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FUNDAMENTAL SAFETY TESTING AND ANALYSIS OF HYDROGEN STORAGE MATERIALS & SYSTEMS. D. Anton , D. Mosher, W. Lohstroh, M. Fichtner, N. Kuriyama, E. Akiba, R. Chahine, D. Dedrick. Hydrogen Storage. Compressed H 2 Gas 5-10 ksi pressures in graphite fiber reinforced epoxy composite tanks - PowerPoint PPT Presentation
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FUNDAMENTAL SAFETY FUNDAMENTAL SAFETY TESTING AND ANALYSIS TESTING AND ANALYSIS OF HYDROGEN STORAGE OF HYDROGEN STORAGE MATERIALS & SYSTEMSMATERIALS & SYSTEMS
D. Anton, D. Mosher, W. Lohstroh, M. Fichtner, N. Kuriyama, E. Akiba, R. Chahine, D. Dedrick
Hydrogen StorageHydrogen Storage
Compressed HCompressed H22 Gas Gas– 5-10 ksi pressures in graphite fiber reinforced epoxy 5-10 ksi pressures in graphite fiber reinforced epoxy
composite tankscomposite tanks Cryogenic Liquid HCryogenic Liquid H22
– Ambient pressure ultra-insulated containers with Ambient pressure ultra-insulated containers with bleed off devicebleed off device
Compressed/Cryogenic HCompressed/Cryogenic H22– Cryogenic Liquid HCryogenic Liquid H22 in a high pressure tank to in a high pressure tank to
minimize boil-off minimize boil-off AdsorptionAdsorption
– Utilizes physisorption on ultra-high surface Utilizes physisorption on ultra-high surface area species. Currently used at LN2 area species. Currently used at LN2 temperatures.temperatures.
Absorption Absorption – Utilizes chemisorption in metal, organic or Utilizes chemisorption in metal, organic or
complex compoundscomplex compounds
Typical Chemisorption Typical Chemisorption ReactionsReactions
LaNi5H6 LaNi5 + 3H2 Mg2NiH4 Mg2Ni + 2H2
Metal Hydrides
NaAlH4 1/3Na3AlH6 + 2/3Al + H2 NaH + Al + 3H2 Complex Metal Hydrides
2LiBH4 + MgH2 2LiH + MgB + 4H2
8LiH + 3Mg(NH2)2 Mg3N2 + 4Li2NH + 8H2
Destabilized Complex Metal Hydrides
AlH3 Al + 3/2H2NH3BH3 BiNjHk + xH2 Chemical Hydrides
US-DoE Technical US-DoE Technical TargetsTargets
TargetTarget 20072007 20102010 20152015Wt % H2 (Useable) 4.5 6 9
Vol. Cap. (kg H2/L) 0.036 0.045 .081
Cycles 500 1000 1500
Minimum rate (g/s)/kW .02 .02 .02
Minimum/Maximum pressure (atm) [FC]
8/100 4/100 3/100
Minimum/Maximum ambient temperature (°C)
-20/50 -30/50 -40/60
Start time to full flow (s) 4 4 0.5
System fill time (min) 10 3 2.5
Safety Meet or exceed applicable standards
ObjectiveObjective
To To fundamentallyfundamentally understand the safety issues understand the safety issues regarding solid state hydrogen storage regarding solid state hydrogen storage systems through:systems through:
Development & implementation of Development & implementation of internationally recognized internationally recognized standard testing standard testing techniquestechniques to quantitatively evaluate both to quantitatively evaluate both materials and systems. materials and systems.
Determine the fundamentalDetermine the fundamental thermodynamics thermodynamics & chemical& chemical kineticskinetics of environmental reactivity of environmental reactivity of hydrides. of hydrides.
Develop Develop amelioration methods and systemsamelioration methods and systems to to mitigate the risks of using these systems to mitigate the risks of using these systems to acceptable levels. acceptable levels.
Task 1: Standard TestsTask 1: Standard Tests
• FlammabilityFlammability Flammability TestSpontaneous IgnitionBurn Rate
DOT/UN Doc., Recommendations on the Transport of Dangerous Goods, Manual of Tests and Criteria, 3rd Revised
Ed., ISBN 92-1-139068-0, (1999).
• Standard Test Method for Pressure and Rate of Pressure Rise for Combustible Dusts (ASTM E1226)(ASTM E1226)
Pmax & (dP/Dt)max
Min. Exp. Conc.Min. Ignition EnergyMin. Ignition Temp.Min. Dust Layer Ignition Temp.
•Water ContactWater ContactImmersionSurface ExposureWater DropWater Injection
• MechanicalMechanical•Impact•Expansion
Task 2: Thermodynamics Task 2: Thermodynamics & Chemical Kinetics& Chemical Kinetics
Quantitative studies will be performed to understand the chemical kinetics and thermo-chemical release of these reactions with air, oxygen and water as both liquid and vapor as a function of temperature.
Task 3: Risk MitigationTask 3: Risk Mitigation
System risk analyses will be performed and methods of System risk analyses will be performed and methods of mitigating these risks including exposure to air and humidity mitigating these risks including exposure to air and humidity will be investigated. will be investigated.
No
Mitigation
WithMitigation
Task 4: Prototype Task 4: Prototype System TestingSystem Testing
Evaluation tests on risk Evaluation tests on risk mitigations strategies will be mitigations strategies will be performed on sub-scale performed on sub-scale prototype storage systems to prototype storage systems to validate their efficacy. validate their efficacy.
