liquid ammonia for hydrogen storage - nh3 fuel association · 2019-02-15 · 21-24 of september...
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21-24 of September 2014 11th Annual NH3 Fuel Association Conference
Yoshitsugu Kojima Hiroshima University
Institute for Advanced Materials Research
Liquid Ammonia for Hydrogen Storage
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
Table of Contents
Peace Memorial City
Itsukushima Shinto Shrine
Hiroshima Peace Memorial
Energy and Environmental Issues Renewable energy
Solar energy Wind Hydro Geothermal
Tidal power Wave power
Solar thermal Solar cell
1. Energy and Environmental Issues
Electric power
Hydrogen (gas)→ Hydrogen carrier (solid, liquid)
(50 times of Annual global energy consumption by humans)
-196 °C
Hydrogen absorbing alloys
Inorganic hydrides (thermolysis) Organic hydrides
Ti-Cr-Mn(AB2)
Methylcyclohexane⇔ Toluene
MgH2 NH3BH3 LiBH4 LiNH2
Carbon
2. Research on hydrogen carrier (hydrogen storage materials) and systems (1999~2014)
CH3
Ti-Cr-V(BCC)
Carbon materials (77K)
200 kinds of hydrogen storage materials
H2
NH3 Inorganic hydrides (hydrolysis)
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
1.Catalyst 2.Composite Hydrides Kinetics Thermodynamics
3.Nano-crystallites Kinetics,Thermodynamics
H2 molecule Hydrogen storage materials
Hydride
Catalyst
AH
A, B, H2
AB H2
BH
NANO-COMPOSITE MATERIALS
10nm 10nm
Hydride (Hδ+)
Catalyst
Milling Hydride (Hδ-)
Exchange
AH HB
∆H ∆S
Y. Kojima, Materials Science Forum, 654-656, 2935 (2010)
Li-Mg-N-H
LiH-NH3 NaH-NH3BH3 Mg-based nano-comoposite Material(Nb2O5:1mol%)
2LiBH4-MgH2
Li-C-H
Li-N-H
Packing densities of solid-state hydrides with light elements
0 5 10 15
Hydrogen storage capacity /mass%
0.2
0.4
0.6
0.8
1.0
Pack
ing
dens
ity /g
/cm
-3
20
NH3BH3
Mg(BH4)2
LiBH4
Al(BH4)3
AlH3
LiH
MgH2
LiAlH4
NaAlH4
Face-centered cubic structure
Packing ratio
Packing ratio: 74% (theoretical value)
Packing ratio: 50% (practical value)
Volumetric H2 density : below 8kgH2/100L
0
2
4
6
8
0 5 10 15 20 100
10
NaH-NH3BH3
12
∼ ∼
Ti1.1CrMn
Li-Mg-N-H
NaBH4-4H2O
LiH-NH3
Super activated carbon 77K
MgH2
Li-C-H
Ti0.22Cr0.39V0.39
NH3BH3 AlH3
N2H4-H2O
2LiBH4-MgH2
LiBH4
Decalin
Mg(BH4)2
H2 densities of hydrogen carrier(solid, liquid) Vo
lum
etric
H2 d
ensi
ty /
kgH
2/100
L
(
Pack
ing
ratio
: 50%
)
Super activated carbon (20K)
Hydride(calculated value) H2 storage materials (experimental value) High pressure tank of 70MPa
Gravimetric H2 density /mass%
Methylcyclohexane
NH3: burnable substance → Energy carrier
Liquid H2 0.1MPa, 20K 1MPa, 31K
NH3 0.1MPa, 240K 1MPa, 298K
14
CH3OH-H2O
Volumetric H2 density of liquid NH3:(1.5-2.5)×H2 density of liquid H2
3. Properties and Safety of Ammonia
Metal Hydride (Ti1.1CrMn)
Filter Fin
High-pressure MH tank (Ti-Cr-Mn + compressed H2)
Fueltank (25L) NaBH4
Byproduct tank (25L) NaBO2
Reactor, catalyst, separator, pump
150 mm
130mm
Hydrogen generator using sodium borohydride
1.7mass%, 4.1kgH2/100L 2.0mass%, 1.5kgH2/100L
<
10mass%, 8.2kgH2/100L Ammonia tank
<
5mass%, 2.8kgH2/100L High pressure H2 tank(70MPa)
0 5 10 15 Hydrogen storage capacity /mass%
NaAlH4
Ca(BH4)2
MgH2
Methylcyclohexane
-80
-60
-40
-20
0
Hea
t of f
orm
atio
n(∆
H) /
kJ/m
olH
2
20
NH3
Ti-Cr-V
Ti-Cr-Mn
Mg(BH4)2
Heat of formation and H2 storage capacity
LaNi5 Heat of formation for NH3 : about 10% of heat of combustion for H2
Costs of NH3 and H2
NH3 Hydrogen
Production cost($/kgH2) 2200ton/day USA
Transportation cost($/kgH2)
Storage cost ($/kgH2) H22664ton 14.95 0.54
0.19 0.51-3.22 (1.87)
3.00 3.80
1610km Pipe line USA
182 day USA 15 day USA 0.06 1.97
Supply cost($/kgH2) USA 4.05-4.53 5.5-21
Item
<
Price in Japan(Yen/Nm3H2) 122 27-36(2013)
Cost of NH3 in Japan: 20-30% of cost of H2
Fatal Incidents
The
num
ber o
f acc
iden
ts
400 300 200 100 0
H2
H2
NH3 NH3
NH3:150 million tonnes / year H2:4 million tonnes / year
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-)
http://www.elucidare.co.uk/news/Ammonia%20as%20H2%20carrier.pdf
Industrial accidents involving ammonia and hydrogen
Hazardous substance
Controlled fuel
Safety
Distribution amount
NaBH4
NH3
0 2 4 6 8 10 120.0
0.2
0.4
0.6
0.8
PCT曲線 19℃アンモニア蒸気圧
NH
3 P
ress
ure
[M
