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Hydrolysis of Complex

Hydrides for Hydrogen


Generation

Submitted
Submittedbyby-Debesh
DebeshSamanta
Samanta
(Roll
(RollNo.
No.12I170014)
12I170014)

Under
Underguidance
guidanceof
of
Professor
Pratibha
Professor Pratibha
Debesh SamantaSharma
Sharma
12I170014

Department of Energy Science & Engineering


Department of Energy Science & Engineering
INDIAN INSTITUTE OF TECHNOLOGY BOMBAY
INDIAN INSTITUTE OF TECHNOLOGY BOMBAY
April, 2013
April, 2013

Introduction
Renewable energy carrier.
Hydrogen on combustion produces clean
exhaust.
Very high energy density (142MJ/kg , around
three times higher than that of petroleum, 47
MJ/kg).
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Different types of possible hydrogen storage and


issues related to them.
Gaseous storage :
Very high pressure
Low volumetric storage density
Very high diffusivity of H2 amd metal embrittlement.
Liquid storage :
Very low boiling point of Hydrogen (20 k)
The refrigerator system is energy intensive process.
boil off losses.
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Advantages of solid storage


The drastic decrease in safety risk.
Easy to initiate the reaction.
Long time storage.

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Solid hydrides used in hydrolysis


Metal organic frameworks (MOF), carbon
nano-tubes, nonporous materials, Pd etc.
The metal hydrides alloys like, MgH2, LaNi5,
TiNi, NiFe.
Light metal complex hydrides

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Why complex hydrides?


Advantage of light metal complex hydrides
low molecular weight.
capability of carrying up to 4H Solubility in water.
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Why hydrolysis?
Thermolysis:
Advantage-Volumetric storage density is
higher
Limitation- Demands a very high temperature.
Hydrolysis:
Reaction starts even in room temperature.
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DOE target
Target

2010
(new)

2010 (old)

2015
(new)

2015
(old)

Ultimate
Full Fleet

System
Gravimetric
Density
(% wt)

4.5
(1.5
kWh/kg)

6
(2.0
kWh/kg)

5.5
(1.8
kWh/kg)

9
(3
kWh/kg)

7.5
(2.5
kWh/kg)

System
Volumetric
Density
(g/L)

28
(0.9
kWh/L)

45
(1.5
kWh/L)

40
(1.3
kWh/L)

81
(2.7
kWh/L)

70
(2.3
kWh/L)

System Fill Time


for 5-kg fill,
min (Fueling
Rate, kg/min)

4.2 min
(1.2
kg/min)

3 min
(1.67
kg/min)

3.3 min
(1.5
kg/min)

2.5 min
(2.0
kg/min)

2.5 min
(2.0
kg/min)

Source: DOE targets for onboard Hydrogen storage systems for light-duty vehicles: current R&D focus is on 2015 targets with potential to meet
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ultimate targets. http://www1.eere.energy.gov/hydrogenandfuelcells/storage/pdfs/targets_onboard_hydro_storage.pdf.
accessed on 08-Apr-13

Hydrolysis of complex hydrides


NaBH4 hydrolysis
NaBH4 + 2H2O NaBO2 + 4H2

H = -75kJ/mol H2

If 1 gm of NaBH4 is fully ionized it produce 2.37 l of


hydrogen at STP.
GSD is 10.8wt% which is greater than the DOE
target.
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NH3BH3 hydrolysis
NH3BH3 + 2H2O NH4+ + BO2 - + 3H2
Gravimetric hydrogen densities -19.6 wt%
LiBH4 hydrolysis
LiBH4 + 4H2O LiOH + H3BO3 + 4H2
LiBH4 + 2H2O LiBO2 + 4H2
Gravimetric hydrogen densities -18.5 wt.%
Volumetric hydrogen densities -121 kg H 2/m3
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N2H4BH3 hydrolysis
N2H4BH3 + 2H2O catalyst N2H5BO2 + 3H2
Gravimetric hydrogen densities 15.4 wt%
MgH2 hydrolysis
MgH2 + 2 H2O 2 H2 + Mg(OH)2
Gravimetric hydrogen densities 7.66%
LiAlH4 hydrolysis
LiAlH4 + 4 H2O LiOH + Al(OH)3 + 4 H2
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Catalytic research
The catalysts generally used in hydrolysis can
be classified as
Transition metal or non-noble metal catalysts
Noble metal catalysts

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Catalytic researches on NaBH4


Non-noble metal catalysts
Most effective
Cobalt (II) chloride followed by Nickel(II)
And Iron, Manganese Chloride.
Cobalt mainly alloy with boron.