Materials Test PlanMaterials Test Plan
NaAlHNaAlH44+2%TiCl+2%TiCl33 LiH+MgNHLiH+MgNH22
MgMg22NiHNiH44
LaNiLaNi55HH66
NaAlHNaAlH44+2%TiCl+2%TiCl33 LiH+MgNHLiH+MgNH22
MgMg22NiHNiH44
LaNiLaNi55HH66
2LiBH2LiBH44+MgH+MgH22
NHNH33BHBH33
Activated Carbon Activated Carbon AlHAlH33
2LiBH2LiBH44+MgH+MgH22
NHNH33BHBH33
Activated Carbon Activated Carbon AlHAlH33
Use Particle Size & Use Particle Size & PackingPacking
Discharge StateDischarge State– Fully ChargedFully Charged– Partially DischargedPartially Discharged– Fully DischargedFully Discharged
Materials Prep PlanMaterials Prep Plan
UTC 1UTC 1stst Prototype 1kg H Prototype 1kg H22 Storage SystemStorage System
316 SS tubing for ParaTherm MR oil
4% dense aluminum foamwith 50% dense Ti catalyzed
NaAlH4 powder
316 SS liner
316 sintered SS filter
316 SS end closure to facilitate loading and inspection
One end closed carbon fiber composite containment
Rated to 1500psi
Burn Rate TestBurn Rate Test
0 sec. 2.97
6.90 11.09
Partially Discharged CCH#0-33
Water Drop TestWater Drop Test
0 sec. 0.11
0.12 0.15
Partially Discharged CCH#0-33
Water DripWater Drip
0 sec. 0.14
0.17 30.03
Partially Discharged CCH#0-33
Flammability Test Flammability Test Results Results (DOT/UN)(DOT/UN)
Class 4.3,Class 4.3, Packing Group IIPacking Group II
Test Method Ref: 100% 33% 0%UN33.
Prelim. Screening 2.4.3.1 Yes, Flammable Solid Yes, Flammable Solid Yes, Flammable Solid
Burning Rate 2.4.3.2 51 mm/sec 222 mm/sec 27 mm/sec
Burning Rate, 80C Note 1 127 mm/sec spontanious ignition 40 mm/sec
Spontaneous Ignition, R.T. 3.1.4.3 6 Tries, Not Pyrophoric 6 Tries, Not Pyrophoric 6 Tries, Not Pyrophoric
Spontaneous Ignition, 80C Note 1 6 Tries, No Ignition 1 Try, Ignited 6 Tries, No Ignition
Dangerous Self-Heat, 100C 3.1.3.3 Yes, Dangerous Yes, Dangerous Not Dangerous
Dangerous Self-Heat, 120C 3.1.3.3 Not Tested (Note 2) Not Tested (Note 2) Not Dangerous
Dangerous Self-Heat, 140C 3.1.3.3 Not Tested (Note 2) Not Tested (Note 2) Yes, Dangerous
Dangerous When Wet 4.1.4.3 Yes, Class 4.3, Pack Gp 1 Yes, Class 4.3, Pack Gp 1 Yes, Class 4.3, Pack Gp 1Note 1: This is not a UN standard test. We want to know what happens when this material is spilled at operating
temperature of 80C. All other details are per UN burn rate and spontaneous ignition test specifications.
Note 2: This test was not necessary, since this material had already shown dangerous self-heating at 100C.
SAFETY TESTING TABLE OF RESULTS
Air Exposure TestAir Exposure Test
0:00min.
24:05 80oC25:10 smoke observed
26:55 fire 34:15 max fire
Partially Discharged CCH#0-33
Gasoline Burn RateGasoline Burn Rate
0 sec. 0.03
0.75 0.88
Dust Explosion Test Dust Explosion Test ResultsResults(ASTM E1226, E1515, E2019 & (ASTM E1226, E1515, E2019 & E1491)E1491)
Test Materials Reference Materials
NaAlH4 NaH+Al Pitt. Seam Coal Dust
Lycopodium Spores
Pmax bar-g
11.9 8.9 7.3 7.4
Rmax bar/s
3202 1200 426 511
Kst bar-m/s
869 326 124 139
Dust Class
St-3 St-3 St-1 St-1
MEC g/m3
140 90 65 30
MIE mJ <7 <7 110 17
Tc oC 137.5 137.5 584 430
Pmax = maximum explosion pressure, Rmax = pressure rise maximum, Kst = maximum scaled rate of pressure rise, MEC = minimum explosive concentration, MEI = minimum spark ignition energy, Tc = minimum dust cloud ignition temperature
CommunicationCommunication
A WEB site will be established to communicate finding and results to the general public as expeditiously as possible.
ConclusionConclusion
The risks associated with The risks associated with manufacturing, handling, utilization manufacturing, handling, utilization and disposal of solid state hydrides and disposal of solid state hydrides needs to be quantitatively identified.needs to be quantitatively identified.
A thorough risk assessment of solid A thorough risk assessment of solid state hydrogen storage materials and state hydrogen storage materials and systems needs to be performed.systems needs to be performed.
Engineering risk mitigations strategies Engineering risk mitigations strategies need to be identified and tested to need to be identified and tested to bring the risks to tolerable levels for bring the risks to tolerable levels for commercial application.commercial application.