Pa]
NH3 [mol/NaBH4mol]
0.09MPa NH
3 pre
ssur
e /M
Pa
NH3 /mol/mol(NaBH4)
NH3 vapor pressure (20℃)
Atmospheric pressure
NaBH4 solution P-C isotherm for NaBH4-NH3 system(ammine complex )
Ammonia absorbing materials using borohydrides and metal halides
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)
>0.8
0.2
0.4
0.6
<0.001 Am
mon
ia p
ress
ure
/MPa
LiF LiCl LiBr Electronegativity difference(χp) 1.98 < 2.18 < 3
Plateau pressure of lithium ammine halide
T. Aoki, T. Ichikawa, H. Miyaoka, Y. Kojima, J. Phys. Chem. C 118, 18412-1846 (2014)
>0.8
0.2
0.4
0.6
<0.001 Am
mon
ia p
ress
ure
/MPa
Plateau pressure of metal ammine chloride
NiCl2 CaCl2 LiCl NaCl Electronegativity difference(χp) 1.05 < 1.25 < 2.18 < 2.23
The smaller the electronegativity difference is, the lower plateau pressure is achieved. Safety improvement
Plateau pressure vs electronegativity difference A
mm
onia
pre
ssur
e /M
Pa
>0.8
3.5 2.5 1.5 0.5
0.2
0.4
0.6
0.001
Electronegativity difference(χp)
χp =2.2
Ammonia absorption: χp <2.2
Solar concentrating system (trough)
Heat storage
H2O N2 NH3
Hydrogen production plant
NH3 utilization
Small scale NH3 production
Energy stock
NH3 production using solar heat
H2→NH3 production
H2 production using solar heat
NH3 power plant, SOFC
H2 e
e
H2
Liq.NH3
NH3 delivery
NH3
H2
NH3 fuel
4. Hydrogen Economy Using Ammonia
CO2: 0
NH3
Domestic use fuel cell
Large-scale moving vehicle
Energy outout
NH3
H2O Conceptive picture of ammonia energy system
NH3 production Power to Liquid (PTL) NH3 utilization
Storage・transportation
N2 H2
NH3 +0.08O2→0.5N2 + 0.16H2O+H2 NH3 +0.75O2→0.5N2 + 1.5H2O
5273 4273 3273 2273 1273 273 0
Hyd
roge
n yi
eld
/%
20
40 50 60 70
Direct thermal decomposition of water (Hydrogen yield calculated by HSC Chemistry 6.0)
30
10
H H2
0.1MPa
Temperature /K
4.1 NH3 production
Yield:64% at 4000°C
Below650°C
Thermochemical water splitting, Steam-electrolysis
Low melting point、 Low voiling point
(High vapor pressure)
Easy Reactivity with water
Easy oxidation and reduction
The possibility of H2 production below 500 °C by water-splitting via reactions of the Na Redox system was experimentally demonstrated.
M-Redox system
H. Miyaoka, T. Ichikawa, N. Nakamura, Y. Kojima, Int. J. Hydrogen Energy, 37, 17709-17714 (2012)
Na metal
Na2O
Na2O2
Na
Entropy (∆S) control
2Na2O→Na2O2 + 2Na(g) 500°C
2NaOH + 2Na(l) → 2Na2O + H2 350 °C
Na2O2 + H2O(l) → 2NaOH + 1/2O2 100 °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
Hydrogen price: barrier to the popularization
Honda will sale in 2015 Price: $70,000 - $80,000
Driving range: 800km Filling time: 3minutes
140-160km/kgH2
NH3 decomposition and removal technology to produce H2
Conversion /% Cartalyst
Nano-Ru/SiO2
673K
34 90
7 27
35 8.5
773K
Nano-Ni/SiO2
Nano-Fe/meso SiO2
Ni/Al2O3 Ni/La2O3
5 6
34 33
873K
97 90
100 82
14.3 64.0 10%Ru/SiO2 97
86
LSZ: Lanthanum-stabilized zirconia, CMK-5: Ordered mesoporous carbon
Ru/CNT-KNO3 Ru-KNO3/MgO-CNTs
50 80 – –
4000 mLg-1h-1 30000 mLg-1h-1 Ru/
LSZ-DP 18 54
75 100
100 100
Fe2O3/CMK-5 NiO/Al2O3
9(723) 6(723)
26 17
96 80
Nano-Ni/Zeolite(1h) – – 22
Ru/Cs2O/Pr6O11 99.6 93(623K) 99.9 >99.9
Catalytic activity NH3 decomposition technology
550℃ 800ppm
Ammonia concentration:<0.1ppm
ISO14687-2
1. Alkali metal hydride- NH3 system(reaction) 2. Metal ammine complex (absorption) 3. Adsorbent 4. Separation membrane
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
SIP (Cross-ministerial Strategic Innovation Promotion Program) “Energy carrier” (Council for Science, Technology and Innovation of the Cabinet Office). 2014-
Program Director (Cabinet Office) Shigeru Muraki (Director and Vice Chairman of the Board of Tokyo Gas Co., Ltd.)
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
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
4. Summary
Tokyo has been chosen to host the World Hydrogen Technologies Convention (WHTC) 2019.
Thank you for your attention. Acknowledgement: This work was partially supported by Council for Science, Technology and Innovation(CSTI), Cross-ministerial Strategic Innovation Promotion Program (SIP), “energy carrier”(Funding agency : JST).」
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