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Hydrogen storage

and
transport
Course 5

By Mihai Varlam

Agenda or Summary Layout


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Hydrogen delivery and transportation


Liquid Hydrogen
Material challlenge for hydrogen storage -options
Hydrogen storage by carbon materials
Conceptual aspects for hydrogen storage
onboard

The use of hydrogen in the energy sector of the worldwide countries is projected to increase
significantly in the future. Current uses are predominantly in the petroleum refining sector, with
hydrogen also being used in the manufacture of chemicals and other specialized products.
Growth in hydrogen consumption is likely to appear in the refining sector, where greater
quantities of hydrogen will be required as the quality of the raw crude decreases, and in the
mining and processing of tar sands and other energy resources that are not currently used at a
significant level. Furthermore, the use of hydrogen as a transportation fuel has been
proposed both by automobile manufacturers and the national
governments.
Assuming that the use of hydrogen will significantly increase in
the future, there would be a corresponding need to transport
This material. A variety of production technologies are available
for making hydrogen, and there are equally varied raw
materials.
Potential raw materials include natural gas, coal, nuclear fuel,
and renewables such as solar, wind, or wave energy. As these
raw materials are not uniformly distributed throughout the
globe, it would be necessary to transport either the raw
materials or the hydrogen long distances to the appropriate
markets. While hydrogen may be transported in a number of
possible forms, pipelines currently appear to be the most
economical means of moving it in large quantities over great
distances.
Many of the features of hydrogen pipelines are similar to those
of natural gas pipelines. Furthermore, as hydrogen pipeline
networks expand, many of the same construction and
operating features of natural gas networks would be replicated.
As a result, the description of hydrogen pipelines will be very
similar to that of natural gas pipelines.

Infrastructure Options
The
hydrogen production strategy
greatly affects the cost and method of
delivery. If the hydrogen is produced
centrally, the longer transport distances
can increase delivery costs. It can be
produced semi-centrally (closer to the
point of use) to reduce this transport
distance. Distributed production at the
point
of
use
eliminates
the
transportation costs but results in higher
production costs because the economies
of larger scale production are lost. In all
cases, the delivery costs associated with
compression, storage, and dispensing at
the refueling station or stationary power
site are significant and need to be
minimized.
There are three primary options for
hydrogen delivery. One option is
gaseous delivery in pipelines or highpressure tube trailers. This is illustrated
in Figure. This option includes the
possibility of transporting a mixture of
hydrogen and natural gas in the existing
natural gas pipeline infrastructure
followed by separation and purification
of the hydrogen.
Gaseous hydrogen
delivery pathway

Infrastructure option (2)


The second option for
hydrogen delivery is to
liquefy it and transport it
by truck in cryogenic
tanks. This is illustrated in
Figure.
Gaseous
and
liquid
delivery are in use today
but there is only a very
limited hydrogen pipeline
infrastructure for gaseous
service

Infrastructure option (3)


A third option is to utilize high energy density carriers that can be cost effectively transported
and then treated to release hydrogen at the point of use. An example of this are conventional
carriers such as natural gas, methanol, ethanol, or other liquids derived from renewable biomass
that can be produced, transported to refueling stations, and reformed to hydrogen. These types
of carriers are more commonly referred to as feedstocks. Novel carriers such as metal hydrides or
other hydrogen containing solids or liquids that can be treated to release hydrogen at a refueling
station, stationary power site, or possibly even directly on-board a vehicle are other promising
alternatives. This carrier approach is illustrated in Figure.
These primary delivery pathways could also be used in combination as steps in the delivery
process. For example, gaseous hydrogen could be transported by pipeline to a terminal where it
could be liquefied and then distributed by
cryogenic tank truck or transformed
to a novel carrier system for distribution.
There are many potential
components to a complete
hydrogen delivery infrastructure:

Pipelines
Compression
Liquefaction
Tube Trailers,
Cryogenic Liquid Tank Trucks,
Rail, Barges,
Ships (liquid and gaseous H2)
Liquid and Gaseous Tanks
Geologic Storage
Terminals
Separation/Purification
Dispensers
Carriers and carrier
transformation systems.

Transportation Hydrogen
Hydrogen can be transported as a
compressed gas, a cryogenic liquid or as a
solid metal hydride. The cheapest method
of transportation will depend on the
quantity delivered and the distance. The
methods of delivering the hydrogen
considered were truck, rail, ship and
pipeline.

Compressed Gas Trasnport

Compressed gas can be transported


using high-pressure cylinders, tube
trailers or pipelines. If hydrogen is to be
transported as a gas, it should be
compressed it to a very high pressure to
maximize
tank capacities. High-pressure gas
cylinders for example are rated as high
as 40 MPa (5,800 psig) and hold about
1.8 kg (4 lb) of hydrogen, but are very
expensive to handle and transport
Tube trailers, consisting of several steel
cylinders mounted to a protective
framework, can be configured to hold
63-460 kg (140-1,000 lb) of hydrogen
(Air Products 1997), depending on the
number of tubes. Operating pressures
are 20-60 MPa (2,900-8,700 psig).

