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