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2222--2255 of of SeptemSeptember 201ber 20133
10th Annual NH10th Annual NH33
Fuel ConferenceFuel ConferenceYoshitsugu KojimaYoshitsugu Kojima
Hiroshima University Hiroshima University Institute for Advanced Materials ResearchInstitute for Advanced Materials Research
A Green Ammonia A Green Ammonia EconomyEconomy
1. Energy and Environmental Issues
2. Research on Hydrogen Storage Materials
and
Systems3. Properties and Safety of
Ammonia 4. A Green Ammonia
Economy5. Summary
Table of ContentsTable of Contents
●TokyoKyoto●
●Niigata
●Fukuoka ●Hiroshima
Itsukushima Shinto Shrine
Hiroshima Peace Memorial
●Nagoya
Sendai●
Peace Memorial City
●Kumamoto
●Fukushima
Sustainable economy using renewable energy 1.
Energy and Environmental Issues
Annual global energy consumption by humans, oil, gas, coal, uranium reserves and annual solar energy
Annual solar energy
Ten thousand times
Energy career for renewable energy Electric power
Solar power generation,0.15-0.3$/kWh(2010),0.05-0.07$/kWh(2030)Onshore wind farms 0.09-0.15/kWh(2010), 0.05-0.08$/kWh(2030)
Electric power
Annual global energy consumption by humans
2. Research on Hydrogen Storage Materials and Systems
Evaluation and characterization of 200
kinds of hydrogen storage
materials
H N
Li
Li
HN
B CH3
-CH3
-CH2-CH
Hydrogen absorbing alloy
Complex hydrides
Organic hydrides
Inorganichydrides Carbon materials
Ammonia: Maximum volumetric H2
density
Mg
H
LiB HNaB
H
2
4
68
Volu
met
ric H
2de
nsity
/kgH
2/1
00L
1012
Gravimetric and volumetric H2
densities of hydrogen storage
systems
00 5 10 15 20 100Gravimetric H2
density
/mass%
High pressure H2
tank(35MPa)
5.7wt%1.5kgH2
/100L
(2002)
High pressure H2
tank(70MPa)
(2010) 5wt%2.8
kgH2
/100L
5.1wt%3.6kgH2
/100L
Liquid H2
tank (-253�)
DOE target
(ultimate)
NH3
tank$1,000 /70L
Deleterious substanceControlled fuel
1.2wt%2.9kgH2
/100L
(2001)
Metal hydride Tank (1MPa)
High-pressure metal hydride (MH) tank
(35MPa)
1.7wt%4.1kgH2
/100L
(2005-2006)(2002)
Hydrogen generatorusing NaBH4
2.0wt%,1.5kgH2
/100L
2.0wt%5.3kgH2
/100LAB2 BCC
3. Properties and Safety of Ammonia
Volumetric H2
density of liquid NH3
:(1.5-2.2)×H2
density of liquid H2
0.1MPa, -253� 0.1MPa, -33�
1MPa, 25�1MPa, -242�
1.7 times
2.2 times
Pressure, temperature Pressure, temperature
1.5 times0.1MPa, -253� 1MPa, 25�
Liquid H2 Liquid NH3 H2
density of NH3/H2
density of H2
Volumetric H2 densities of Liquid NH3
and H2
Gravimetric H2
density(wt%)
Volumetric H2
density(kg/100L)0.1MPa, -33� (1MPa, 25�) 12.1(10.7)
NH3
17.8
Hydrogen
100
0.010(0.082)
Production cost($/kgH2
)2200ton/day
Transportation cost($/kgH2
)
Storage cost($/kgH2
)H2
2664ton 14.95 0.54
0.19 0.51-3.22 (1.87)
3.00 3.80
1610kmパイプライン
182
day
15
day 0.06 1.97
Supply cost($/kgH2
) 4.05-4.53 5.5-21
Properties and costs of NH3
and H2
Item
<Volumetric H2
density in NH3 at the same pressure and temperature
: 100-1000 times
<
Flammability of Ammonia
From above it is seen that ammonia is the least hazardous due to flammability.
