Dihydrogen Storage and distribution

Dihydrogen

Storage & distribution

Frédéric Stevens

Thesis seminar

LCIS-GREENMat

Presentation’s main points



_Introduction



_{Targets and problems}



_{Storage & Distribution method}



_{Materials for solid storage}



_Conclusions

Cavendish Henry : Inflammable air (1766)

Introduction

Hydro = water



_Etymology

Luft erhebt sich und bricht herfdir gleichwie ein Wind

(‘Archidoxa‘, Paracelsus (1493-1541))

Lavoisier Antoine: Hydrogen (1783) 2 H₂ + O₂  H₂O

Dihydrogen



_History

Di

hydrogen

Di

hydro

gen

4

Introduction

Internal combustion engine (1806 Rivaz)

Hydrogen maser 1952 :Pr Robert H. Dicke Hydrogen fuel cell

(W. R.G roove 1839)

5 1923 - BASF C₂H₅-S-C₂H₅ + 2 H₂  H₂S + 2 C₂H₆ 1949 - Hydrodesulfuration

Introduction



_{Popular reactions}

6

Ammoniac production; 34.00%

15.00% 51.00%

World consumption of dihydrogen in chemical industry and refinery1

57,6.10

ton/year

Introduction

7

Phase diagram

H

+ ½ O

 H

O

∆H= -285,97 kJ/mol at 25°C

Fuel Type

Energy Content (kJ/g)

dihydrogen

120

Natural gas

50

Kerosene

46

Methanol

20

H

CH

Flammability limit

4-76%

5-15%

density

0,09 kg/m³

0,67 kg/m³

Introduction

Why H

is not use as fuel for our cars?

8

 Production

 distribution and storage

H

is too volatile  unexploitable quantities in the nature

 Must be produced

9

10

Produced from other compounds

CH

H

O

C

H

11

Production: Synthesis

Steam reforming

CH

+ H

O CO + 3

⇌

H

CO + H

O → CO

+

H

C

H

+ n/2 O

→ nCO

+ m/2

H

CO

+ CH

→ 2CO + 2

H

3C + O

+ H

O → 3CO +

H

2H

O + Energy → O

+ 2

H

Electrolysis E= external applied voltage Thermolysis E= heat

Photobiological water splitting E= sun

Catalyst = biomolecule Photocatalytic water splitting E= sun

Catalyst = inorganic compound Thermochemical process E= heat + other molecules

12

Targets & Possibilities

Immobile and huge quantities

Pipelines

13

Pipelines

 _{Old technology (1938)}

 _{Underground steel pipes (50 years old)}  _{No famous damage registered}

 _{For more than 1 ton}  _{P= 3.4 to 100 bars}  _{Ø = 10 – 300mm}  _{Under development:}

 _{To reduce the cost}

 _{To reduce the weakening of steel provoked by}

H2

 _{To improve the soldered joints}

 _{To improve the compression technology} USA: 1150 km

H

O

N

14

Targets & Possibilities

Mobile and/or limited quantities

Immobile and huge quantities

Pipelines

< 100kg 100 kg - 1 ton and more

100 kg -1 ton

15

Requirements for cars

16

Summary of the requirements

Cars



_{500km /full tank}



_{Storing device (to compete fossil fuel)}



6kg d’H

/100kg of storing device

45kg d’H

/m³ of storing device



Working temperature: -30°C to 150°C

Suitable pressure

17

Solid

High pressure hydrogen storage

Gas, supercritical fluid

Cryogenic hydrogen storage

Liquid

Possibilities

Phase diagram

18

Gas storage: Composite pressurized tank

Internal pressure: 700 bar but still too voluminous

most developed technology

19

 70.8 kg/m3

x Liquefaction require too much energy

x Loss of efficiency due to evaporation

x Voluminous insulation

Liquid storage:

Cryogenic hydrogen storage

Organic liquid

x Rest products must be recycled in plants for rehydrogenation

x Conversion Yield <<100%

x Expensive

x Dirty

Conclusions

Unprofitable from practical

and economical point of view

at least for on-board storage

system

20

Solid state hydrogen storage



_{Adsorbed on surfaces}



_{metallic glasses}



_{carbon-based compound}



_Zeolithe



_MOFs



_Structural



_hydrides

21



Zr

Cu

Ni

Ti

Al

alloy*

Solid state hydrogen storage

Adsorption on surface

Morphology of metallic glass

* Cheng 2009

•

_{Amorphous storage capacity ~ micro-structure}

22

Solid state hydrogen storage

Adsorption on surface



_conclusion

•

_{partially controlled porosity storage capacity}

x

_{1315 m²/g 2 wt. % (not enough)}



_Synthesis

1)

