11--2 of October 20122 of October 20129th Annual NH9th Annual NH33

Fuel Association ConferenceFuel Association Conference

Yoshitsugu KojimaYoshitsugu KojimaHiroshima University Hiroshima University

Institute for Advanced Materials ResearchInstitute for Advanced Materials Research

NHNH33 as a Hydrogen as a Hydrogen

CareerCareer

1. Energy and Environmental Issues

2. Research on Hydrogen Storage Materials

3. Characteristics of NH3

4. NH3

utilization5. Future perspective6. Summary

Table of ContentsTable of Contents

Itsukushima Shinto Shrine

Hiroshima Peace Memorial

HiroshimaUniversityHiroshimaUniversity

●Tokyo●Kyoto

●Sendai

JapanJapan

●Fukushima I Nuclear Power Plant

800km

Fossil energy economy

First Industrial Revolution （18th～19th century）

Second Industrial Revolution （End of the 19th century～Early 20th century）

Coal

History of Industrial Revolution

Oil（Natural gas）

12 billion ton of oil equivalent

Sustainable economy

Third Industrial Revolution（21st century？）

Renewable energy

Secondary energy →H2

1. Energy and Environmental Issues

2. Research on Hydrogen Storage Materials

Liquid hydrogen(20K) , 7kgH2

/100L

3.7 billion ton /yearLiquefying the hydrogen uses 30-40%

of

the hydrogen’s energy content

Hydrogen career ?

Liquid hydrogen

Honda FCX(35MPa) Toyota FCHV(70MPa)

Internal volume: 171L, 3.9kgH2

Cruising distance: 620km, Cruising distance: 830km

Internal volume: 156L, 6.1kgH2

130-160km/1kgH2

Development of FCV（2000～）

Hydrogen storage materialsToyota aims for $50,000 production hydrogen sedan by 2015

Hydrogen storage materials (1999～2012)

Evaluation and characterization of 200

kinds of hydrogen storage 

Mn

Mn

Mn

Cr

Mn

Mn

Ti

MnTi

Mn

Cr

Cr

Cr

TiCr

Ti

Cr

Cr

Cr

Mn

Cr

Mn

Hydrogen absorbing alloy

LiBH

H N

Li

Li

H

N

B

Complex hydrides

CH3

Organic hydrides

-CH3

-CH2-CH

Inorganichydrides

Porous materials

AlH3

0

2

4

6

8 NH3

BH3

0 5 10 15 20 100

10

Hydride(calculated value)H2

storage materials (experimental value)High pressure tank of 70MPa

MgH2

Mg(BH4

)2NaH‐NH3

BH3

NH3

(1MPa, 

298K, liquid)

12

∼∼Liquid H2

Ti1.1

CrMn

Super activated carbon (20K)

LiH-8/3Mg(NH2

)2

HCOOH

Gravimetric H2

density /mass%Volu

met

ric H

2de

nsity

/kg

H2/1

00L

（Pa

ckin

g ra

tio: 5

0％）

Gravimetric and volumetric H2

densities of hydrogen storage materials

Gravimetric and volumetric H2

densities of hydrogen storage materials

C10

H18

C7

H14

NH3

Maximum volumetric H2

density

Volumetric H2

density in NH3

:1.5×liquid H2

California farmer, Injection of liquid ammonia in a sugar beet field

NH3

: Inclusion of hydrogen

Renewable fuel independent of fossil fuel

3. Characteristics of NH3

Annual production of the world

153

million ton (2008)

N2

+3H2

→ 2NH3

10-25MPa, 573-823KHaber-Bosch process

$2-4/gge（2010～2011)

NH30.18kgH2

/kg material0.107kgH2

/L material

Gasoline gallon equivalent

H/M: 3,H2

:18mass%ΔH: -31kJ/molH2

H/M:2,H2

:11mass%ΔH: -285kJ/molH2

Mg(BH4

)2

NH3

H2

absorbing alloy(LaNi5

)15mass% 18mass%

1.5mass%

-57～-75kJ/molH2

-31kJ/molH2

-31kJ/molH2

H2

contentΔH

Specimen

Partial atomic charges

δ+δ−

NH3H2

O

Stable under water and oxygen

“Safety Assessment of Ammonia as a Transport Fuel”Risø

National Laboratory, Denmark (2005)