132�-188�-157�-104�
11�
-40�
SubstanceAmmonia
MethaneHydrogen
MethanolGasoline
Flash point
LPG(propane)
Flammable limits16-25%5-15%4-74%2.1-9.5%6-36%1.4-7.6%
GWP: Global warming potential
GWP: 0
GWP: 0
GWP: 21
Ignition point651�537�530�450�464�300�
Editor-in-Chief David R. Ride, CRC Handbook of Chemistry and Physics 2008-2009 89th edition CRC Press, Taylor & Francis Group, Boca Raton,London, New York, http://www.jaish.gr.jp/anzen/gmsds/7664-41-7.html, http://www.toyokokagaku.co.jp/product/01_02_51.html, http://www6.nsk.ne.jp/toyama-kak/1hoanjoho/MSDSshu/MSDS/04.pdf,
Safety of Ammonia(flammability)
Medicine for insect bites
Ammonia (2.3%)21�(70F), AmmoniaVapor pressure 0.003MPa
Ammonia (9.5-10.5%)21�(70F), AmmoniaVapor pressure 0.011MPa
Stimulant
Familiar material
(Toxicity)American Conference of Industrial Hygienists (ACGIH): 25ppm
Household Ammonia(Cleaner)
Ammonia (5-10%)21�(70F), AmmoniaVapor pressure 0.006-0.011MPa
minor aches,pains of muscles
Annual production of the world
198
million ton (2012)N2
+3H2
→ 2NH3
20-40MPa, 573-823K
Methane steam reforming: hydrogenHaber-Bosch process
Fertilizer Energy career
NH 3
Game-changing technology
EnergyEnergyoutoutoutout
NH3
H2
O
N2
Conceptive picture of ammonia energy system
NH3
production NH3
utilization
Storage・transportation
Solar concentrating system
(trough)
Heat storage
H2
O N2 NH3
Hydrogen production plant
NH3
utilization
Small scale NH3
production
Energy stock
NH3
production using solar heat
H2
→NH3
production
ThermochemicalWater splitting
NH3
power plant,SOFC
H2 e
e
H2
Liq.NH3
NH3
delivery
NH3
H2
NH3
NH3
4. A Green Ammonia Economy
527342733273227312732730
Hyd
roge
n yi
eld
/%
20
40506070
Direct thermal decomposition of water(Hydrogen yield calculated by HSC Chemistry 6.0)
30
10
HH2
0.1MPa
Temperature /K
4.1 NH3
production
Yield:64% at 4000°C
Below 650°C
Heat Pipe Solar Collector
Focusing mirror
Heat carrier Thermochemical water splitting,Steam-electrolysis
(1) Heat collecting system
Heat storage
H2
O→H2
+1/2O2
Iodine–Sulfur thermochemical water-splitting process
Hydrogen
H2
SO4
Oxygen
I2SO2
H2
O+
H2+I2
2HI1/2O2
+SO2+H2
O
Sulfur(S)Iodine(I)Circulation
Solar heat
2HI + H2
SO4
I2 + SO2 + 2H2
O
H2
O
Water
Rejectedheat
100°C
Circulation
Iodine–Sulfur thermochemical water-splitting process
SO2
+ I2
+ 2H2
O→2HI
+ H2
SO4
(3)
400°C800°C
Below650°C
(2) Hydrogen and ammonia production
2HI→ I2
+ H2
(1)Hydrogen iodide H2
SO4
→SO3
+ H2
O→SO2
+ 0.5O2
+ H2
O (2)Sulfuric acid
■H2
O-Na oxide system
� 2NaOH + 2Na(l)
→
2Na2
O + H2
� 2Na2
O
→
Na2
O2
+ 2Na(g)
� Na2
O2
+ H2
O(l) →
2NaOH + 1/2O2
H2
O → H2
+ 1/2O2
H2
and Na2
O were formed at 350 °C (20 h). : ∼
70 %
The hydrolysis can be completed at 100 °C. : ∼ 100 %
Na can be generated at 500 °C
(20 h). : ∼
70 %
The possibility of H2 production below 500 °C by water-splitting via reactions of the H2
O-Na oxides system was experimentally demonstrated.
H. Miyaoka, T. Ichikawa, N. Nakamura, Y. Kojima, “Low-Temperature water-splitting by sodium redox reaction”, Int. J. Hydrogen Energy, 37, 17709-17714 (2012)
Haber-Bosch process
0 1000 2000
3000 4000
1000
800
600
400
200
0
Am
mon
ia c
apita
l cha
rge
with
A
SU a
nd g
as tu
rbin
e/$
t-1
Plant size /t/day
146.46 $/t
935.55 $/t
Cost of ammonia as a function of plant size
0.82 $/kgH2
5.3 $/kgH2
100 t/day
Cost of ammonia drastically increases below the plant size of 100t/day.
