Using Metal Hydride to Store Hydrogen - Higher Intellect Metal... · 2012. 10. 1. · Hydrogen...
Transcript of Using Metal Hydride to Store Hydrogen - Higher Intellect Metal... · 2012. 10. 1. · Hydrogen...
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Using Metal Hydride to Store Hydrogen
L. Kit HeungSavannah River Technology Center
Fuel Cells 2003 - Third Annual BCC ConferenceStamford, CT
March 31 - April 1 2003
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Outline
• Challenges of hydrogen storage & its importance to the fuel cycle
• Comparing present storage methods from energy point of view
• Challenges of using metal hydrides for hydrogen storage
• Metal hydride vessel design• Demonstrated applications: city bus & utility
vehicle• Summary
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Challenges of Hydrogen Storage• Low energy content (by volume) compared to hydrocarbon fuel
H2 CH4 C8H18 H2 : C8H18
Heat of combustionMJ/kg 120 50 45 2.7:1
Heat of combustionMJ/liter at ambient 0.011 0.036 31.4 0.00035:1
Heat of combustionMJ/liter at liquid state
8.5(-253 oC)
20.7(-161 oC) 31.4 0.27:1
Density at ambientg/liter 0.09 0.072 703 1:10,000
Density at liquidkg/liter 0.071 0.415 0.703 0.1:1
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Importance of Hydrogen storage
Production On site storage Transportation Station
storageOnboard storage
EnergyIn
WorkDone
Energy CycleEfficiency
Work Consumed
Energy In Work Done
ProductionStorageTransportationConversion ….
Efficiency =Energy In - Consumed
Energy In(Must > 0)
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Present Storage Options
• Compressed hydrogen (5,000; 10,000 psi)• Liquid hydrogen (-253 oC)• Adsorbed hydrogen (MH, others)
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Energy to Compress H2
Adiabatic Compression of Hydrogen
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Final Pressure, atm
Com
pres
sion
E
nerg
y, M
J/kg
0%
10%
20%
30%
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50%
Ene
rgy
Use
d to
LH
V
Eff .:H2 to electric 60%, compressor 85%HHV=61,000 Btu/lb (141 MJ/kg)LHV=51,600 Btu/lb (120 MJ/kg)
5k psi, 36 MJ/kg
10k psi, 47 MJ/kg
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Energy to Liquefy H2
Theoretical:Gas from 25 C to 20 K: 2.94 MJ/kgGas to liquid @ 20 K: 0.45 MJ/kgTotal: 3.4 MJ/Kg (MJ=1,055 Btu)
Actual:Refrigeration efficiency: 7.2 %*Energy for refrigeration: 0.45/7.2% = 47 MJ/kgVaporization & warm up: 3.4 MJ/KgTotal: 50.4 MJ/kg (42% of LHV)
* Reversed Carnot cycle: T1/(T2-T1) = 20/(298-20) = 7.2%
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Energy to Operate Metal Hydride
M + 1/2 H2 MH + EnergyT, P
Compress H2 to 20 atm: 12 MJ/kg
Heat of absorption = ~ 7 kcal/mol (14.6 MJ/kg)
Refrigeration for 10 oC COP = 5
Cooling energy: 14.6/5 = 3 MJ/kg
Energy for desorption: 0 (use waste heat)
Total: 15 MJ/kg (12.5% LHV)
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Comparing Storage OptionsGas
Hydrogen(340-atm)
LiquidHydrogen
MetalHydride
EnergyRequired
MJ/kg36 50 15
% LHV 30 42 13
Conditions very high P very low T moderate P& T
Hydrogendensity,kg/liter
0.03 0.07 ~0.06
Hydrogenwt% 100 100 ~1.5
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Using MH to Store Hydrogen
• Advantages:– Low operation energy– High density without high pressure & low temp
• Disadvantages:– Heavy (low wt% hydrogen)– Sensitivity to impurities
• R&D Needed:– Lighter material (higher wt% hydrogen)– Resistance to impurities
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Challenges of Using MH
• Fines confinement• Expansion & Contraction• Hydrogen density - gravimetric & volumetric• Heat transfer
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Fines Confinement• Filter of proper pore size and area must be used. (10 µ, 5 cm2/kg H2)
mm size particle after 1 absorption
After 10 absorptionsparticles size ~10 micron
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Expansion/ContractionStress on Container Wall
Effect of Metal Hydride Loading on Wall Stress
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Hydrogen to Metal Atomic Ratio, H/M
Stre
ss, M
Pa
85% 95% 100%
Reference:Mckillip et al, Fusion Technology, vol.21, March 1992, p1011.
