CRYOGENICS LIQUID HYDROGEN

STORAGE

Submitted by
M.Gokul (1263002)
N.gowtham (1263003)
INTRODUCTION
Hydrogen has the highest energy content per unit of weight of any known element. It
is also the lightest element. As a result, it is characterized by low volume energy density,
meaning that a given volume of hydrogen contains a small amount of energy. This presents
significant challenges to storing the large quantities of hydrogen that will be necessary in the
hydrogen energy economy.
A critical challenge for transportation applications is balancing the need for a
conventional driving range (>480 km) with the vehicular constraints of weight, volume,
efficiency, safety, and the cost of on-board hydrogen storage systems. A second set of
challenges for transportation applications relate to durability over the performance lifetime of
on board storage systems. To overcome the on-board storage challenge, an alternative may be
on-board reformation of higher density fuels such as natural gas, gasoline, and methanol. An
added benefit of this approach is that it does not require the development of new distribution
infrastructure for pure hydrogen. However, on board reformation of higher density fuels
results in the emission of carbon dioxide, although in lesser quantities than the traditional use
of these fuels.

PROPERTIES AND EFFECTS OF HYDROGEN

Physical Properties
Hydrogen is the least dense of all gases. At normal temperature and pressure the
density of gaseous hydrogen is one fourteenth that of air. Due to its low density gaseous
hydrogen tends to rise and diffuse rapidly in the air. Hydrogen can therefore collect in the
roof spaces of buildings. Hydrogen can diffuse rapidly through certain porous materials or
systems with small openings, which would normally be gastight with respect to air or other
gases. At ambient temperature gaseous hydrogen (contrarily to most other gases) is heated by
throttled expansion. The temperature rise is only small and this alone cannot cause self-
ignition. The thermal conductivity of hydrogen is much higher than that of other gases. This
influences combustion behaviour (e.g. burning velocity).
Chemical Properties
Hydrogen is not significantly reactive. Hydrogen is not corrosive but depending on
temperature, pressure and other conditions it may cause embrittlement of certain steels. From
the chemical point of view, hydrogen is a reducing agent. Hydrogen is flammable and
therefore presents a possible explosion hazard. Hydrogen is easily ignited; its minimum
ignition energy is very low. In practice hydrogen venting or leaking to atmosphere,
particularly from a pressure source can ignite due to electrostatic or self igniting impurities in
the hydrogen. Hydrogen burns with a hot flame. Burning hydrogen produces no soot.
Therefore the flame is pale, colourless and almost invisible in daylight. The heat radiated by a
hydrogen flame is relatively low (only 10 percent that of propane). Therefore a hydrogen
flame gives little warning of its presence either by sight or heat. The range of flammability
both in air and oxygen is wide. Confined mixtures of hydrogen and air or oxygen explode
very strongly and may detonate. An unconfined gas cloud explosion of hydrogen is very
unlikely to occur and up to date such a detonation has not been observed. Hydrogen flames,
especially those emanating from a high-pressure source, are extremely difficult to extinguish.
The best way of extinguishing is to shut off the flow.
Biological Effects
Hydrogen is colourless (transparent), odourless and tasteless and therefore not
detectable by the human senses. Hydrogen is not toxic but can act as an asphyxiant by
displacing the oxygen in the surrounding air.
Breathing a pure hydrogen atmosphere will produce immediate loss of consciousness
and almost immediate death. The amount of hydrogen necessary to produce dangerous
oxygen deficiency is significantly higher than the lower flammability limit. Therefore the
primary risk of hydrogen is not asphyxiation but fire and explosion. Liquid hydrogen has
special effects on the human body (see below).
Special Properties And Effects Of Liquid Hydrogen
Liquid hydrogen is colourless and odourless. Its density is one fourteenth that of
water. Liquid hydrogen is extremely cold -and except for helium- has the lowest boiling point
of all gases. Hydrogen consists of ortho-hydrogen and para-hydrogen. These forms have
differences in physical but not in chemical properties. At the temperature of liquid hydrogen
ortho-hydrogen tends to convert into para-hydrogen. This conversion liberates heat, which
encourages evaporation. However, commercial liquid hydrogen mainly consists of para-
hydrogen. Liquid hydrogen and also the cold "boil off' gas, evolving from the liquid, can
produce severe burns (similar to thermal burns) upon contact with skin. Delicate tissue, such
as those of the eyes can be injured by exposure to the cold gas or splashed liquid in a brief
period of time, which would normally be too short to affect the skin of the hands or face.
Contact between unprotected parts of the body with uninsulated piping or vessels containing
liquid hydrogen can cause the flesh to stick and tear.
Liquid hydrogen and cold "boil off' gas can cause many common materials such as
carbon steel, plastic or rubber to become brittle and prone to fracture under stress. At the
temperature of liquid hydrogen all gases, except helium, condense and then solidify. Such
solid particles can plug restricted areas such as valves and orifices, which could lead to a
failure of, flow and/or pressure increase. Furthermore, condensed or solidified air in liquid
hydrogen is a potential explosion hazard. Liquid hydrogen has a very low heat of
vaporisation (related to a volume basis). Therefore a small heat input (e.g. inserting solids or
liquids at room temperature) will create a violent evolution of gas and splashing of liquid.
Liquid hydrogen in poorly insulated or uninsulated containers and piping will liquefy the
surrounding air. Due to the different boiling points of nitrogen and oxygen condensed air is
oxygen-enriched and can cause a fire risk.
 Liquid hydrogen, spilled to the atmosphere evaporates rapidly. One litre of liquid
hydrogen gives approximately 850 litres of gaseous hydrogen at ambient conditions.
Cold boil-off hydrogen is a little denser than air and may accumulate in pits and trenches, for
short periods depending on temperature and quantity. After that hydrogen rises and diffuses
rapidly.
Cold boil-off hydrogen condenses the moisture in the air, thus creating a highly
visible fog.
HYDROGEN STORAGE SYSTEM