A small-scale ammonia synthesis process
ASU: air separation unit
Surplus electricity storage using NH3
for high efficiency utilization
Specifications
Hydro carbon(C1)Water(H2
O)Oxygen(O2
)N2
(Ar)HeCarbon dioxide(CO2
)Carbon monooxide(CO)Sulfur compoundFormaldehydeFormic acidAmmoniaHalide
Hydrogen purity 99.97%2ppm5ppm5ppm100ppm300ppm2ppm0.2ppm0.004ppm0.01ppm0.2ppm0.1ppm0.05ppm
ISO14687-2
Specifications of hydrogen fuel for FCV
Ammonia concentration:
<0.1ppm
Non-hydrogen components
4.2 NH3
utilization(1) Hydrogen carrier for Fuel Cell Vehicles
International Standard, December 2012
H2
NH3decomposition
NH3
removalNH3
Catalysts (1) Alkali metal hydride-NH3
system(2) NH3
absorbing materials
H2
NH3
concentration:<
0.1 ppm
To purify hydrogen Ru-based catalysts
H. Miyaoka, H. Fujii, H. Yamamoto, S. Hino, H. Nakanishi, T. Ichikawa, Y. Kojima, Int. J. Hydrogen Energy 37, 16025-16030 (2012)
LiH+NH3
→ LiNH2
+H2 (1)
ΔH0: -43kJ/molH2H2
content:8.1mass%
H2
generation at room temperature
523-573K, 0.5MPa, H2
flow(1)LiH-NH3system
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)
ScCl3milled
Rea
ctio
n yi
eld
/%
3040506070
2010
rawTiCl3
VCl3CrCl3
FeCl3NiCl2
ZrCl4NaCl
TiO2
BN
0
1h at RT
Reaction yield of LiH-NH3
system using additives
(2) NH3
absorbing materials
NH3
/Mg(BH4
)2
/mol/mol
P-C isotherms for Mg(BH4
)2
-NH3
and CaCl2
-NH3
systemsP-C isotherms for Mg(BH4
)2
-NH3
and CaCl2
-NH3
systems
NH3
storage capacity: 65wt% 55wt%
T. Aoki et ai., Abstract of MH2012, Kyoto Japan (2012)
NH
3pr
essu
re/M
Pa
0
Vapor pressure of
NH3
at 19°C
0.06MPa
0.8
0.6
0.4
0.2
6mol/mol
0
0.2
0.4
0.6
0.8
8420 6NH3
/CaCl2
/mol/molN
H3
pres
sure
/MPa
420 6
Ammonia
vapor pressure(20°C)
8mol/mol
Ammonia absorption behavior in CaCl2
7mm
Ammonia gas turbine (NH3
100%)Ammonia engine(NH3
100%)
Energy career (liquid fuel)
NH3
4NH3
+3O2
→2N2
+ 6H2
O
Controlled fuel
AmmoniaSOFC
1/2O2
H2
O
H2
+O2-→H2
O+2e-
O2-
1/2O2
+2e-
→O2-
2/3NH3
→1/3N2
+H2
Air crafts
Ships
Trucks Electric power plants
1. Ammonia has been expected as an energy carrier because it has a high H2
storage capacity with 17.8 mass% and the volumetric hydrogen density is 1.5-
2.2 times of liquid hydrogen.2.
CO2
free hydrogen (ammonia) will be synthesized using solar heat below 650°C.
3. A small-scale ammonia synthesis process will be developed to store various renewable energies.
4. Ammonia has advantages in cost and convenience as a renewable fuel for fuel cell vehicles, SOFC, electric power plants, air crafts, ships and trucks.
5.Summary
Power to liquid NH3
is a promising technology which converts electrical power to fuel.
Thank you for your attention.Thank you for your attention.http://www.afdc.energy.gov/afdc/fuels/emerging.html
The use of ammonia as a potential hydrogen carrier for hydrogen delivery or off-board hydrogen storage was evaluated by the DOE.
NH3
: Emerging Alternative Fuel
Website