Max. stress
Loading
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Gravimetric and Volumetric Densities
Hydrogen Content in Materials
0.01
0.1
1
0.01 0.1 1
Hydrogen wt. fraction, g/g
Hyd
roge
n de
nsity
in b
ulk,
g/c
c
5kpsi GH
SHLH
LaNi5H6GfE C5H3FeTiH2
NaAlH4 totalNaAlH4 1st step
5kpsi CH4
GasolineEthanolMethanolPropane
MgH2
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Heat TransferRefueling rate function of coolant rate & hydrogen pressure
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Time, min
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3.1 lpm400 psig
17.4 lpm400 psig
26 kg MH in 3.5 diameter bed w ith Al foams
17.4 lpm200 psig
1.1 lpm350 psig
*
*
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Design of MH Storage Vessel
H2
Coolant
FilterCoolant tubeAluminum foamDivider plate
Metal hydride powder
US patent 6,015,041EP 0 891 294 B1
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Demonstration of Storage Vessel
Hydrogen storage vessels
IC engine Generator Power
Control
Batteries
AC motor Wheels
170 kW70 kW230 kW (6 kg/hr)
• IC engine at high efficiency • Ultra low emission
Advantages60 kW
Half of 15-kg hydrogen
City transit bus with hydrogen powered IC-generator hybrid (33-ft, 27 passenger)
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Metal Hydrides Demonstrated
Desorption Isotherms
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Atom Ratio, H/M
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rptio
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essu
re, k
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Lm1.06Ni4.96Al0.04 40 oC
Fe0.9Mn0.1Ti at 15 oC
15 oC
Figure 4. Typical desorption isotherms of Lm1.06Ni4.96Al0.04 and Fe0.9Mn0.1Ti (data from producers)
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H2 Fuel Cell Utility Vehicle
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Metal Hydride H2 Fuel Cell Power System
Hydride hydrogen storage vessels
Coolant tank
Pressure regulator
Humidifier
Air compressor
Humid pump
Coolant pump
Hydrogen circ. pump
Back pressure regulator
Water separator
Coolant HX
Fuel cell
stackHX for humid system
Hydrogen Air Coolant Water
Figure 2. The power system of Gator 2.
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H2 Fuel Cell System Demonstrated
Table 2. Specifications of Hydrogen Fuel Cell Gator UtilityVehicleVehicle chassis mfr./type Deere & Co. / Gator Utility
VehicleFuel cell type NG2000 60 cellsFuel cell operating pressure 150 kPa (122 to 308 kPa)Fuel cell operation temperature 60 oCHydrogen / air flow rates 1.5x / 2.5x stoichiometricFuel cell power @ 163 kPa 8.3 kW at 38 VHydride material Fe0.9Mn0.1TiStorage system weight 244 kgHydrogen storage capacity 2 kgHydrogen discharge temp./ pressure @50% loading
50 oC / 756 kPa
Refueling pressure / time 2170 kPa / 60 minutesVehicle weight ~ 900 kgOperating range 7 hours, or 80 km @ 11.5 km/hr
avg.Maximum cruising speed 19 km/hr
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Summery
• Present hydrogen storage methods are feasible but not practical for a hydrogen economy
• Metal hydrides though heavy do have advantages and may find niche applications
• Lighter metal hydrides (solid absorbents) are needed• SRTC metal hydride vessel technology is applicable
to both stationary and mobile applications• Hydrogen economy requires a better storage method
that is to be discovered.