Hydrogen delivered by rail


Hydrogen is delivered by pipeline in

several industrial areas of the United


States, Canada, and Europe.
Typical operating pressures are 1-3 MPa
(145-435 psig) with flows of 310-8,900
kg/h (685-20,000 lb/h). Germany has a
210 km (130 mi) pipeline that has been
operating since 1939, carrying 8,900
kg/h (20,000 lb/h) of hydrogen through
a 0.25 m (10 in.) pipeline operating at 2
MPa (290 psig). The longest hydrogen
pipeline in the world is owned by Air
Liquide and runs 400 km (250 miles)
from Northern France to Belgium. The
United States has more than 720 km
(447
mi)
of
hydrogen
pipelines
concentrated along the Gulf Coast and
Great Lakes .

Pipeline transmission of hydrogen dates back to late 1930s.


These pipelines have generally operated at less than 1,000
pounds per square inch (psi), with a good safety record.
Estimates of the existing hydrogen transmission system in
the
United States range from about 450 to 800 miles.
Estimates for
Europe range from about 700 to 1,100 miles. These
seemingly
large ranges result from using differing criteria in
determining
pipeline distances. For example, some analysts consider
onlytransport hydrogen from a
Others count only those pipelines that
a certain
diameter as transmission lines.
producer to a customer (e.g., thosepipelines
pipelinesabove
designed
for in-plant
transport of hydrogen for use as feedstock or fuel are not
counted). Operational status and hydrogen purity levels are also
factors in defining these ranges. Hydrogen pipelines in the United
States are predominantly along the Gulf Coast and connect major
hydrogen producers with well-established, long-term customers.
These hydrogen transmission systems pall by comparison with the
180,000-mile natural gas transmission pipeline. Since 1939,
Germany has had a 130-mile pipeline carrying 20,000 lb/hour of
hydrogen in a 10-inch pipe at 290 psi gauge (psig). The longest
hydrogen pipeline in Europe is owned by Air Liquide and extends
250 miles from Northern France to Belgium.

TRANSMISSION PIPELINES
Design requirements for hydrogen pipelines are still evolving.
Although there are several hundred miles of hydrogen pipelines
throughout the world, most hydrogen pipelines are designed to
transport hydrogen only short distances, from the production
facility to the end user. Many such applications typically
represent only a few hundred feet of pipeline and operate with
maximum pressures of considerably less than the 1,000 psi
absolute (psia) or more that would likely be required for longdistance pipeline
transmission of hydrogen.
The safety record for these
pipelines is considered to be
very good. This safe
history notwithstanding, the definition of
required
safety margins, codes, and standards for application
to large-scale hydrogen transport remains a work in
progress. It is therefore not possible at this time to
definitively specify the design details of hydrogen
transmission pipelines. However, based on the
design
parameters of some hydrogen pipelines and on
experience with natural gas pipelines, it is
reasonable to suggest some design parameters that could very
well be applicable to the flow rates, distances, and
pressures
associated
with
long-distance
transmission of
hydrogen via pipeline.

At a given pressure, the energy density of hydrogen is approximately one-third that of natural gas. However,
for the same pipe diameter and pressure, hydrogen flows approximately three times as fast as natural gas.
As a result, if hydrogen compressors could be operated to meet similar pressure requirements as natural gas
compressors, it could be expected that hydrogen pipe diameters would approach those for natural gas
transmission pipelines. As noted in the discussion of natural gas pipelines, pipe diameters of up to 48 inches
are seen. Actual hydrogen pipeline diameters would of course depend on hydrogen demand, the pressures
achievable, and codes and standards that are yet to be developed.

Historically, carbon steel or stainless steel has been used to transport hydrogen. Gray, ductile,
or cast iron and nickel steels have been used but are not considered suitable for high pressure
hydrogen transmission. Austenitic stainless steels, aluminum (including alloys), copper
(including alloys), and titanium (including alloys) are generally applicable for most hydrogen
service applications. High-strength steels (above 100 ksi) are more susceptible to hydrogen
embrittlement, so the use of thicker, low-strength steels is sometimes recommended for
hydrogen pipelines. Polymer/fiberglass-reinforced pipes have been used in specific applications
such as for in-plant piping at moderate temperatures. As is the case with natural gas pipelines,
welding is the preferred joint technology for hydrogen pipelines.
One of the questions to be resolved before hydrogen pipelines can be economically built is that
of potential hydrogen embrittlement, which tends to occur with higher strength steels.
Additional questions such as loss of material strength, fracture toughness, enhanced fatigue
crack growth rates, low cycle fatigue, subcritical and sustained load cracking, susceptibility to
stress corrosion cracking, and hydrogen-induced cracking in welds and joints must also be
answered before there can be a large-scale application of hydrogen pipelines.