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

132�-187�-187�-157�-104�60.4�-43�

SubstanceAmmoniaNatural gasMethaneHydrogen

MethanolGasoline(92 octane)

Health311

0111

Flash point

LPG(propane)

Flammability1

44

4433

GWP: Global warming potential

GWP: 0

GWP: 21

GWP: 0

GWP: 21

Energy carrier4NH3

+3O2

→2N2

+ 6H2

O

Hydrogen carrier4NH3

→2N2

+ 6H26H2

+3O2

→6H2

O

4. NH3

utilization

NH3Energy carrierGas turbine SOFCICE vehicleHydrogen carrierFCVDomestic fuel

Liquid H2systemItem

Energy after transportation

Energy loss by transportation

(5000km)

Energy generated(Efficiency: 60％)

Plant cost /million dollars

Input electric energy

NH3

system

100

(2.5)

70.4

100

(1.6)

68.7

7400 5400

42

Energy after production 70.372.9

Preliminary calculation of energy balance

(WE-NET: 1996)

http://www.enaa.or.jp/WE-NET/report/1996/japanese/3_1.html

H2

gas turbine(100-300MW)

4.1 Large scale power generation using gas turbine（Output power

Million kW, 1000MW）

41 NH3

gas turbineenergy carrier

hydrogen carrier

32 H2

gas turbine

Combined Cycle

NH3SOFC1kW-1MWEfficiency: 60％

Fuel consumption of next�generation vehicle

Gasolinevehicle

EV FCVHybridvehicle

0

4

10

Fuel

con

sum

ptio

n/k

m/k

Wh

8

1700km1310kg

830km156L70MPa1880kg

6

2

630km88L1MPa

1300km88L1MPa

NH3hybrid Vehicl

e

790km

Calculation

Without emission of CO2

NH3Vehicl

e294kg, 24kWh

200km

Fuel consumption ∝ Tank to wheel ∝

efficiency

4.2 Next�generation vehicle development

Ammonia is both caustic and hazardous

Hybrid-

truck(controlle

d fuel)

30-40% 60%

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

1. Conversion from ammonia to hydrogen (mixture of H2

and NH3

, generation of high purity H2

) , Cold start2.

Ammonia storage materials (lower vapor pressure), Harmless

NH3

4.3 Energy and hydrogen career

Research purposes

LiH+NH3

→ LiNH2

+H2 (1)ΔH0: -43kJ/molH2

H2

generation at room temperature

523-573K, 0.5MPa, H2

flow

H2

content:8.1mass%

MHMH--NHNH33

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

NH3

LiH

A. Yamane, F. Shimojo, K. Hoshino, T. Ichikawa, Y. KojimaJ. Mol. Struct. THEOCHEM

944, 137 (9pp) (2010)

TiCl3

-doped(1mol%) LiH

Hyd

roge

n yi

eld

/%

15 255Reaction time /h

0 20100

20

40

60

80

100

Activated LiH

LiH

Hydrogen desorption curves of LiH-

NH3

system(room temperature)

(1) Conversion from ammonia to hydrogen at RT

Hydride

NH3

Conversion system between NH3

and H2

Pressure gauge 1

Pressure Gauge

2

NH3

Flow meter

Gas circulationpump

Reaction cell

Gas densitometer

Gas sampler

NH3

+LiH↔LiNH2

+H2

0.1-0.6MPa

100-900rpm NH3

flow rate～50cc/min(0°C, 1atm)

0.5gHeater50-400°C

Collaborative research with Toyota Industries

Anode3NH2

−→ 1/2N2

+ 2NH3

+ 3e−Cathode

3NH3

+ 3e−

→ 3/2H2

+ 3NH2−

3NH3

3NH2−

1/2N2

3e− 3e−

3/2H2

2NH3

H2 N2

Power

supply

AnodeCathode

Electrolysis of NHElectrolysis of NH33

ΔG0: Standard Gibbs free energy difference=13.1kJ/mol

n=3: Electron number responsible for reaction

E : Theoretical decomposition voltage

E = − ΔG0/3F + RT ln(pN21/2pH2

3/2)/nFE(H2

O)=1.23V→E(NH3

)？

N. Hanada, S. Hino, T. Ichikawa, H. Suzuki, K. Takai, Y. Kojima,

Chemical Communications, 46, 3982-3984

(2010)

