NH 3 BH 3 TGA Comparison
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Transcript NH 3 BH 3 TGA Comparison
Hypothetical Accident Scenario
Modeling for Condensed Hydrogen
Storage Materials
Charles W. James Jr, Matthew R. Kesterson, David A.
Tamburello, Jose A. Cortes-Concepcion, and Donald
L. Anton
Savannah River National Laboratory
September 14, 2011
1
Objectives
The objective of this study are to understand the safety issues
regarding solid state hydrogen storage systems through:
Development & implementation of internationally recognized
standard testing techniques to quantitatively evaluate both
materials and systems.
Determine the fundamental thermodynamics & chemical kinetics
of environmental reactivity of hydrides.
Build a predictive capability to determine probable outcomes of
hypothetical accident events.
Develop amelioration methods and systems to mitigate the risks of
using these systems to acceptable levels.
2
Modeling and Risk Mitigation
Accident Scenario (from UTRC risk assessment):
Storage system ruptured and media expelled to
environment in either dry, humid or rain conditions.
Risk: Under what conditions will there be an ignition
event? What are the precursors to the ignition
event?
Punctured / Ruptured Tank
Penetration
Storage
Vessel
Temperature
Humidity
Water presence
Media geometry
Spilled Media
Media Temperature Depends on
Ta, Ti, dH/dt, keff, cpeff, …
Heat Generated by
Chemical Reaction Volume
H2
Ambient Atmosphere at Temperature
Contains O2, N2, CO2 & H2O(l), H2O(g)
Possible Water Film
Liquid
Water
y
t
Surface
x
3
Groundwork - Ammonia Borane
United
Nations
UN Test
Result
Pyrophoricity
Pass
Self-Heat
Fail
Burn Rate
Fail
Water Drop
Pass
Surface
Contact
Fail
Water
Immersion
Pass
4
NH3BH3 TGA Experimental Results
TGA experiments were
conducted in an Argon
atmosphere.
First and second
dehydrogenation
reactions occurred
5
NH3BH3 TGA Numerical Simulation
COMSOL model:
2-D, axisymmetric
Conduction, Convection, & Radiation Heat Transfer
Weakly Compressible Navier-Stokes Equations
Maxwell-Stefan Species Convection and Diffusion
Ea
Reaction Kinetics:
R T
Reaction 1-2:
Ea
= 128 [kJ/mol]
A0
= 3.836x10-11 [1/s]
c
= 0.1573 [1/K]
mol% = 14% borazine*
R Ae
Argon
Gas
Phase
5 mm
A A0 ecT
Sample
1 mm
1 mm
Reaction 3-4:
Ea
= 76 [kJ/mol]
A0
= 106 [1/s]
c
=0
mol% = 41% borazine*
6
NH3BH3 TGA Comparison
Theoretical curve only
takes into account H2
reaction (no other
products)
Additional 14 mol-%
and 41 mol-% material
loss during reaction
(for simplicity, all
losses assumed
borazine)
7
NH3BH3 Calorimetry Simulation
Setaram C-80 Calorimeter options :
-Dry Air/Argon
-Air/Argon with water vapor
-Temperature
Wall temperatures were ramped at
0.5 ºC/min
Atmosphere: Dry Air
Air
Phase
Sample
Sample
(5-20 mg)
Not to scale
8
NH3BH3 Calorimetry in Dry Air
2.5
Experimental Data
Simulation
Normalized Heat Flow (mW/mg)
2
Furnace ramped to
150ºC
1.5
Additional exothermic
heat flow during the
temperature ramping
1
Endothermic dip due
to foaming and
melting of the material
for T > 110 oC
0.5
0
0
0.5
1
1.5
2
2.5
3
3.5
4
4.5
5
Time(h)
9
Accident Scenarios
50 grams of NH3BH3 was assumed to collect on the ground following a Gaussian
distribution.
Mesh consisted of over 9,000 triangular elements
Scenario 1
A heat source (ex. Car muffler) sits 4 inches above the NH3BH3.
Multiple iterations of Scenario 1 were simulated modifying the heat source temperature from
225ºC to 300ºC
Scenario 2
The NH3BH3 falls onto a heated surface
Multiple iterations of Scenario 2 were simulated modifying the heat source temperature from
100ºC to 125ºC
Top Surface
1.5cm
t
Bottom Surface
20 cm
10
Results – Overhead Heating
Reactions 1 and 2 went to completion
Reactions 3 and 4 started, but the reaction rate was slow.
Highest overhead temperature was 300ºC.
Simulations were initiated at higher temperatures, but the timestep needed
by the solver was too small for the simulation to conclude in a reasonable
timeframe.
11
Results – Overhead Heating Continued
Above 250ºC, the first reaction goes to
completion under 1 hour.
At 300ºC, the first reaction is
completed within 11 minutes
Below 250ºC, the second dehydrogenation
does not start within the simulation time.
At 300ºC, the second
dehydrogenation reaction is
progressing (slowly).
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Results – Ground Heating
Ground temperatures above 125ºC were not modeled due to the high rate
of hydrogen release and the resulting decrease in simulation timestep.
Initial release of hydrogen occurs at the outer rim of the NH3BH3 mound.
The maximum mound temperature progresses inward toward the center
axis, at which point high pressure spikes due to hydrogen release were
observed.
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Results – Ground Heating
At 125ºC, the first
dehydrogenation reaction
proceeds quickly.
First reaction goes to
completion within 2
minutes.
Second dehydrogenation
reaction starts, but proceeds
very slowly due to the ground
temperature being held at 125ºC
14
Conclusions
COMSOL Multiphysics models successfully modeled
dehydrogenation of Ammonia Borane as seen in the TGA and
Calorimetry experimental comparisons.
Additional models were developed to simulate the release of
hydrogen in postulated accident scenarios.
Temperatures above 125ºC (below heat) and 300ºC (above
heat) yielded extremely fast hydrogen release rates.
High pressure spikes were observed during the hydrogen
release which could be a precursor to the foaming seen
experimentally.
15
Acknowledgements
Special Thanks to the following people:
SRNL
Bruce Hardy
Stephen Garrison
Josh Gray
Kyle Brinkman
Joe Wheeler
Department of Energy
Ned Stetson, Program Manager
THIS WORK WAS FUNDED UNDER THE U.S.
DEPARTMENT OF ENERGY (DOE) HYDROGEN
STORAGE PROGRAM MANAGED BY DR. NED
STETSON
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