COMPRESSOR STATIONS
As noted above, the volumetric energy density of hydrogen gas is only
about one-third that of natural gas at the same pressure. Because
compressors operate on the basis of volume rather than energy
content, considerably higher compression horsepower would be
required to move comparable amounts of energy as compared to the
power requirements for a natural gas system.
Hydrogen is difficult to compress, as it consists of very small
molecules, so positive displacement compressors are typically used.
Hydrogen compressors are expensive due to the required materials,
the physical size needed to supply the needed compression power,
and the redundancy needed to provide reliability. Hydrogen
compressors must have tight tolerances and/or special seals to reach
the pressures required for high-volume transmission. At elevated
pressure and temperature, hydrogen can permeate carbon steel,
resulting in decarburization.
Conventional mild steel has been used as pipeline material in Germany
and France since 1938, and alloy steels with chromium and
molybdenum have been suggested as compressor materials.
Multistage reciprocating machines to produce pressures of 700 to 1,000
psig are considered state-of-the-art, and additional research and
development activities are under way in both the private and public
sectors. These units have high maintenance costs due to wearing
components such as valves, rider bands, and piston rings. These
compressors are typically nonlubricated (oil-free) so as to reduce the
potential for oil contamination of the hydrogen
In selecting equipment for pipelines, it should be noted that centrifugal
compressors create more operating problems than reciprocating
compressors. Considering the relative lightness of hydrogen, its
recompression ratio is four times lower than for natural gas for a given
rotor speed. This necessitates a greater number of stages. Because of
its low specific gravity, hydrogen tends to return to the compressor inlet
of centrifugal compressors, thereby limiting their efficiency.

PIPELINES COMPONENTS
Metering stations
Although details of hydrogen transmission pipelines have yet to be developed, it is likely that
metering stations would be placed along the pipelines. In a manner similar to that for natural gas
pipelines, these metering stations would allow pipeline companies to monitor and manage the
hydrogen in their pipes. Essentially, these metering stations measure the flow rate and pressure
of the hydrogen along the pipeline, thus allowing pipeline companies to track it as it flows along
the pipeline.
SCADA center
Hydrogen pipeline networks can be expected to have supervisory control and data acquisition
(SCADA) systems that are similar to those for natural gas pipeline networks. The basic objective of
such a system is to monitor conditions (e.g., flow rate, pressure, temperature, and valve positions)
throughout the pipeline network and make any necessary changes in these conditions.
CITY GATE STATIONS
The potential uses for large quantities of
hydrogen are as a feedstock or fuel for
industrial facilities or as a transportation fuel.
In either case, it is likely that hydrogen
pressure would have to be reduced from
transmission pipeline levels to distribution
system levels. In a manner similar to that for
natural gas systems, pressure regulators
would likely be used to control the hydrogen
flow rate through the station and to maintain
the desired pressure in the distribution
system.
Should it be decided to add any additives to
the hydrogen as it enters a distribution
system, such as the odorant added to natural
gas, it is likely that this would be done at the
city gate stations.

Pending significant advancements and breakthroughs in


material-based
hydrogen
storage
technologies,
compressed gas cylinders and cryogenic liquid tanks
may be the most viable methods of storing hydrogen onboard vehicles. Significant advances have been made
recently in fabricating high strength composite fiber
tanks capable of storing compressed H2 (CH2) at 350700
bar. However, the prospect of meeting the goal of 4560
g/L system volumetric capacity is limited since, at room
temperature, the density of CH2 is only 23.5 g/L at 350
bar and 39.5 g/L at 700 bar and the volumetric efficiency
(defined as volume of storage medium divided by the
total system volume) may be less than 60% . There are
some other issues associated with CH2 storage including
electrical energy consumed in compressing H2 to
elevated pressures, possible decrease of storage density
at fast fill without external cooling, limited capacity of H2
tube trailers, and capital expenditure in creating a H2
pipeline infrastructure.

Cryogenic liquid H2 tanks can be more


compact than compressed H2 cylinders
because of the high density of liquid H2 (LH2) at
low pressures (70.8 g/L for saturated liquid at
1 bar). Liquid H2 trucks can have more than 10
times the transport capacity of gaseous H2
tube trailers. Liquid H2 tanks onboard vehicles
can be refueled rapidly (in 3 min) without
evaporative losses Although it is possible to
fabricate insulated cryogenic tanks with
extremely low heat transfer from the ambient
(13 W), evaporative losses remain an issue as
H2 has to be vented after 35 days of inactivity,
and in extreme cases, after longer periods of
inactivity, H2 in the vehicle may be depleted,
leaving the driver stranded.

