Career. NH as a Hydrogen of October th Annual NH 3 Fuel Association Conference
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1 NH as a Hydrogen 3 Career 1-22 of October th Annual Fuel Association Conference Yoshitsugu Kojima Hiroshima University Institute for Advanced Materials Research
2 Table of Contents 1. Energy and Environmental Issues 2. Research on Hydrogen Storage Materials 3. Characteristics of 4. utilization 5. Future perspective 6. Summary Hiroshima University 800km Kyoto Sendai Fukushima I Nuclear Power Plant Tokyo Japan Itsukushima Shinto Shrine Hiroshima Peace Memorial
3 1. Energy and Environmental Issues History of Industrial Revolution Coal First Industrial Revolution (18th~19th century) Fossil energy economy Oil(Natural gas) Renewable energy Second Industrial Third Industrial Revolution Revolution (End of the 19th century (21st century?) ~Early 20th century) Sustainable economy 12 billion ton of oil equivalent Secondary energy H 2
4 2. Research on Hydrogen Storage Materials Hydrogen career? Liquid hydrogen Liquid hydrogen(20k), 7kgH 2 /100L 3.7 billion ton /year Liquefying the hydrogen uses 30-40% of the hydrogen s energy content
5 Development of FCV(2000~) Honda FCX(35MPa) Toyota FCHV(70MPa) Cruising distance: 620km, Cruising distance: 830km Internal volume: 171L, 3.9kgH 2 Internal volume: 156L, 6.1kgH km/1kgH 2 Toyota aims for $50,000 production hydrogen sedan by 2015 Hydrogen storage materials
6 Hydrogen storage materials (1999~2012) Li B CH 3 H N N H Cr Mn Ti Mn Mn Cr Cr Mn B H Li Li -CH 3 Organic hydrides Cr Cr Cr Ti Mn CrTi Mn Cr Mn Ti Mn Mn Cr -CH -CH 2 Hydrogen absorbing alloy Complex hydrides Inorganic hydrides Evaluation and characterization of 200 kinds of hydrogen storage Porous materials
7 Volumetric H 2 density /kgh 2 /100L (Packing ratio: 50%) Gravimetric and volumetric H 2 densities of hydrogen storage materials Super activated carbon (20K) (1MPa, 298K, liquid) C 10 H 18 8 AlH 3 BH 3 C 7 H 14 HCOOH MgH 2 6 Liquid H 2 Mg(BH 4 ) Ti CrMn NaH BH 3 LiH-8/3Mg(NH 2 ) 2 Hydride(calculated value) H 2 storage materials (experimental value) High pressure tank of 70MPa Gravimetric H 2 density /mass% Volumetric H 2 density in : 1.5 liquid H 2 Maximum volumetric H 2 density
8 3. Characteristics of California farmer, Injection of liquid ammonia in a sugar beet field : Inclusion of hydrogen Haber-Bosch process 10-25MPa, K N 2 +3H 2 2 Annual production of the world 153 million ton (2008) Renewable fuel independent of fossil fuel
9 0.18kgH 2 /kg material 0.107kgH 2 /L material Gasoline gallon equivalent $2-4/gge (2010~2011)
10 H/M:2,H 2 :11mass% H/M: 3,H 2 :18mass% ΔH: -285kJ/molH 2 ΔH: -31kJ/molH 2 Mg(BH 4 ) 2 H 2 absorbing alloy Specimen H 2 content ΔH (LaNi 5 ) 15mass% 18mass% 1.5mass% -57~-75kJ/molH 2-31kJ/molH 2-31kJ/molH 2 H 2 O Partial atomic charges δ δ+ Stable under water and oxygen
11 Safety Assessment of Ammonia as a Transport Fuel Risø National Laboratory, Denmark (2005) Substance Ammonia Natural gas Methane GWP: 0 GWP: 21 GWP: 21 Health Flammability Flash point Hydrogen LPG(propane) GWP: 0 Methanol Gasoline(92 octane) GWP: Global warming potential From above it is seen that ammonia is the most hazardous due to health effects, but the least hazardous due to flammability. All considered substance /compounds are ranked as not reactive in emergency situations. Safety number: Ammonia=Hydrogen
12 4. utilization Hydrogen carrier 4 2N 2 + 6H 2 6H 2 +3O 2 6H 2 O Energy carrier 4 +3O 2 2N 2 + 6H 2 O Energy carrier Gas turbine SOFC ICE vehicle Hydrogen carrier FCV Domestic fuel
13 4.1 Large scale power generation using gas turbine(output power Million kw, 1000MW) Preliminary calculation of energy balance 1996) Liquid H Item 2 system Input electric energy 100 Energy loss by transportation (5000km) Energy after transportation (2.5) 70.4 system 100 Energy after production Plant cost /million dollars Energy hydrogen generated carrier (Efficiency: 60%) energy Combined Cycle carrier (1.6) H 2 gas turbine ( MW) (WE-NET: 32 H 2 gas turbine 41 gas turbine SOFC 1kW- 1MW Efficiency: 60%
14 4.2 Nextgeneration vehicle development Fuel consumption of nextgeneration vehicle Without emission of CO 2 Fuel consumption /km/kwh km Gasoline vehicle 1700km 1310kg Hybrid vehicle 200km EV 830km 156L 70MPa 1880kg 30-40% 60% 294kg, 24kWh FCV Calculation 630km 88L 1MPa Vehicl e 1300km 88L 1MPa hybrid Vehicl e Fuel consumption Tank to wheel efficiency Ammonia is both caustic and hazardous Hybridtruck (controlle d fuel)
