SOFC Stack Under Test CPOX Stack Temperatures @20A Average Delta T = 131C (Top to Bottom) 850 30 825 25 800 Stack Temperatures (deg C) 775 750 725 20 15 10 9 T206 Stack Bottom A 10 T207 Stack Bottom B 11 T208 Stack Bottom C 12 T209 Stack Middle A 13 T210 Stack Middle B 16 T213 Stack Top B 17 T214 Stack Top C Avg. Stack Temp Stack Amps 700 5 675 650 0 12:12 12:14 12:15 12:17 12:18 12:20 12:21 12:23 12:24 12:25 Date/Time CPOX (Natural Gas) Operation @20A
Direct NH3 Fuel Cells: Acumentrics SOFC Stack Under Test NH3 Stack Temperatures @ 20 Amps Average Delta T = 63C (Top to Bottom) 850 30 825 25 800 Stack Temperatures 775 750 725 20 15 10 9 T206 Stack Bottom A 10 T207 Stack Bottom B 11 T208 Stack Bottom C 12 T209 Stack Middle A 13 T210 Stack Middle B 16 T213 Stack Top B Avg Stack Temp Stack Amps 700 675 5 650 0 18:59 19:00 19:01 19:03 19:04 19:06 19:07 19:09 19:10 19:12 19:13 19:14 Time NH3 Operation @20A
Direct NH3 Fuel Cells: Acumentrics NH3 SOFC Field Test Knowledge Gained: Long term operation (~1400h) showed no adverse effects or drop off in stack performance for conventional SOFC. No residual NH 3, or NOx was detected in the stack effluent gas, or effectively zero emissions operating on ammonia. NH3 performance surpasses natural gas due to lower stack temperature gradient There is potential to simplify the system design considerably by using NH3, lowering cost to build the system Independently in 2010, Topsoe Fuel Cells (Denmark) presented similar findings using their near commercial SOFC s
Production and Use of Renewable Green NH3 NextHydrogen Study
NEXTHydrogen is a Canadian clean technology company who is developing MW scale electrolyzers as well as green applications of this technology NEXT HYDROGEN Economical Clean Hydrogen, at Scale Innovation in Water Electrolysis
Canadian Opportunity for Green NH3: NextHydrogen Study Renewable NH3 (by water electrloysis, air separation, Haber Bosch synthesis) from low cost hydroelectricity ($0.02/kWh -$0.35/kWh) can be competitive with fossil NH3 in the near future. Windfarms with low installed costs and good to very good wind availability may also compete. Renewable (green) NH3 addresses energy security for both energy and food production by reducing the industry s dependency on Canada s NG, heavy oil and coal resources. Green NH3 is an emerging decentralized (off grid) energy resource. It has the potential to reduce the GHG emissions related to fossil NH3 production. Demonstration ready technologies for using green NH3 as a fuel are available today. They include NH3 in internal combustion engines, and solid oxide fuel cell combined heat and power systems. NH3 production technology based on electrolysis is also at demo stage of development.
Economics of Natural Gas and Coal Based NH3 Production NH3 Cost $/tonne 1000 900 800 700 600 500 400 300 200 100 0 0 5 10 15 20 NG Cost $/MMBtu Fig.1 NG NG + $30/tonne CO2 NH3 Cost $/tonne 1000 900 800 700 600 500 400 300 200 100 0 Coal Coal + 30$//tonne CO2 0 50 100 150 Coal Cost $/tonne Fig.2 Fig.1 and Fig. 2 show that low-cost NG and/or coal based NH3 production remain economical for large scale production. Carbon Capture adds incrementally to production cost, more so for coal than NG.
Economics of Green NH3 NH3 Cost $/tonne 1000 900 Hydroelectricity 800 700 Hydrogen 600 500 400 300 200 100 0 0.00 1.00 2.00 3.00 4.00 Hydro, cents/kwh; Hydrogen, $/Kg Fig.3 Fig. 3 shows that renewable NH3 from low cost hydroelectricity ($0.02-$0.35 /kwh) can be competitive with fossil NH3 in the near future. Hydrogen costing $1.50-$2.50 /Kg from wind energy will also be competitive.
Economics of Green NH3 NH3 Cost $/tonne 1000 900 800 700 600 500 400 300 200 100 0 CP=0.45 CP=0.35 0 1000 2000 3000 4000 Windfarm Cost $/KW Fig.4 Fig. 4 shows the strong influence of wind farm installed cost and wind capacity factor (CP) on renewable NH3 cost. Wind farms require an installed cost approaching ~1000/kW, good wind (CP=0.35) or even very good wind (CP=0.45) to be competitive in today s NH3 market.
Next Steps Pursue renewable NH3 production and technology demonstration tailored to match economic advantages of a given region. Pursue new applications for green NH3, e.g. farm vehicles, SOFC for CHP and refrigeration in regions where existing NH3 infrastructure can be leveraged. Pursue R&D on proton conducting ceramic electrolyte materials for efficient solid state electrochemical synthesis of ammonia. Nurture emerging Canadian expertise and technology development in related areas, and strengthen linkages nationally and internationally with entities having similar interests. R&D to advance biomass gasification for green NH3
Potential for Green NH3 Production From Biomass Gasification ENERKEM (right) and NEXTERRA (below) are two Canadian companies who are developing syngas technologies based on biomass residues and MSW. These syngas processes could be utilized to produce liquid fuels, RNG, and green ammonia.
Green NH3 An option for distributed clean energy and distributed NH3 production in Canada?
Thank You Acknowledgements: Nicola Maffei, Ph.D., CanmetENERGY Luc Pelletier, formerly CanmetENERGY now at Health Canada Contact information: Andrew McFarlan, Ph.D. Manager, Bioenergy R&D Natural Resources Canada CanmetENERGY, 1 Haanel Dr. Ottawa K1A 1M1 Ph: 613-995-2376 E-mail: andrew.mcfarlan@nrcan.gc.ca