Hydrogen liquefaction is an energy intensive process that,


depending on scale, may require >10 kWh/kg of electricity.
Finally, because LH2 expands considerably as it warms between
20 K and its critical point (33 K), LH2 tanks are filled to only 85
95% capacity to prevent spills, leaving 515% of empty space
(ullage).
Storing liquid hydrogen in insulated pressure vessels (the socalled cryo-compressed H2 storage option or cCH2 for short)
overcomes many of the above shortcomings and may even open
new possibilities. The dormancy is greatly extended as the
allowable pressure inside the vessel increases. The vessel has
higher heat receptivity since H2 contained in the vessel is vented
at a higher temperature and this further augments dormancy. A
vehicle equipped with an insulated pressure vessel cannot be
stranded due to evaporative losses because venting stops when
the tank reaches ambient temperature at allowable pressure
(>240 bar), at which point the H2 density is still 30% of the initial
liquid density. It may be possible to reduce or eliminate ullage
space in insulated pressure vessels since H2 becomes a
supercritical fluid at a pressure above 13 bar before there is a
need to vent. The storage density may be higher in insulated
pressure vessels since LH2 is slightly
compressible: at
21 K, the liquid density is 87 g/L at 240
bar compared to
70 g/L at 1 bar. It was
suggested that an insulated pressure
vessel can be fueled flexibly with LH2
for extended range and inexpensive CH2
for normal driving with short trips.

It is shown a liquid refueling interface with


separate fill and vent lines (a double-flow refueling
device). A feed and bleed type of arrangement can
be used with this interface to refuel the tank with
LH2 in the event that the internals are initially at
near-ambient temperature. Liquid refueling can
also be
accomplished with a single line by
alternately feeding the tank with LH2 and venting
hydrogen that boils off. The vent is not to the
atmosphere but to an off-board hydrogen
compression and storage system.
LLNL Generation 2 cryocompressed storage tank
including an in-tank
heater, ex-vessel
components and double
flow
refueling interface

CHOICE OF TRANSPORTATION
The main factors affecting the choice of hydrogen
transport are the application, quantity, and distance
from the production site to the customer. As mentioned
under storage, if liquid hydrogen is needed for the
application, it should be delivered as liquid hydrogen.

Quantities
For large quantities of hydrogen, pipeline delivery is cheaper than all other methods except in
the case of transport over an ocean, in which case liquid hydrogen transport would be cheapest.
The next cheapest method of delivery would be liquid hydrogen. Pipeline delivery has the
benefit of a very low operating cost, consisting mainly of compressor power costs, but has a high
capital investment. Liquid hydrogen, on the other hand, would have a high operating cost, but
possibly a lower capital cost, depending on the quantity of hydrogen and the delivery distance.
The break-even point between liquid hydrogen and a pipeline will vary depending on the
distance and quantity.
For smaller quantities of hydrogen, pipeline delivery is not competitive, but compressed gas
delivery may be competitive. Compared to liquid hydrogen, compressed gas has lower power
requirements and slightly lower capital costs for the tube trailers, but many more tube trailers
are required to deliver the same quantity of hydrogen. Which delivery method is more
economical will depend on the delivery distance, because it may be possible to use the same
tube trailer for several trips per day if it is a short distance.
For still smaller quantities, the high capital cost of a pipeline eliminates it as an option. The
deciding factor between liquid hydrogen and compressed gas becomes a matter of distance. For
long distances, the higher energy costs of liquefaction will balance out against the higher capital
and transportation expense of many compressed gas tube trailer trips back and forth. If the
distance is relatively short, and the quantity of hydrogen transported is small, compressed gas
may win out.

Choice of hydrogen
transportation (2)

DISTANCE

SPECIAL CASE--POWER SUPPLY

As mentioned earlier, distance is an important


factor. For a short distance a pipeline can be
very economical because the capital expense of
a short pipeline may be close to the capital cost
of tube trucks or tankers, and there are no
transportation or liquefaction costs. As the
distance increases, the capital cost of a pipeline
increases rapidly, and the economics will
depend on the quantity of hydrogen-- pipelines
will be favored for larger quantities of hydrogen.
For small quantities of hydrogen, at some point
the capital cost of the pipeline will be higher
than the operational costs associated with
delivering and liquefying the hydrogen.
Distance is a deciding factor between liquid and
gaseous hydrogen. At long distances, the
number of trucks required to deliver a given
quantity of compressed hydrogen will be
greater than the increased energy costs
associated with liquefaction and fewer trucks.

One special case related to hydrogen is


when energy must be transmitted a long
distance.
Currently,
energy
is
transmitted by high-voltage power lines,
and current losses result in a 7%-8% loss
in transmitted energy. Hydrogen gas
transport through a pipeline on the other
hand, results in somewhat lower losses,
meaning it may be cheaper to produce
hydrogen and pipe it to a location
requiring heat or electrical energy
because the energy losses are less with
a hydrogen pipeline. One source
indicated the cutoff where hydrogen
energy transport is cheaper than
overhead lines is 1,000-2,250 km