Anaerobic pyrolysis of wood or other C-based

compound

2)

* Physical Activation: 950°C + pressurized water

steam  small pores

* Chemical activation: 450°C + H

PO

 big pores

23

Solid state hydrogen storage

Adsorption on surface



_{Native element}



_{No intercalation}

Graphite

x

1315 m²/g

 3,3 wt. %

24

Solid state hydrogen storage

Adsorption on surface

Carbon Nanotube



_Synthesis



_{A) High Temperature}

vaporisation  condensation



_{Electric arc, T= 6000°C}



_{Laser, T= 4800°C}

SWCNT (zig-zag, armchair, chiral) MWCNT graphite plasm a Pyrolysis (750°C) + air MWCNT

25

CH₄,C₂H₂, C₆H₆, … +

Metallic precursor (Co, Ni, Fe, Pt or Pd)

Ar

800°C



_{B) CVD}

Solid state hydrogen storage

Adsorption on surface

Carbon Nanotube



_{C) Catalysis}

CO, C₂H₂, CH₄, …

Fe, Ni,Co,… Fe, Ni,Co,… Pyrolysis

700-1200°C

MWCNT/Co SWCNT

26

Solid state hydrogen storage

Adsorption on surface

Carbon Nanotube

dissolution du template Al

27

SWCNT and MWCNT (zig-zag)

Carbon-based compound

Solid state hydrogen storage

Red circle = CNT

Blue triangle = Nanostructured carbon sample

Adsorption on surface

28

Solid state hydrogen storage

Adsorption on surface

Zeolithe



Aluminosilicate: [Al

Si

O

]

x-

_Variables



_{Pore size  size of organoamonium}



_{Si/Al ratio}

Na₂SiO₃ + Al(OH)₃ Low Si/Al ratio

(Me₄N)OH 100-200°C

High Si/Al ratio (n-Pr₄N)OH 100-200°C Sodalite Na₆Al₆Si₆O₂₄.2H₂O ZSM-5 Na₃Al₃Si₉₃O₁₉₂.16H₂O



_Synthesis

29

Solid state hydrogen storage

Adsorption on surface

Zeolithe

Sodalite:

Zeolite + H₂ Zeolite-H₂ High P and/or Low T

High T and/or Low P

1,1 wt. % < 6 wt. % (not enough) ZSM-5 NaX

70bar, 20°C

30

Solid state hydrogen storage

Adsorption on surface

MOFs

31

N₂- and H₂-adsorption isotherms (Mg-MOF, Basolite M050)

Solid state hydrogen storage

Adsorption on surface

MOFs

Huaxue 2011

Best MOFs for hydrogen storage:- Mg - smallest pores - 77K



_{Simple Metal hydride: MHx where M = Li, Na, Mg}

32

Solid state hydrogen storage

Structural

Hydrolysis MHx + xH

O  M(OH)x + x

H

reversibility protected by US patent

Pyrolysis

2M + x

H

 2MH

x

Reversibility for MgH

: 300°C, 1 bar

x

_{Kinetic too slow}



7,6 wt. %

33



Complex metal hydride: MXH

where X=trivalent element

Metal

Li

Na

K

T

100°

C

100°

C

300°

C

T

120°

C

150°

C

340°

C

T

650°

C

425°

C

-Wt.%

10,6

7,5

5,7

Wt. %

7,9

5,6

4,3

Global reaction

3 MAlH

 3 M + 3 Al + 6 H

Reversible reaction

3 MAlH

 3 MH + 3 Al + 9/2 H

Solid state hydrogen storage

Structural

Alanates (MAlH

)

Borohydrides (MBH

)

34



_{Intermetallic compounds}

Solid state hydrogen storage

Structural

Metal

Hydride

Mass %

Pd

PdH

0.56

LaNi

LaNi

H

1.37

ZrV

ZrV

H

3.01

FeTi

FeTiH

1.89

Mg

Ni

Mg

NiH

3.59

TiV

TiV

H

2.6

35

Solid state hydrogen storage

Conclusion

Adsorption on surface

Small pores (high specific surface)

Mg

In the structure

36

Fuel Type

Energy Content (kJ/g)

dihydrogen

120

Conclusion

?

37

Conclusion

Pressurized Gas

Liquid H

Solid state storage

Adsorption on surface _{In the structure}

>700 bar

Volume not suitable

metallic glasses

carbon-based compound Zeolite

MOFs

Small pores (high specific surface) Mg

Best results with complex metal hydride

Simple metal hydride Complex metal hydride Intermetallic

38

Thanks for your attention !

If « Water is life  » and « hydrogen generates water »… Does hydrogen generate life?