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GDR - 5/2/96 - H2 Rev

Glass Microspheres
for Hydrogen Storage
Presented to
The DOE Hydrogen Program Review
Miami, FL
May 2, 1996
Glenn Rambach
Lawrence Livermore National Laboratory
(now at Third Orbit Power Systems, Inc.)

Charles Hendricks
W. J. Schafer Associates, Inc.
GDR - 5/2/96 - H2 Rev
Approach/rationale
 Analytically and experimentally identify the properties of large beds of
glass microspheres that are relevant to hydrogen storage
 Model for hydrogen mass fraction, density, charge/discharge rates
and process energy
 Measure hydrogen mass fraction, density, charge/discharge rates
and energy
 Measure bulk handling behavior
 Analysis of relationships between physical properties and
economics
 Identify avenues for improvement

 Identification of bulk, bed properties and any needed improvements is
necessary to show how glass microspheres can be commercialized
GDR - 5/2/96 - H2 Rev
Past results
 Model shows:
 Hydrogen mass fractions to 12%
 Fill time constant of 6 minutes at 350C
 Retention time constant of 10
4
hours at 20C
 Process energy of 12 - 20% of hydrogen LHV
 One truck trailer containing glass microspheres developed in
this project would:
Carry 5 times the hydrogen of a jumbo tube trailer.
Carry 1/3 - 1/2 the hydrogen of a liquid hydrogen dewar
trailer.
 Require 1/2 the energy to convert to, and from
transportable form as LH2.

GDR - 5/2/96 - H2 Rev
Current year results
 Crush measurement method identifies maximum
charging pressure differential

 WJSA system for microsphere precursors completed
and operating

 P-V-T charge/discharge test system designed and
hardware purchased

 WJSA drop furnace for producing microspheres from
precursors is operational

GDR - 5/2/96 - H2 Rev
 Complete P-V-T test system

 Measure charge and discharge rates vs T and material

 Characterize handling behavior of microsphere beds


FY 1996 remainder
GDR - 5/2/96 - H2 Rev
Plans for future work
 Complete economic model of microsphere use, given
the properties measured in this project.
 Experimental safety study
Rapid decompression of packed bed
Flammability limits
Pressure failure propagation (fratricide)
Cycle life
Inhalation risk of intact and fractured spheres
Not experimental
 Tests on multiliter beds
 Production scale-up
GDR - 5/2/96 - H2 Rev
Status of economic evaluation
 Bulk transport capital equipment costs compares
favorably with liquid transport.

 Contribution of process time and energy to cost to be
determined.

 Detailed system study (LLNL) compares delivery costs
for microspheres and 3 other technologies.
GDR - 5/2/96 - H2 Rev
Projected goals
 Measure charge and discharge kinetics for glass
microsphere beds and compare to model.

 Relate kinetics to material properties.

 Relate sphere strength and durability to material and
geometric properties.

 Create a complete understanding of the applications where
microsphere hydrogen storage can be commercialized
GDR - 5/2/96 - H2 Rev
Major barriers to meeting goals
 The possibility that large beds of microspheres
degrade in strength during handling

 Charge and discharge kinetics for all material and
process possibilities too slow to be economically
viable.

GDR - 5/2/96 - H2 Rev
.5 - 20µm
25 - 200µm
100 µm diameter glass spheres with 1 µm thick membrane walls
can contain H
2
at 410 bar with a 1.5 factor of safety

Geometry and dimensions of glass
microspheres for hydrogen storage
GDR - 5/2/96 - H2 Rev
Microsphere failure from compressive buckling
45 µm diameter glass spheres with 0.9 µm thick membranes
GDR - 5/2/96 - H2 Rev
Tensile and compressive failure limits
and crush data for glass microspheres
GDR - 5/2/96 - H2 Rev
 Microsphere heating and handling hardware is deployed
at transport endpoints

 12-tube pressurized trailer truck at 180 bar:
 Carries 335 kg of hydrogen

 53,000 liter liquid hydrogen trailer:
 Carries 3500 kg of hydrogen
 Trailer capital cost is about $143/kg
H2
capacity

Microsphere containerized trailer (2.5m x 2.5m x 12m):
 Can carry 1500 kg of hydrogen at P
s
= 613 bar
 Can carry 750 kg of hydrogen at P
s
= 245 bar
 Trailer capital cost is about $66/kg
H2
capacity
(f
m
1%) s
(f
m
1%) ))
Hydrogen transport comparisons
GDR - 5/2/96 - H2 Rev
Microsphere burst pressure:
P
b
=
r
d
Fill pressure rise rate:
P
i
P
i
o
P(1- e
Time constant (filling or exhausting):
=
r r
3RTKr
Gas permeability of glass:
K = K Te
Q, K = f(mol% of network modifiers)

i
2
0
0
-
Q
T
0
t
4oA
t
t
= +
÷
A
A
)
Hydrogen filling of glass microspheres
GDR - 5/2/96 - H2 Rev
 The microspheres used in this project will be derivatives of the glass
microspheres used in the LLNL laser fusion program
 Very low in geometric and material defects relative to commercially
made microspheres
 LLNL and W. J. Schafer Associates (WJSA) are collaborating in this
effort

 Commercial microspheres fail at 345 MN/m
2
membrane tensile stress,
LLNL microspheres fail at greater than 1040 MN/m
2
stress
 All previous H
2
storage development in microspheres was based on
commercial spheres

 The LLNL/WJSA manufacturing method permits experimental control of
material properties and dimensions to optimize microsphere bed properties

 The application is for bulk transport and storage of hydrogen
Storage of hydrogen in beds
of glass microspheres
GDR - 5/2/96 - H2 Rev
Glass microspheres
 Microsphere hydrogen storage characteristics
 Hydrogen can be stored at high pressures within microspheres
 Accidental release of spheres from container does not
release hydrogen

 Low pressure outer storage vessel
 Less constrained in shape than a pressure vessel
 Less mass and cost than a single primary pressure vessel

 Glass microspheres store hydrogen at room temperature
 Passive long-term storage

 Impurity tolerance

 Fill/release temperatures are currently 200
o
C or higher
GDR - 5/2/96 - H2 Rev
 The project requirements and market applications for glass
and advanced-material microspheres have been identified

 Project plan for current, glass microspheres identified
(this project)
 First application is in bulk hydrogen transport
 Storage density and system complexity preclude
microsphere use for on-board storage

 Identified separate development plan for advanced
microspheres (CRADA project)
 Optimize microsphere properties and fill processes
specifically for hydrogen storage and transport
FY 1996 progress
GDR - 5/2/96 - H2 Rev
 Purchase order contract with W. J. Schafer Associates
(WJSA)
 New microsphere production system designed
and fabricated
 New method of freeze drying tested
 Identified materials for early microsphere candidates

 Operating contract with WJSA placed to carry out
remainder of project

FY 1996 progress (con't.’)
GDR - 5/2/96 - H2 Rev
 Measure microsphere bed properties relevant to large bed
applications, using the best, current glass microspheres
 Burst/crush statistics
 Compare to model prediction
 Evaluate microsphere durability in realistic environment
 Evaluate microsphere handling characteristics
 Packing fractions for mono and polydispersions
FY 1997