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Revised Hydrolysisofcomplexhydridesforhydrogengeneration 130423222627 Phpapp02
Revised Hydrolysisofcomplexhydridesforhydrogengeneration 130423222627 Phpapp02
Submitted
Submittedbyby-Debesh
DebeshSamanta
Samanta
(Roll
(RollNo.
No.12I170014)
12I170014)
Under
Underguidance
guidanceof
of
Professor
Pratibha
Professor Pratibha
Debesh SamantaSharma
Sharma
12I170014
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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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)
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
H = -75kJ/mol H2
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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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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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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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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
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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-
k
n
a
h
T
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