Liquid Hydrogen

Liquid hydrogen (LH2 or LH2) is the liquid state of the element hydrogen. Hydrogen

is found naturally in the molecular H2 form.

To exist as a liquid, H2 must be cooled below hydrogen's critical point of 33 K.

However, for hydrogen to be in a full liquid state without evaporating at atmospheric
pressure, it needs to be cooled to 20.28 K (−423.17 °F/−252.87°C). One common method of
obtaining liquid hydrogen involves a compressor resembling a jet engine in both appearance
and principle. Liquid hydrogen is typically used as a concentrated form of hydrogen storage.
As in any gas, storing it as liquid takes less space than storing it as a gas at normal
temperature and pressure, however the liquid density is very low compared to other common
fuels. Once liquefied it can be maintained as a liquid in pressurized and thermally insulated
containers.

Liquid hydrogen consists of 99.79% parahydrogen, 0.21% orthohydrogen.

Requirements Of Liquid Hydrogen Storage System

In the early 1980's, Los Alamos National Laboratory, in conjunction with DFVLR32 (a
German government research agency), studied hydrogen powered internal combustion engine
vehicles utilizing LH2 onboard storage and their corresponding LH2 refueling requirements.
That study produced the following list of storage requirements and recommendations:
 Heat leak into the tank should be minimized to yield low boil-off
 The pressure capability of the LH2 tank should be high enough to allow a lockup time
of several days or preferably a week
 The LH2 tank should be as crash resistant as feasible
 The filled LH2 tank weight should be no greater than a gasoline tank
  The energy storage should be sufficient for satisfactory unrefueled range preferably
equivalent to a conventional gasoline-fueled vehicle
 The LH2 tank volume and shape should allow safe and unobtrusive mounting
 The LH2 tank design should allow practical and economic fabrication, operation, and
maintenance
 Extraction and delivery of the hydrogen from the tank to the engine should correlate
to the engine fuel delivery requirements
 Tank filling and operation should, at all times, be acceptably safe.