Future of Hydrogen Transportation


Several trends in hydrogen transportation were identified.
First, there is continued research in long range transport of
hydrogen using barges or ships. Canada is especially
interested because it has large hydroelectric resources that
could be used to produce hydrogen. It has designed several
vessels for carrying hydrogen across the Atlantic. One
design uses five barges contained on a single ship,
designedto go for 50 days without venting hydrogen. Once
overseas, the barges can be separated to go to different
destinations without incurring transfer losses. Another
option mentioned was the use of airplanes to delivery
hydrogen over great distances to reduce transport times
and consequently reduce boil-off loses. Work is also being
done to reduce transfer losses in hydrogen transportation,
with a goal of reducing losses to 8%
Pipeline delivery of liquid hydrogen is also considered for the next
future. One special case of using a liquid hydrogen pipe is when it
is combined with a superconducting wire. The liquid hydrogen
could keep the wire cool enough to be a superconductor for very
efficient transport of electricity, possibly justifying the higher
capital costs of the liquid hydrogen pipeline.
Large-scale distribution networks for hydrogen must address
storage issues to provide a buffer between production facilities and
customers and to cover fluctuations in demand . Natural gas
pipelines could be converted to hydrogen gas, but there is some
concern that hydrogen embrittlement of the fittings and piping
would cause them to crack and leak

Hydrogen
storage
Hydrogen as an energy carrier
needs to be stored effectively
and safely, particularly for
vehicular applications. It may be
stored as a gas, a liquid, or an
atomic solid, e.g. in a hydride.
The latter represents the safest
method with a relatively large
H-storage capacity per unit volume,
compared with all other forms of H2. For
optimum H-storage, an ideal storage
system should possess: a high Hstorage capacity (>6 or 9 mass%
hydrogen, or 5.5 kg H2 in a tank that
can be fitted under the car seat), a low
thermodynamic stability (leading to a
low desorption temperature <150 C,
under a moderate pressure), high
kinetics
for
hydrogen
absorption/desorption
(<12
mass
%/min, e.g. 5 min re-filling time), high
stability against O2 and moisture
(hence a long cycle life >500 cycles),
good thermal conductivity (for rapid
conduction of sorption heat), and low
cost < 2.5/kWh

The main options for storing hydrogen are as a


compressed gas, as a liquid, or combined with a
metal hydride. Underground storage is also
considered, although it is just a special case of
compressed gas storage. Each alternative has
advantages and disadvantages. For example,
liquid hydrogen has the highest storage density
of any method, but it also requires an insulated
storage container and an energy
intensive
liquefaction process.

Liquefaction process liquid hydrogen


Liquefaction is done by cooling a gas to form a liquid.
Liquefaction
processes
use
a
combination
of
compressors, heat exchangers, expansion engines, and
throttle valves to achieve the desired cooling. The
simplest liquefaction process is the Linde cycle or JouleThompson expansion cycle. In this process, the gas is
compressed at ambient pressure, then cooled in a heat
exchanger, before passing through a throttle valve
where it undergoes an isenthalpic Joule-Thompson
expansion, producing
some liquid. This liquid is removed and the cool gas is
returned to the compressor via the heat exchanger . A
flowsheet of the Linde process is shown in Figure. The
same process is represented on a temperature-entropy
diagram in the bellow Figure.
The Linde cycle works for gases, such as nitrogen, that
cool upon expansion at room temperature. Hydrogen,
however, warms upon expansion at room temperature.
In order for hydrogen gas to cool upon expansion, its
temperature must be below its inversions temperature
of 202 K (-95F). To reach the inversion temperature,
modern hydrogen liquefaction processes use liquid
nitrogen pre-cooling to lower the temperature of the
hydrogen gas to 78 K (-319F) before the first expansion
valve. The nitrogen gas is recovered and recycled in a
continuous refrigeration loop.

Liquefaction process (2)


An alternative to the pre-cooled Linde process is to pass
the high-pressure gas through an expansion engine.
An expansion engine, or turbine, will always cool a
gas, regardless of its inversion temperature. The
theoretical process referred to as ideal liquefaction
uses a reversible expansion to reduce the energy
required for liquefaction. It consists of an isothermal
compressor, followed by an isentropic expansion to
cool the gas and produce a liquid. It is used as a
theoretical basis for the amount of energy required for liquefaction, or ideal work
of liquefaction, and is used to compare liquefaction processes. In practice, an
expansion engine can be used only to cool the gas stream, not to condense it
because excessive liquid formation in the expansion engine would damage the
turbine blades. Figure is a flowsheet for an ideal liquefaction process; The bellow
Figure shows the process using a temperature-entropy diagram.
The ideal work of liquefaction for hydrogen is 3.228 kWh/kg . For comparison, the
ideal work of liquefaction for nitrogen is only 0.207 kWh/kg.
Other processes include the Dual-Pressure Linde Process, the
Claude Cycle, the Dual-Pressure Claude Cycle, and the
Haylandt Cycle. They are similar to the above processes, but use
extra heat exchangers, multiple compressors, and expansion
engines to reduce the energy required for liquefaction. This energy
reduction is offset by higher capital costs.