15 4.3 Energy and hydrogen career Ammonia storage issue (Energy and hydrogen careers for gas turbine, SOFC, ICE vehicle FCV) 1. High flash point, High Decomposition temperature (above 400 C) 2. Toxic to humans Research purposes 1. Conversion from ammonia to hydrogen (mixture of H 2 and, generation of high purity H 2 ), Cold start 2. Ammonia storage materials (lower vapor pressure), Harmless
16 (1) Conversion from ammonia to hydrogen at RT MH-NH K, 0.5MPa, H 2 flow LiH+ LiNH 2 +H (1) 2 ΔH 0 : -43kJ/molH 2 H 2 generation at room temperature H 2 content:8.1mass% Y. Kojima, K. Tange, S. Hino, S. Isobe, M. Tsubota, K. Nakamura, M. Nakatake, H. Miyaoka, H. Yamamoto and T. Ichikawa, J. Mater. Res., 24, 2185 (2009) Molecular dynamics simulation LiH A. Yamane, F. Shimojo, K. Hoshino, T. Ichikawa, Y. Kojima J. Mol. Struct. THEOCHEM 944, 137 (9pp) (2010) Hydrogen yield /% 100 Hydrogen desorption curves of LiH- system(room temperature) TiCl 3 -doped(1mol%) LiH Activated LiH LiH Reaction time /h
17 Conversion system between and H 2 +LiH LiNH 2 +H MPa Pressure Gauge 2 Gas sampler Gas densitometer Reaction cell Hydride 0.5g Heater C rpm Gas circulation pump Pressure gauge 1 Collaborative research with Toyota Industries Flow meter flow rate ~50cc/min (0 C, 1atm)
18 Electrolysis of Power supply E(H 2 O)=1.23V E( )? E= ΔG 0 /3F + RT ln(pn 2 1/2 ph 2 3/2 )/nf H 2 N 2 3e 3e 3NH 2 ΔG 0 : Standard Gibbs free energy difference=13.1kj/mol n=3: Electron number responsible for reaction E : Theoretical decomposition voltage Vapor Pressure of (25 ºC ) Cathode Cathode 3 + 3e 3/2H 2 3 2NH3 1/2N 2 3/2H 2 + 3NH 2 Anode Liquid containing electrolyte (metal amide) 1/2N 2 +3/2H 2 Anode 3NH 2 1/2N e E( )=0.038V V=0.077V(theory) 0.5V(experimental) N. Hanada, S. Hino, T. Ichikawa, H. Suzuki, K. Takai, Y. Kojima, Chemical Communications, 46, (2010)
19 Mechanocatalysis We have detected hydrogen and nitrogen gas when SrTiO 3 and BaTiO 3 powder is mechanically milled under ammonia gas at room temperature. Steel ball H 2 Intensity /arb. unit N 2 Milling ATiO 3 (A:Sr, Ba) SrTiO 3 BaTiO Time /min B. Paik, M. Tsubota, T. Ichikawa, Y. Kojima, Chemical Communications, 46, (2010)
20 (2) absorbing materials P-C isotherm for CaCl 2 - system pressure /MPa Pressure [MPa] kJ/mol 0.06MPa Vapor pressure of at 19 C PCT curve 19 Liq.ammonia vapor [mol/cacl 2 mol] 6 8 /CaCl 2 /mol/mol 42kJ/mol 41kJ/mol 115g/L Cl C a 107g/L T. Aoki et ai., Abstract of MH2012, Kyoto Japan (2012) Rasmus Z. Sørensen et al., J. AM. CHEM. SOC. 130, 8660 (2008) 102kg Ca( ) 8 Cl 2 56kg Liquid
21 ab initio molecular-dynamics (MD) simulation based on density functional theory (DFT). Lower vapor pressure Absorption energy A. Yamane et ai., Abstract of MH2012, Kyoto Japan (2012)
22 5.Future perspective H 2 production H 2 O N 2 utilization H 2 Passenger car production 9000km Energy stock H 2 e power plant SOFC Liq. Station e Truck Controlled fuel Passenger car
23 Realization of sustainable economy (renewable energy economy) (2030) Controlled fuel Electricity H 2 Best mix of, H 2 and electricity
24 6.Summary 1. Ammonia has advantages in cost and convenience as a fuel for vehicle, electric power plant and SOFC. 2. LiH- system with TiCl 3 desorbed 6 mass% of H 2 at room temperature. 3. Hydrogen gas was generated by the electrolysis of liquid ammonia. 4. We have detected hydrogen and nitrogen gas when SrTiO 3 and BaTiO 3 powder is mechanically milled under ammonia gas. 5. The vapor pressure of ammonia was decreased in metal chlorides. economy is a practical H 2 economy
25 Ministry of Education, Culture, Sports, Science and Technology (MEXT) Ministry of Economy, Trade and Industry (METI) Liquid Hydrogen Fuel for Hydrogen Delivery $20 million September 21, 2012
26 Acknowledgement: This work was partially supported by the Advanced Fundamental Research Project on Hydrogen Storage Materials supported by NEDO ( FY), Japan. Staff: 6, PD: 2, M1: 4, M2: 4, D1: 1, D2: 1, D3: 3, D4: 1,D5: 1 (24) (2012) Emerging Fuels(DOE) Alternative Fuels?
27 Thank you for your attention.
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