Liquid Ammonia For Hydrogen Storage - Ammonia Energy
Liquid Ammonia for Hydrogen Storage 21-24 of September 2014 11th Annual NH3 Fuel Association Conference Yoshitsugu Kojima Hiroshima University Institute for Advanced Materials Research
Table of Contents 1. Energy and Environmental Issues 2. Research on Hydrogen Storage Materials and Systems 3. Properties and Safety of Ammonia 4. Hydrogen Economy Using Ammonia 5. Summary Hiroshima Peace Memorial Itsukushima Shinto Shrine Peace Memorial City
1. Energy and Environmental Issues Energy and Environmental Issues Renewable energy Geothermal Solar energy Hydro Wind (50 times of Annual global energy consumption by humans) Tidal power Wave power Solar thermal Solar cell Electric power Hydrogen (gas) Hydrogen carrier (solid, liquid)
2. Research on hydrogen carrier (hydrogen storage materials) and systems (1999 2014) Inorganic hydrides (thermolysis) Organic hydrides CH3 MgH2 NH3BH3 LiBH4 LiNH2 Hydrogen absorbing alloys Methylcyclohexane NH3 Toluene Inorganic hydrides (hydrolysis) Ti-Cr-Mn(AB2) Ti-Cr-V(BCC) Carbon materials (77K) Carbon -196 C H2 200 kinds of hydrogen storage materials Y. Kojima, H. Miyaoka, T. Ichikawa: "Hydrogen Storage Materials". In Steven L. Suib editor. New and Future Developments in Catalysis: Batteries, Hydrogen Storage and Fuel Cells Amsterdam, Elsevier, 2013.
Thermolysis of inorganic hydrides Control heat of formation and kinetics NaH-NH3BH3 LiH-NH3 Mg-based nano-comoposite Material(Nb2O5:1mol%) 2LiBH4-MgH2 NANO-COMPOSITE MATERIALS 2.Composite Hydrides 1.Catalyst Kinetics Catalyst H2 molecule Hydrogen storage materials Thermodynamics 3.Nano-crystallites A, B, H2 AB AH Hydride Kinetics,Thermodynamics Li-N-H H2 Catalyst Hydride (Hδ ) Milling Hydride (Hδ-) 10nm Y. Kojima, Materials Science Forum, 654-656, 2935 (2010) BH HB AH Exchange H Li-C-H S Li-Mg-N-H
Packing densities of solid-state hydrides with light elements Face-centered cubic structure Packing ratio: 74% (theoretical value) Packing ratio: 50% (practical value) Packing density /g/cm-3 Packing ratio 1.0 MgH2 AlH3 0.8 NH3BH3 LiBH4 Mg(BH4)2 0.6 0.4 0.2 0 NaAlH4 5 LiAlH4 LiH 10 Al(BH4)3 20 15 Hydrogen storage capacity /mass% Volumetric H2 density : below 8kgH2/100L
3. Properties and Safety of Ammonia 8 NaBH44H2O 6 2 0 MgH2 Liquid H2 0.1MPa, 20K Methylcyclohexane LiH-NH3 Li-C-H Li-Mg-N-H Super activated carbon 77K 0 3 LiBH4 Mg(BH4)2 NaH-NH3BH3 2LiBH4-MgH2 Ti1.1CrMn 4 3 AlH3 5 10 1MPa, 31K Hydride(calculated value) H2 storage materials (experimental value) High pressure tank of 70MPa 15 Volumetric H2 density /kgH2/100L （Packing ratio: 50％） H2 densities of hydrogen carrier(solid, liquid) 14 NH3 0.1MPa, 240K N2H4-H2O Volumetric H2 12 density of liquid Decalin CH3OH-H2O 1MPa, 298K NH3:(1.5-2.5) H2 Super activated 10 Ti0.22Cr0.39V0.39 carbon (20K) density of liquid H2 NH BH 20 100 Gravimetric H2 density /mass% NH3: burnable substance Energy carrier
10mass%, 8.2kgH2/100L Ammonia tank 5mass%, 2.8kgH2/100L High pressure H2 tank(70MPa) High-pressure MH tank (Ti-Cr-Mn compressed H2) Hydrogen generator using sodium borohydride Reactor, catalyst, separator, pump Fin Filter Fueltank (25L) NaBH4 130mm 150 mm Metal Hydride (Ti1.1CrMn) 1.7mass%, 4.1kgH2/100L Byproduct tank (25L) NaBO2 2.0mass%, 1.5kgH2/100L
Heat of formation( H) /kJ/molH2 Heat of formation and H2 storage capacity LaNi5 0 -20 -40 Heat of formation for NH3 : about 10% of heat of combustion for H2 Ti-Cr-Mn NH3 NaAlH4 Ti-Cr-V Ca(BH4)2 -60 -80 0 Mg(BH4)2 Methylcyclohexane MgH2 5 10 15 Hydrogen storage capacity /mass% 20
Costs of NH3 and H2 Item Price in Japan(Yen/Nm3H2) Production cost( /kgH2) 2200ton/day USA 27-36(2013) 3.80 Transportation cost( /kgH2) 1610km Pipe line USA 0.19 Storage cost ( /kgH2) H22664ton 15 day USA 0.06 182 day USA 0.54 Supply cost( /kgH2) USA Hydrogen NH3 4.05-4.53 122 3.00 0.51-3.22 (1.87) 1.97 14.95 5.5-21 Cost of NH3 in Japan: 20-30% of cost of H2