Ortho-to-Para Conversion

This can be accomplished using a number


of catalysts including activated carbon,
platinized asbestos, ferric oxide, rare
earth
metals,
uranium
compounds,
chromic
oxide,
and
some
nickel
compounds.
Activated
charcoal
is
used
most
commonly, but ferric oxide is also an
inexpensive
alternative.
The
heat
released in the conversion is usually
removed by cooling the reaction with
liquid nitrogen, then liquid hydrogen.
Liquid nitrogen is used first because it
requires less energy to liquefy than
hydrogen, but still cools the hydrogen
enough to achieve an equilibrium
concentration of roughly 60% para-

Hydrogen molecules exist in two forms, para and ortho,


depending on the electron configurations in the two
individual hydrogen atoms. At hydrogens boiling point of 20
K (-423F), the equilibrium concentration is almost all parahydrogen, but at room temperature or higher, the
equilibrium concentration is 25% para-hydrogen and 75%
ortho-hydrogen.
The uncatalyzed conversion from ortho to para-hydrogen
proceeds very slowly, so without a catalyzed conversion
step, the hydrogen may be liquefied, but may still contain
significant quantities of ortho-hydrogen. This orthohydrogen will eventually be converted into the para form in
an exothermic reaction.
This poses a problem because the transition from ortho to
para-hydrogen releases a significant amount of heat (527
kJ/kg [227 Btu/lb]). If ortho-hydrogen remains after
liquefaction, this heat of transformation will slowly be
released as the conversion proceeds, resulting in the
evaporation of as much as 50% of the liquid hydrogen over
about 10 days. This means long-term storage of hydrogen
requires that the hydrogen be converted from its ortho form
to its para form to minimize boil-off losses.

Liquid Hydrogen storage


A major concern in liquid hydrogen storage is minimizing hydrogen losses from liquid boil-off.
Because liquid hydrogen is stored as a cryogenic liquid that is at its boiling point, any heat transfer
to the liquid causes some hydrogen to evaporate. The source of this heat can be ortho-to-para
conversion, mixing or pumping energy, radiant heating, convection heating or conduction heating.
Any evaporation will result in a net loss in system efficiency, because work went into liquefying the
hydrogen, but there will be an even greater loss if the hydrogen is released to the atmosphere
instead of being recovered. The first step in avoiding boil-off losses is to perform an ortho-to-para
conversion of the hydrogen during the liquefaction step to prevent any conversion and subsequent
evaporation from occurring during storage. Another important step in preventing boil-off is to use
insulated cryogenic containers.
Cryogenic containers, or dewars, are designed to minimize conductive, convective, and radiant heat
transfer from the outer container wall to the liquid. All cryogenic containers have a double wall
construction and the space between the walls is evacuated to nearly eliminate heat transfer from
convection and conduction. To prevent radiant heat transfer, multiple layers (30-100) of reflective,
low-emittance heat shielding--usually aluminized plastic Mylar--are put between the inner and outer
walls of the vessel. A cheaper alternative to Mylar film is perlite (colloidal silica) placed between the
vessel walls.
Some large storage vessels have an
additional outer
wall with the space filled with liquid
nitrogen. This
reduces heat transfer by
lowering the temperature
difference driving the heat
transfer.
Most liquid hydrogen tanks are spherical, because
this
shape has the lowest surface area for heat transfer
per unit volume. As the diameter of the tank
increases,
the volume increases faster than the surface area,
so
a large tank will have proportionally less heat
transfer
area than a small tank, reducing boil-off. Cylindrical
tanks are sometimes used because they are easier
and cheaper to construct than spherical tanks and
their volumeto- surface area ratio is almost the

Metal Hydride Storage


Metal hydrides store hydrogen by chemically
bonding the hydrogen to metal or metalloid
elements and alloys. Hydrides are unique
because some can adsorb hydrogen at or below
atmospheric pressure, then release the
hydrogen at significantly higher pressures when
heated--the
higher the temperature, the higher the
pressure. There is a wide operating range of
temperatures and pressures for hydrides
depending on the alloy chosen. Each alloy has
different performance characteristics, such as
cycle life and heat of reaction.
Fig.
illustrates
the
temperature
and pressure
relationship for a typical hydride. When the hydrogen
partial pressure is first increased, the hydrogen
dissolves in the metal or alloy, then begins to bond to
the metal. During the bonding period the equilibrium or
plateau pressure remains constant from the time that
10% of the hydrogen has been stored until about 90%
of the storage capacity is reached. After the 90% point,
higher pressures are required to reach 100% of the
hydride storage capacity. Heat released during hydride
formation must be continuously removed to prevent the
hydride from heating up. If the temperature is allowed
to increase the equilibrium pressure will increase until
no more bonding occurs.