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Effect of introduction of other materials


Introduction of other elements into Co-B
catalysts increases its activity.
Reason(s)

An increase in electron density of the


metallic Co active site.

Surface area increases because the


additive metals inhibit Co agglomeration.
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Stability of Catalyst
Example
a filamentary Ni catalyst is studied over 200
catalytic cycles, and retained 76% of its initial
activity.
Reason:
Gradual formation of a film, consist of
hydrated borax (Na2B4O7.10H2O) and boron
oxide (B2O3), on the catalyst surface.
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Noble metal catalyst

Higher concentration of NaOH stabilizer in


solution decreases the activity of Ru. So Ru-based
catalysts may not be the most ideal choice.
The Pt catalyst loaded on LiCoO 2 - one of the
most efficient catalysts for NaBH4 hydrolysis.
The most active catalyst reported is Rh loaded on
TiO2
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Catalytic research on NH3BH3


Non-noble metal catalyst
1. Co, Ni and Cu supported catalyst- the most catalytically
active.
2. supported Fe is catalytically inactive.
3. the amorphous Fe nano-particles form in situ in presence
of NaBH4 show exceptionally high catalytic activity .
Reasons(3)
.much greater structural distortion
.much higher concentration of active sites for the catalytic
reaction
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Noble metal-based catalysts


The 20 wt% Pt/C catalyst shows the super high
activity and the reaction is completed in less
than 2 min.
Reason
reduction of Ptn+ (n = 4, 6) to Pto during the
course of the reaction,
Rh[(1,5-COD)(-Cl)]2 and Pd black have
lower activity and some noble metal oxides
(RuO2, Ag2O, Au2O3, IrO2) are almost inactive.
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Issues related with hydrolysis


Water handling
Catalytic cycle
Reversibility of the reaction
Heat management
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Water handling
NaBH4 + 2H2O NaBO2 + 4H2 + heat
NaBH4 + (2 + x) H2O NaBO2xH2O + 4H2 + heat
where x is the hydration factor.
In practice, the hydrated by-product is usually either
NaBO22H2O or NaBO24H2O, which requires an
excess of water.

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Catalytic cycle
The activity loss in case of noble metal catalyst is
very much lower than that of non-noble metal
catalysts.
Reason of decrease in activity:
In case of NaBH4 it is the gradual formation of a
film, consist of hydrated borax (Na 2B4O7.10H2O)
and boron oxide (B2O3), on the catalyst surface.
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Reversibility of the reaction


More the reversibility of the reaction cost of the
hydrolysis will be lower.
NaBO2 + 2MgH2
NaBO2 + 2CH4

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NaBH4 + 2MgO
NaBH4 + 2CO + 2H2

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Issues at a glance
Issue:
Cost

Issues:
Catalytic reactivity
Catalytic durability
Catalyst cost

Issues:
Recycling
Solubility

NaBH4 + (2 + x) H2O NaBO2xH2O + 4H2 + heat


Issues:
Excess water
Storage capacity
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Issue:
Heat
management

Conclusion
Boron based compound are dominating in the process
of hydrogen generation.
low molecular weight.
capability of carrying up to 4Hd-

The non-noble metal catalysts have been developed


with activity of similar level of noble metal catalysts.
A lower-cost alternative.
There are other issues like water handling, recovery of
reactant etc.
Hydrolysis of NaBH4 - exothermic process and the heat
must be controlled.
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k
n
a
h
T
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