Safety Industrial accidents involving ammonia and hydrogen Australia(1920-), Canada(1917-), China (1978-), France (1905-), Germany (1900-), India(1944-), Italy (1907-), Japan (1922-), Mexico (1950-), Netherlands (1807-), Russia (1992-), Spain(1958-), Sweden (1864-), UK(1879-), USA(1873-) The number of accidents Distribution amount NH3：150 million tonnes / year H2：4 million tonnes / year 400 300 200 H2 NH3 H2 100 Controlled fuel NH3 0 Incidents Fatal 20carrier.pdf Hazardous substance
Ammonia absorbing materials using borohydrides and metal halides Pressure [MPa] NHNH3 3 pressure /MPa P-C isotherm for NaBH4-NH3 system(ammine complex ) NaBH4 solution 0.8 0.6 0.4 NHPCT曲線 19 アンモニア蒸気圧 3 vapor pressure (20 ) NH3 0.2 0.0 0 0.09MPa 2 NaBH 6 84 4 10 12 [mol/NaBH4mol] ) NHNH3 /mol/mol(NaBH 3 4 Atmospheric pressure NH3 vapor pressure of NaBH4 NH3 vapor pressure Safer ammonia T. Aoki, T. Ichikawa, H. Miyaoka, Y. Kojima, J. Phys. Chem. C 118, 18412-1846 (2014)
Ammonia pressure /MPa Plateau pressure of lithium ammine halide 0.8 0.6 0.4 0.2 0.001 LiBr Electronegativity 1.98 difference(χp) LiCl 2.18 LiF 3 T. Aoki, T. Ichikawa, H. Miyaoka, Y. Kojima, J. Phys. Chem. C 118, 18412-1846 (2014)
Ammonia pressure /MPa Plateau pressure of metal ammine chloride 0.8 0.6 0.4 0.2 0.001 Electronegativity NiCl2 difference(χp) 1.05 CaCl2 1.25 LiCl 2.18 NaCl 2.23 The smaller the electronegativity difference is, the lower plateau pressure is achieved. Safety improvement
Ammonia pressure /MPa Plateau pressure vs electronegativity difference 0.8 0.6 χp 2.2 0.4 0.2 0.001 0.5 1.5 2.5 3.5 Electronegativity difference(χp) Ammonia absorption: χp 2.2
4. Hydrogen Economy Using Ammonia NH3 production using solar heat Large-scale moving vehicle Solar concentrating system (trough) H2 production using solar heat H2O N2 Heat storage NH3 NH3 utilization Liq. NH3 Domestic use fuel cell H2 NH3 production NH3 delivery NH3 NH3 fuel NH3 H2 H2 e H2 Energy stock Hydrogen production plant Small scale NH3 production e NH3 power plant, SOFC CO2: 0
Storage・transportation NH3 production Power to Liquid (PTL) NH3 NH3 utilization NH3 0.08O2 0.5N2 0.16H2O H2 H2 N2 Energy outout NH3 0.75O2 0.5N2 1.5H2O H2O Conceptive picture of ammonia energy system
4.1 NH3 production Direct thermal decomposition of water (Hydrogen yield calculated by HSC Chemistry 6.0) Hydrogen yield /％ 70 60 50 40 0.1MPa Yield:64% at 4000 C H H2 Below 650 C 30 20 Thermochemical water splitting, Steamelectrolysis 10 0 273 1273 2273 3273 4273 5273 Temperature /K
M-Redox system Low melting point、 Low voiling point （High vapor pressure） Easy oxidation and reduction Easy Reactivity with water The possibility of H2 production below 500 C by watersplitting via reactions of the Na Redox system was experimentally demonstrated. H. Miyaoka, T. Ichikawa, N. Nakamura, Y. Kojima, Int. J. Hydrogen Energy, 37, 17709-17714 (2012)
Entropy ( S) control Na metal Na Na2O2 Na2O 2Na2O Na2O2 2Na(g) 500 C Na2O2 H2O(l) 2NaOH 2Na(l) 2NaOH 1/2O2 100 C 2Na2O H2 350 C Haber-Bosch process
4.2 NH3 utilization Toyota will sale in California the summer of 2015, Price: around 70,000 . Driving range: 700km Filling time: 3 minutes Honda will sale in 2015 Price: 70,000 - 80,000 Driving range: 800km Filling time: 3minutes 140-160km/kgH2 Hydrogen price: barrier to the popularization NH3 decomposition and removal technology to produce H2
NH3 decomposition technology Catalytic activity 550 800ppm Conversion /% Cartalyst 673K 773K 873K Ru/CNT-KNO3 Ru-KNO3/MgO-CNTs Ru/ 30000 mLg-1h-1 LSZ-DP 4000 mLg-1h-1 50 80 18 54 – – 75 100 100 100 10%Ru/SiO2 14.3 64.0 97 99.9 99.9 90 Ru/Cs2O/Pr6O11 Nano-Ru/SiO2 99.6 93(623K) 34 8.5 35 100 82 Nano-Fe/meso SiO2 7 27 86 Ni/Al2O3 Ni/La2O3 5 6 34 33 97 90 9(723) 6(723) 26 17 96 80 – 22 – Nano-Ni/SiO2 Fe2O3/CMK-5 NiO/Al2O3 Nano-Ni/Zeolite(1h) ISO14687-2 Ammonia concentration: 0.1ppm 1. Alkali metal hydrideNH3 system(reaction) 2. Metal ammine complex (absorption) 3. Adsorbent 4. Separation membrane LSZ: Lanthanum-stabilized zirconia, CMK-5: Ordered mesoporous carbon