Metal Hydride storage (2)


To recover the hydrogen from the metal hydride, heat must be added to
break the bonds between the hydrogen and the metal. Again, the higher
the temperature, the higher the release pressure. Initially the pressure of the gas
is high as any free hydrogen is released, then the pressure plateaus as the
hydride bonds are broken. When only about 10% of the hydrogen remains the
equilibrium pressure drops off. This last bit of hydrogen dissolved in the metal
matrix is difficult to remove, and represents strongly bonded hydrogen that
cannot be recovered in the normal charge/discharge cycle.
Metal hydride beds can be configured similar to carbon adsorption columns.
This results in a reaction front moving through the bed with a very high
upstream concentration of hydrogen and a low residual concentration
downstream of the reaction front. Using this configuration, it is easy to determine when the bed is
completely charged because the outlet hydrogen concentration will suddenly increase. Using multiple
columns allows semi-continuous charging and discharging of the hydrides
Hydrides store only about 2%-6% hydrogen by weight, but have high volumetric storage densities. The
heats of reaction for hydrides can range from 9,300 to greater than 23,250 kJ/kg of hydrogen, and
operating pressures
can reach more than 10 MPa. Some hydride release temperatures can
also be quite
high-greater than 500C. With this wide range in pressures and
temperatures, the
construction of the storage unit becomes a challenge. The vessel
containing the
hydride must be pressurized and contain sufficient heat exchange
area to allow
rapid heat transfer for charging and discharging the hydride. The
metal hydride alloy
must also be structurally and thermally stable to withstand numerous
charge/discharge cycles. Some hydrides can also be poisoned by
carbon dioxide,
sulfur compounds, or water

Compressed Gas
Storage
Compressed gas storage of hydrogen is the simplest
storage solution--the only equipment required is a
compressor and a pressure vessel. The main problem
with compressed gas storage is the low storage density,
which depends on the storage pressure. Higher
storage pressures result in higher capital and operating
costs. Low-pressure spherical tanks can hold as much as
1,300 kg of hydrogen at 1.2-1.6 Mpa (1,700-2,300 psig).
High-pressure storage vessels have maximum operating
pressures of 20-30 MPa (2,900-4,350 psig). European
countries tend to use low pressure cylindrical tanks with a
maximum operating pressure of 5 MPa (725 psig) and
storage capacities of 115-400 kg of hydrogen.
One concern with large storage vessels (especially underground storage) is the cushion gas that
remains in the empty vessel at the end of the discharge cycle. In small containers this may not
be a concern, but in larger containers this may represent a large quantity of gas. One option is to
use a liquid such as brine to fill the volume of the container and displace the remaining hydrogen
gas.
Another storage option - Underground Storage
Depending on the geology of an area, underground storage of hydrogen gas may be possible. Underground
storage of natural gas is common and underground storage of helium, which diffuses faster than hydrogen, has
been practiced successfully in Texas. For underground storage of hydrogen, a large cavern or area of porous rock
with an impermeable caprock above it is needed to contain the gas. A porous layer of rock saturated with water
is an example of a good caprock layer. Other options include abandoned natural gas wells, solution mined salt
caverns, and manmade caverns. As mentioned with compressed gas containers, one consideration is the cushion
gas that occupies the underground storage volume at the end of the discharge cycle. This can be as much as
50% of the working volume, or several hundred thousand kilograms

Technical challenges
for hydrogen storage
The grand challenge in identifying
an ideal hydrogen storage system is
to meet simultaneously all the targets
for practical on-board vehicular
applications (Fig.) .

These targets or required properties are closely


associated with three sets of parameters: structure
(crystalline form, specific surface area or particle size,
and structural defects), chemistry (components,
composition, phases, catalysts, and impurities), and
reaction or diffusion path (elementary reactions,
transient species, . . . , etc.). These are interacting
and the critical issues differ for different types of
hydrogen storage materials

Capacit
y

Most metallic elements can form hydrides at


various conditions, with relatively strong
chemical bonding. However, the requirement
for a high system storage capacity of more
than 6 mass% immediately eliminates hydride
systems beyond the first 20 elements in the
Periodic Table, primarily leaving us with Li, B,
Na, Mg, Al, N and C when other chemical
characteristics of the elements are taken into
consideration.
Several promising hydrogen storage systems,
based on MH, MNH and MBH (M= Li, Na,
or Mg) or their mixtures, have been under
development in the past decade (Fig.). When
multi-component alloys, compounds and
polymorphs are counted, there are still a large
number of possible candidates that meet the
capacity requirement. It is usually the
thermodynamic, kinetic and/or reversibility
issues that limit their practical applications.

Technical
challenge for
Thermodynamic
stability storage
hydrogen
Hydrogen may be stored
in a system dominated
either by chemisorption,
e.g. hydrides, or
physisorption, e.g.
carbon structures,
zeolites and
metal-organic
frameworks (MOFs).
The former is usually too
strong (>60 kJ/mol H2)
and demand high
desorption temperatures
to break up the bonds,
whereas the latter
is too weak (<10 kJ/mol H2)
and requires cryogenic temperatures to achieve a useful
capacity. For practical applications, rapid hydrogen
desorption is required around 100 C and one
atmospheric pressure, which corresponds to an enthalpy
of formation around 1525 kJ/mol H2. Hence, an ideal
hydrogen storage system is likely to involve hybrid
sorption mechanisms and/or reaction paths that can
result in an effective enthalpy change lower than that of
simple chemisorption but much higher than that of
physisorption.