NH3

→1/2N2

+3/2H2

E(NH3

)=0.038V+0.039V=0.077V(theory)

Vapor Pressure of NH3

(25 ºC )

Liquid NH3

containing electrolyte (metal amide)

0.5V(experimental)

NH3

SrTiO3

Steel ball

BaTiO3

0.6 0.8 1.0 1.2 1.4Time

/min

Inte

nsity

/arb

. uni

t

N2

H2

ATiO3

(A:Sr, Ba)Milling

We have detected hydrogen and nitrogen gas when SrTiO3

and BaTiO3

powder is mechanically milled under ammonia gas at room temperature.

B. Paik, M. Tsubota, T. Ichikawa, Y. Kojima, Chemical Communications, 46, 3982-3984 (2010)

MechanocatalysisMechanocatalysis

(2) NH3

absorbing materials

0 2 4 6 80.0

0.2

0.4

0.6

0.8

PCT curve 19℃ Liq.ammonia vapor

NH

3 Pre

ssur

e [M

Pa]

NH3 [mol/CaCl2mol]0 2 4 6 8NH3

/CaCl2

/mol/mol

NH

3pr

essu

re/M

Pa

0.8

0.6

0.4

0.2

0

Vapor pressure of

NH3

at 19°C

P-C isotherm for CaCl2

-NH3

systemP-C isotherm for CaCl2

-NH3

system

0.06MPa

ClC

a NH3

Liquid NH3Ca(NH3

)8

Cl2102kg 56kg

115g/L 107g/L

T. Aoki et ai., Abstract of MH2012, Kyoto Japan (2012)

69-63kJ/mol 42kJ/mol

Rasmus Z. Sørensen et al., J. AM. CHEM. SOC. 130, 8660 (2008)

41kJ/mol

Lower vapor pressure

Absorption energy

M >C

>Li>N

>K

ab initio molecular-dynamics (MD) simulation based on density functional theory (DFT) .

A. Yamane et ai., Abstract of MH2012, Kyoto Japan (2012)

5.Future perspective

H2

O

NH3

utilization

H2 production

NH3

production

9000km

Liq.NH3

NH3Station

NH3

power plant SOFC

N2

Passenger car

Passenger car

TruckH2

H2

e

e

NH3

Energystock

Controlled fuel

NH3

NH3

H2

Electricity

Realization of sustainable economy （renewable energy economy）

（2030）

Best mix of NH3

, H2

and electricity

Controlled fuel

1. Ammonia has advantages in cost and convenience as a fuel for vehicle, electric power plant and SOFC.

2. LiH-NH3

system with TiCl3

desorbed 6 mass% of H2

at room temperature.3.

Hydrogen gas was generated by the electrolysis of liquid ammonia.

4. We have detected hydrogen and nitrogen gas when SrTiO3

and BaTiO3

powder is mechanically milled under ammonia gas.

5. The vapor pressure of ammonia was decreased in metal chlorides.

6.Summary

NH3

economy is a practical H2

economy

Liquid HydrogenFuelfor Hydrogen Delivery

$20 million

Ministry of Education, Culture, Sports, Science and Technology(MEXT)Ministry of Economy, Trade and Industry (METI)

September 21, 2012

Emerging Fuels(DOE)http://www.afdc.energy.gov/afdc/fuels/emerging.html

Alternative Fuels ?

Acknowledgement: This work was partially supported by the “Advanced Fundamental Research Project on Hydrogen Storage Materials”

supported by NEDO

(2007-2011FY), Japan.

Staff: 6, PD: 2, M1: 4, M2: 4, D1: 1, D2: 1, D3: 3, D4: 1,D5: 1

(24)

(2012)

Thank you for your attention.Thank you for your attention.