NH3 production and utilization technologies Japan Science and Technology (JST) Strategic Basic Research Program Advanced Low Carbon Technology Research and Development Program Special Priority Research Areas Energy Carrier, July 2013-2014 SIP (Cross-ministerial Strategic Innovation Promotion Program) “Energy carrier” (Council for Science, Technology and Innovation of the Cabinet Office). 2014Program Director (Cabinet Office) Shigeru Muraki (Director and Vice Chairman of the Board of Tokyo Gas Co., Ltd.) Outline Promote the realization of a hydrogen-oriented society through research on efficient and low –cost hydrogen production technology, liquid hydrogen for efficient transport and storage, and energy carrier technology
4. Summary 1. We have evaluated 200 kinds of hydrogen storage materials(hydrogen absorbing alloys, Inorganic materials, carbon materials) 2. Liquid Ammonia has been expected as a hydrogen energy carrier because it has a high H2 storage capacity with 17.8 mass% and the volumetric hydrogen density is 1.5-2.5 times of liquid hydrogen. 3. Ammonia has advantages in cost and convenience as a renewable liquid fuel for fuel cell vehicles, SOFC, electric power plants, air crafts, ships and trucks. 4. Power to liquid ammonia (PTL) is a promising technology to establish hydrogen economy
Tokyo has been chosen to host the World Hydrogen Technologies Convention (WHTC) 2019. WHTC Venue History 1st 2005 Singapore 2nd 2007 Montecatini Terme 3rd 2009 Delhi, India 4th 2011 Glasgow, UK 5th 2013 Shanghai, China 6th 2015 Sydney, Australia 7th 2017 Prague, Czech 8th 2019 Tokyo, Japan Thank you for your attention. Acknowledgement: This work was partially supported by Council for Science, Technology and Innovation(CSTI), Crossministerial Strategic Innovation Promotion Program (SIP), “energy carrier”(Funding agency : JST).」
Liquid Ammonia for Hydrogen Storage. 1. Energy and Environmental Issues 2. Research on Hydrogen Storage Materials . and Systems 3. Properties and Safety of Ammonia . High-pressure MH tank (Ti-Cr-Mn compressed H. 2) Fueltank (25L) NaBH4 . Byproduct tank (25L) NaBO2 . Reactor, catalyst, separator, pump . 150 . mm . 130mm .
2 Ammonia as a fuel . 2.1 Properties of ammonia . The basic properties of ammonia are summarized and compared with methane in . Table 2-1. Under atmospheric temperature and pressure, ammonia is a colourless, toxic gas with a sharp and penetrating odour. Ammonia in its pure form is referred to as anhydrous (“without water”) ammonia. Ammonia
Ammonia Tank Storage N 2 Air Separation Plant Electricity Air Novel Ammonia Synthesis: Simplify ! Reduce cost RE Ammonia Transmission Storage Scenario "Atmospheric" Liquid Ammonia Storage Tank (Corn Belt) -33 C 1 Atm Each: 30,000 Tons, 190 GWh 15M turnkey 80 / MWh 0.08 / kWh capital cost .
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Ammonia is typically created by combining nitrogen with hydrogen. Therefore, the emissions from producing hydrogen as feedstock and the emissions arising from the synthesis of ammonia should be considered as part of the life cycle emissions of ammonia fuel. Table 1 shows the well-to-tank emissions for ammonia production, transmission,
and experience of ammonia storage tank design and operations. 3. DESCRIPTION OF SPECIFIC AREAS OF CONCERN 3.1 Ammonia Storage Facilities Liquid ammonia is stored either at ambient temperature under high pressure or at -33 C under atmospheric pressure. (The description liquefied is also sometimes used for liquid, see Glossary for explanation).
Ammonia: An Essential Chemical Ammonia is a naturally occurring chemical in the atmosphere, as well as an essential man-made chemical. It is represented by the chemical formula nH 3. Ammonia in this form is also known as ammonia gas or anhydrous (“without water”) ammonia. At room temperature, amm
DESCRIPTION OF AMMONIA STORAGE TANK . The complex has two ammonia storage tanks common for both streams, T-2301A of 10000 MT and T-2301B of 5000 MT capacity for storage of liquid ammonia at near atmospheric pressure and at -330C. The tanks were commissioned in 1987 and 1995 respectively. Both Tanks
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