Kinetics
Hydrogen needs to be supplied
at
a sufficiently high rate to a fuel
cell in order to accelerate a car
and then maintain it at a
desirable speed. A relatively
high
hydrogen desorption
rate is
thus required (rapid rate for
absorption is also required for
rapid
charging).
Hydrogen
desorption
actually
involves
multi-steps: de-bonding from
host atoms, diffusion in a host
structure, diffusion to/along
surfaces,
formation
of
hydrogen
molecules and dissociation
from the surface of the material (the reverse occurs in
absorption). The slowest step determines the overall
kinetics of sorption. It is usually difficult but important
to pin point which step is rate controlling in hydrogen
sorption. Particle refinement/activation and catalysis to
reduce energy barriers for hydrogen diffusion or
molecule
formation/dissociation are common approaches to
enhance the overall kinetics.

Hydrogen storage by carbon materials

Activated carbon
(AC) is a synthetic carbon modification containing
very small graphite crystallites and amorphous
carbon. The pore diameters are usually less than 1
nm and form a specific surface up to 3000 m2 g1.
AC is prepared from carbon-rich organic precursors
by a thermal method (dry distillation) to form
carbonized organic precursors, which can be
activated to increase the pore volume either
thermally or chemically:
Thermal method:
Treatment at 7001000 C in the presence
of oxidizing gases such as steam, CO2,
steam/CO2 mixtures, or air.
Chemical method:
Treatment at 500800 C in the presence
of dehydrating substances such as ZnCl2,
H3PO4, or KOH,
which are leached out afterwards.

HTSE efficiency -performance


Graphite
Graphite is one of the four ordered carbon
allotropes (diamond with sp3-bonding, graphite
with sp2-bonding, fullerene with perturbed sp2bonding, and carbyne with sp1-bonding).
Graphite has a sheet-like structure where the
atoms all lie in a plane and are only weakly
bonded, via van der Waals forces, to the graphite
sheets above and below. It has a perfect basal
cleavage (Fig. bellow).
Graphite is a naturally occurring mineral with up
to 20 wt%
impurities. Graphite can also be made artificially,
usually by
heating petroleum coke or coal pitch at very high
temperatures ~2500 C.

Graphene is not an allotrope of


carbon, it is a single planar
sheet of sp2 bonded carbon atoms, identical
to one of the layers of the
graphite structure but
isolated. The sheet is of
finite size and other
elements can appear at
the edge of the sheet.
A typical graphene sheet
has the chemical formula
C62H20, where the hydrogen
is used to terminate the
dangling bonds.
Graphenes are aromatic.
Graphenes are normally formed only of hexagonal cells. If
a pentagonal cell is present then the plane warps into a
conical shape. The insertion of 12 pentagons can lead to
the formation of a fullerene.
Planar graphene itself has been presumed not to exist in
the free state, as it would be unstable with respect to the
formation of curved structures such as soot, fullerenes,
and nanotubes. Nevertheless, attempts have been made
to isolate a single graphene sheet by mechanical
exfoliation (repeated peeling) of small fragments of highly
oriented pyrolytic graphite, in order to study the electrical
properties of graphene.

Carbon nanostructures
Fullerene
Fullerenes were first observed in molecular beam experiments, where
discrete peaks were found corresponding to C60 and C70 molecules.
Fullerenes are a class of carbon molecules in which the carbon atoms are
arranged into 12 pentagonal faces and 2 or more hexagonal faces. The
fullerene structure can be understood (although not practically manufactured
this way) as a rolled up single layer of graphene. Whereas graphite is built up
of many graphene sheets of linked hexagonal carbon atoms, the fullerenes
are formed by pentagonal (or sometimes heptagonal) carbon rings, which
prevent the formation of planar structures. These fullerene molecules can
take the form of spheres, ellipsoids, or tubes.
Spherical fullerenes are often referred to as buckyballs, and cylindrical
fullerenes as buckytubes or nanotubes. The names fullerene, buckyball,
and buckytube refer to the architect Richard Buckminister-Fuller, who
popularized the geodesic dome (shaped like an incomplete buckyball). In fact
this structure had already been used in 1913 by Carl Zeiss in Jena for its
planetarium dome.
Both the spherical and the cylindrical fullerenes are hollow.
The smallest possible complete fullerene molecule could be built
up
from 32 carbon atoms.
Fullerenes are formed when carbon is vaporized (e.g. by a pulsed
laser, or an arc discharge), mixed with an inert gas, and then
slowly
condensed. If metal catalysts are included in the
process
nanotubes are formed. If not, then spherical fullerenes are
formed.

Reversible amounts of hydrogen


adsorbed vs. surface area (Circles)
Carbon nanotubes, high surface area
graphite
(electrochemical
measurement at 298 K). (Squares)
Hydrogen adsorption measurement at
77K (Dotted line)

See you next week


!