Hydrogen Infrastructure Implications

If LH2 is to be stored onboard the vehicle, it must first be available at the refueling station.
This requires LH2 to be either generated on site from gaseous H2 or delivered to the refueling
station and stored at the station in liquid form. Both present difficulties. First, creation of LH2
from gaseous H2 is energy intensive, requiring electrical energy equaling approximately 40%
of the hydrogen's lower heating value. Secondly, the liquefaction equipment is expensive
thereby discouraging small scale refueling site liquefaction and favoring large scale remote
liquefaction plants with LH2 truck transport to the individual refueling sites. Third, unlike
compressed gas H2, LH2 cannot be stored for long periods without boil-off losses or energy
expenditure to re-liquefy the boil-off. Boil-off loses increase with smaller storage tanks, again
favouring large, central storage facilities. None of these problems is insurmountable and Ford
and the hydrogen production community are currently examining many infrastructure
options. However, we can surmise that the LH2 infrastructure is more cost-effective when
demand for hydrogen is very high. Very early FCV demonstration might utilize LH2 from
excess capacity at existing LH2 plants. But industrial demand for hydrogen is growing, due in
part to the need for reformulated gasoline. Therefore new LH2 plants would have to be built
early in any FCV market penetration, and the industrial gas companies may not be able to
justify the large capital investments necessary for central LH2 plants. Consequently, while
LH2 may ultimately be a good choice for onboard H2 storage, during the transition to
widespread FCV usage, LH2 infrastructure may not be available at reasonable cost.

Structure Of Liquid Hydrogen Storage Tank

Liquid hydrogen storage systems, consist of double-wall cylindrical tanks that hold a
hydrogen storage mass of about 10 kg. Preferred shell materials are stainless steel or
aluminum alloy, since they are very resistant against hydrogen brittleness and show
negligible hydrogen permeation. Low specific weight combined with high modules and
strength as well as high coefficients of thermal expansion and very good characteristics of
heat conductivity have given aluminum a major role in the aerospace and automotive
industries. In case of stainless steel, the minimum wall thickness of the shells is between 2
and 4 mm according to the regulation for cryogenic vessels. Therefore, the weight of the
whole tank system including valves and heat exchanger is about 150 kg.
The space between the inner and outer vessel is mainly used for the thermal super
insulation. The heat entry by thermal radiation is reduced by about 40 layers of super
insulation foils with an area weight of 1.5 to 3.0 kg/m², composed of reflective aluminium or
aluminized polymer foils separated by glass fiber spacers. The vacuum pressure of about 10 -3
Pa at 20 K reduces the thermal convection to a minimum. The support structures, keeping the
inner tank in position to the outer tank, are made of glass or carbon fibre reinforced plastics.
If the vehicle is not used for more than three days, the heat entry leads to a boil-off rate of 1
to 3 % per day.
 Figure.1.1 Structure of liquid hydrogen storage tank

