Hydrogen
Storage
2/6/2020 1
Presentation
Outline
Small-scale to large-scale hydrogen storage provides attractive
options
Months
• H2 physical properties Hydrogen
Week Texas,
• Overview H2 production, transportation
s & utilization US
• H2 storage technologies Days
• Compressed storage
CAES
• Liquid storage
• Materials based storage Hours
• C hemical hydrogen storage
Pumped Hydro
• Storage in NG Minutes
0. 1 1 10 100
pipelines 1 0 0 0
GWh
• Summary
• Vehicle & portable
applications
Ref:
1. Crotogino F, Donadei S, Bu¨ nger U, Landinger H. Large-scale hydrogen underground storage for securing future energy supplies. Proceedingsof 18thWorld Hydrogen
Energy
2.
Conference (WH2C2010), Essen, Germany;May 16e21, 2010. p. 37e45.
Kepplinger J, Crotogino F, Donadei S, Wohlers M. Present trends in compressed air energy and hydrogen storage in Germany. Solution Mining Research Institute SMRI
2/6/2020 2
Fall 2011 Conference, York, United Kingdom; October 3e4, 2011.
Physical Properties of H2 vs
CH 4
H2 has a very low density and energy density, and a high specific
volume
Hydrogen
0.08 12 11.9 10,05
5
Densit Lower0Heating 8 Volume
Specific 0
Energy
Propert y Density 3
Value m3/kg
y (kg/m3) kJ/m
(kJ/kg)
0.6 5 1.4 32,56
5 0 8 0
Methane
1 1 atm, 1 atm, 1 atm,
atm,15°C 25°C 21°C 25°C
3
Laminar Flame Speeds
Hydrogen burns ten times as fast as
methane
H2
CO
CH4
0. 1 2 3
4 meter/
0.
3 second
Ref: NAC A Report 4
1300
Flammability Limits In
Air
Hydrogen has broad flammability limits compared to
methane
H2 4 to 75
CO 12 to 75
CH4 5 to 15
0 2 50 7 10
5 % in 5 0
Air
5
Diffusivity in
Air diffuses over three times as fast compared to
In air, hydrogen
methane
H2
CO
CH4
0. 0.5 0. 1
2 cm2/ 7
sec
Ref: Vargaftik, N. B., Vinogradov, Y. K., and Yargin, V. S. (1996) Handbook of
Physical Properties of Liquids and Gases, 3rd Ed., Begell House, Inc., New 6
York.
Auto Ignition Temperature & Minimum Ignition Energy
H2 auto ignition temp. safely higher than compressor exit
temperatures
CO 630oC Minimum Ignition Energy (mJ)
CH4 CO 0.3 (2)
595oC …
CH…4…
…………
..… . 0.3 (1)
H2 H2 …………… 0.017
(1)
560oC
Coffee…….... 160
(1)
~ C ompressor
Discharge
315oC
Temperature
References
1. Babrauskak, V. (2003) Ignition Handbook, Fire Science Publishers, Issaquah 7
WA
Overview of Hydrogen
Technologies
Production, Transportation and Utilization
Hydrogen Production
• Produced using domestic resources – water, natural gas and c oal
• DOE supports R&D for a wide range of H2 production technologies
• Electrolytic – electrolyzers to split water into H2 and O2
• Thermochemical - NG reforming (SMR, SOEF, etc.)
• Solar – use light energy to split water into H2 and O2
• C hallenge – C ost & Efficiency
Hydrogen Transport
• Develop infrastructure to deliver H2 from points of production to end-use
• Mixed into the natural gas pipe line system
• Pressurized and delivered as a c ompressed gas or liquefied
• DOE supports R&D to develop H2 transport technologies and reduce
costs
• Challenges –delivery cost, purity, compression efficiency, reduce
leakage 8
Overview of Hydrogen
Technologies
Production, Transportation and Utilization
Hydrogen Utilization
• Develop technologies to utilize H2 as an energy source
• Combustion turbines, fuel cells, other heat engines, domestic appliances
• Challenges – H2 fuel properties: low energy density, broad
flammability
limits, high flame speed, low ignition energy
• DOE supports R&D to improve the understanding of H2 combustion
and develop advanced H2 utilization technologies
9
Hydrogen Storage
Technologies
Generalized groups of hydrogen storage technologies
Hydrogen Storage
Technologies
Physic a Chemical
Adsorption
l Storage
Storage
Metal Chemical
H2(g) H2(l
H2(l
Hydrides Hydrides
)
Elemental Intermetalli
Intermetalli Complex
Hydrides c c Hydrides
Hydrides
Ref: Andersson, J. and S. Gronkvist, 2019, “Large-scale storage of hydrogen.”
2/6/2020 10
International
Journal of Hydrogen Energy, Vol. 44.
Physical Storage - Gaseous
•
hydrogen
Spheric al pressure vessels (20 bar)
• Pipe storage (100 bar)
• C ommon for industrial use
• Underground
• Salt caverns
• Several
in use
at full
industri
al sca le
• Not
applica
ble in
all
geograp
hic
regions
• Many advantages: Low construction costs, low leakage
rates, fast withdrawal and injection rates, low cushion gas
Ref: Salt Cavern Image: KBB. Untertagespeicher. Kavernen Bau und Betriebs GmbH; 2/6/2020 11
requirements, minimal
1988. H2 contamination
Physical Storage - Liquid
hydrogen
• High storage density (70kg/m3 at 1 bar)
• Utilized in the space industry
• Energy intensive (BP: -253ºC @1 bar,
does not c ool during throttling above
-73ºC Ref ( )
• Expensive containment vessels
• Boil-off is an issue
• mitigated if stored near liquefac tion plant
• Installations exist globally (355 tpd
capacity)
Ref: H2 Phase diagram and Spherical container: 2/6/2020 12
NASA
Adsorption
• Van der Waals forces bond H2 to materials with
large spec ific surface area
• Adsorbents
• Porous c arbon-based materials
• Metal-organic frameworks
• Porous polymeric materials
• Zeolites
• Low temperatures and elevated pressures are
typically required to promote VWF
• Exothermic process, heat management
necessary
• Lab-scale only, low TRL
• Storage capacity likely limited to 40 – 50
kg/m^3 at – 196 oC
Ref: Andersson, J. and S. Gronkvist, 2019, “Large-scale storage of hydrogen.” 2/6/2020 13
International Journal of Hydrogen Energy, Vol. 44.
Chemical Storage – Metal
• H2
Hydrides
c hemically bonds with the material
• Wide range of available materials
• Elemental (magnesium, aluminum)
• Intermetallic
• Complex metal
• H2 is released with:
• Water (hydrolysis, exothermic, irreversible)
• NaBH4
• Heating(thermolysis, endothermic, reversible)
• MgH2 and AlH3
• Issues
• Heat management
• Dehydrogenation energy
• C ostly materials
• A popular c hoice for vehicle
applications
• MgH2 storage c apac ity ~ 86 kg /m^3
Ref: Andersson, J. and S. Gronkvist, 2019, “Large-scale storage of hydrogen.”
2/6/2020 14
International
Journal of Hydrogen Energy, Vol. 44.
Chemical Storage - Chemical
hydrides
• Highest energy density of all chemical storage
methods
• Formic acid (53 kg/m^3)
• Low hydrogen storage density
• Easily dehydrogenated
• Methanol (99 kg/m^3)
• Can be dehydrogenated with steam reforming
• Synthesized from CO 2 and hydrogen, (also stores CO2)
• Ammonia(123 kg/m^3 at 10 bar)
• High hydrogen storage density
• Requires high heat to completely dehydrogenate
• Liquid organic hydrogen c arriers
• Remain liquid at ambient conditions in both hydrogenated
and
dehydrogenated states
Ref: Andersson, J. and S. Gronkvist, 2019, “Large-scale storage of hydrogen.”
2/6/2020 15
International
Journal of Hydrogen Energy, Vol. 44.
Hydrogen Storage for Vehicle
Applications
• Primary solution: High pressure cylinders
• Vehicles have different storage
characteristics than large scale
storage:
• c ompac t, light, stable, quic k
charging/discharging, strict delivery
conditions
• Large scale storage would require:
• Low energy and c apital c osts
• Low leakage/loss rates
• Research for vehicle H2 storage has
driven
material development
• Similar to battery development
• Metal hydrides c ould
Ref: be the
Vehicle answer
storage to
image: https://str.llnl.gov/2018-01/wood and H2 Storage
2/6/2020 16
density density image: http://www.hydrogengas.biz/metal_hydride_hydrogen.html
Natural G as Pipeline System as Storage Capacity
• 3 million miles of natural gas
pipeline in the US: Vast potential for
immediate H2 storage
• Mixing10-20% hydrogen in natural
gas pipelines c ould be possible
today
• Combustion apparatus c an handle
some amount of H2/CH4 fuel blending
• Applianc es: 10-20% (depending on
applianc e)
with no issues
• Turbines: c an handle 10% blending with
no modifica tions or up to 30% with
minor alterations
References
1. Energy Information Administration (EIA), 2020, “Natural gas explained.” https://www.eia.gov/energyexplained/natural-gas/natural-gas-pipelines.php
2. McDonell, V. et al., 2019, “Implications of Increase Renewable Natural Gas on Emissions and Stability Behavior of Appliances.” Presentation, CEC Grant PIR-16-017, October 23, 2019.
3. ETN Global, “Hydrogen Gas Turbines: The Path Towards a Zero-Carbon Gas Turbine.”
2/6/2020 17
Operating Costs of H2 Storage Technologies
Storage Process Release Process
Storage Heat Tem Pressur Electricity Heat Tem
Technology (kWh/kg p e (bar) (kWh/kg (kWh/kg p
H 2) (°C) H 2) H 2) (°C)
Gas 100 bar - - 100 1 - -
Gas 200 bar - - 200 1.2 - -
Gas 700 bar - - 700 1.6 - -
Liquid Hydrogen - -253 - 6 - -
Adsorption - -176 40 6.7 - -
AlH3 54 <70 - 10 1 100
MgH2 - 300 30 0.7 10.3 350
Intermetalli - <80 50 0.8 ~2-6 <80
c Hydride
Formic Acid 64 100-180 105 6.7 4.3 <100
Ammonia - 400 250 2-4 4.2 >425
Methanol - 250 50 1.3-1.8 6.7 250
Ref: Andersson, J. and S. Gronkvist, 2019, “Large-scale storage of hydrogen.”
International 2/6/2020 18
Journal of Hydrogen Energy, Vol. 44.
Summary
Hydrogen a potential ca rbon free energy ecosystem
• H2 is a challenging fuel compared to methane
• Utilizing H2 as an energy source can be c arbon free
• Need CCS for FE based; Renewable or NE electricity for
electrolysis
• H2 storage offers a long term / high c apac ity ES option
c ompared to other methods (CAES, pumped hydro, batteries)
• The existing NG pipeline system could accommodate storage now
• In part decarbonizing NG
• H2 could provide for a carbon free energy ecosystem
(production, storage, distribution and use) and leverage existing
assets while allowing future technology development and
insertion
2/6/2020 19
Ref: https://www.sciencedirect.com/topics/engineering/hydrogen-production-cost and
https://www.hydrogen.energy.gov/pdfs/16014_h2_production_cost_solid_oxide_electrolysis.pdf 2/6/2020 20