During the filling procedure both valves, the cryogenic filling valve (7) and the
cryogenic return valve (8), are opened. Liquid hydrogen flows from the filling station via a
Johnston-Cox coupling (3) and the cryogenic filling valve into the inner vessel (1). In order to
keep the inner tank pressure low, evaporated gaseous hydrogen leaves the inner tank via the
cryogenic return valve and flows back to the filling station. After finishing the filling
procedure, both cryogenic valves will be closed. For hydrogen extraction, the cryogenic
filling valve remains closed while the cryogenic return valve is open. Gaseous hydrogen
leaves the inner tank to the cooling water heat exchanger (5). Hydrogen heats up above
ambient temperature and flows further into the pressure regulation valve (9). If the inlet
pressure is above the defined set pressure of the pressure regulator, the partial flow inlet will
be closed and no hydrogen can pass through the tank heater (4). Therefore, no additional heat
will be led to the inner tank heater and the pressure will decrease. During stand-by, both
cryogenic valves are closed. During long-term parking the hydrogen pressure in the inner
tank rises until the boil-off valve (11) will limit the boil-off pressure.
Overpressure in the inner tank must not open the cryogenic valves. In case of a fault of the
boil-off valve the pressure in the inner tank rises until the safety relief valve (12) opens. The
last device that prevents the explosion of the tank is a rupture disk (16), which is needed in
case of a default of the safety relief valve.
LH2 Tank Design, Operation, And Cost
A representative liquid hydrogen tank based on a Los Alamos/DFVLR design is shown in
figure below. The tank consists of a 2 mm (0.08 in) thick aluminum alloy inner dewar
surrounded by 5.08 cm (2 inches) of multi-layer insulation (MLI) which, in turn, is
surrounded by a 3 mm (0.12 inches) aluminum alloy outer shell. The outer shell functions to
both protect the fragile MLI and allow the MLI chamber to be evacuated thereby greatly
increasing its thermal resistance. The shape of the dewar and outer shell is cylindrical with
ellipsoidal end cap and was selected as a compromise between manufacturing ease, vehicle
packaging, and volume to surface area concerns. The inner dewar is supported by six fibre
glass epoxy supports extending radially from the centre of the end caps, three at each end.
This arrangement of 0.635 cm (0.25 inch) diameter, low conductivity supports is designed to
provide a long thermal conduction pathway yet still survive a 10-g acceleration load in any
direction. To remove gaseous hydrogen from the tank for use by the fuel cell and to reduce
insulation thickness, the GH2 removal conduit is helically wrapped around the outside of the
dewar, half way through the insulation thickness and exits the system through a port in the
outer shell dome end. The primary purpose of this helical winding is to create a long thermal
conduction path thereby limiting heat leak. In addition, the GH2 line acts as a partial vapor
cooling shield (VCS) where the exiting cold hydrogen gas cools the insulation layer thereby
minimizing heat leakage into the tank. Use of a full VCS effectively cuts the insulation
thickness in half for a given boil-off rate. No VCS credit (other than a long conduction path)
is assumed in the tank design. The GH2 removal conduit is stainless steel with a 12 mm (0.47
inch) ID and 1 mm wall thickness.
The LH2 fill line enters through a port in the outer shell at one end cap, is routed around the
tank through the insulation to increase the thermal conduction path and enters the dewar
through a port in the centre of the tank. The line extends from the top of the dewar to the
bottom and holds 10 Allen -Bradley carbon resistors along its length. These resistors use
variation in electrical resistance to estimate tank temperature and variation in heat transfer to
estimate the level of the LH2/GH2 boundary. The electrical line leading to the resistors
follows the same path to the outside as the LH2 fill line. Two perforated aluminum baffle
plates are mounted vertically within the dewar to reduce sloshing and thermal stratification of
the LH2.
Since only GH2 is removed from the tank for use by the fuel cell, a small 50W electrical
heater is mounted on the bottom of the dewar to ensure there is always sufficient gas pressure
available. The electrical line for the heater also follows the LH2 feed line pathway. An
evacuated chamber also composed of 3 mm (0.12 inch) thick aluminum alloy is mounted on
the outside of the outer shell at the end cap. This enclosure houses the LH2 feed and GH2
return lines emerging from the dewar and protects the connection devices for these lines.
Both are female receptacles designed to accept a bayonet style connector. Figure 4.2-3
displays typical bayonet connectors suitable for use in this role. The chamber is evacuated to
further reduce thermal leakage into the feed and return lines but also to help maintain the

vacuum between the dewar and the outer shell.

Small heat exchangers measuring 20 cm x 9.9 cm x 3 cm (7.9" x 3.9" x 1.2") are currently
used by industry to heat LH2 from 20 to 280K at a flow rate of 100 liters/hr.36 This equates
to approximately 9 kW of heat capacity. Similar heat exchangers will be used onboard the
vehicle to warm the hydrogen prior to fuel cell entry. Fuel cell waste heat can also be used to
warm the hydrogen. LH2 tank cost is projected by summing component material and
manufacturing costs. Near and far term costs are summarized in Figure 4.2-2. Near term
insulation material cost is based on price quotes for the two main components of MLI (metal
foil and separator cloth) and is based on bulk purchases consistent with 5,000 to 10,000
vehicles per year. Far term materials costs are DTI projections based on a 1,000,000
vehicle/year production rate. All components except the insulation have an estimated
manufacturing cost of $6.6/kg. Near term insulation manufacturing cost is based on an
estimate from Lydall-Manning indicating assembly of the insulation around the tank would
cost approximately seven times the cloth material cost, i.e., $71/kg of insulation. Far term
manufacturing cost is set at $13.2/kg to reflect highly automated, but delicate, foil/spacer
interlacing and tank mounting.

Lh2 Tank Insulation

As listed in Figure below, many types of thermal insulation are available, with the
main design choice being between load bearing and non-load bearing insulations. Load
bearing insulations, in general, allow more thermal leakage but carry loads through the
insulation allowing the inner tank to "sit" on the insulation. Non-load bearing insulation
cannot carry the inner tank load and must be mounted inside the insulation by mounting
support rods or straps. The mounting supports conduct heat, reducing the thermal advantages
of the non-load bearing insulation, and thus are usually composed of a low conductivity
material themselves and often designed with a long conduction path before attachment to the
outside support.
Non-load bearing, multi-layer insulation (MLI), such as SI-62, has been chosen for
the LH2 system conceptual design. MLI consists of alternate layers of low-emittance
radiation shields separated by low conductivity spacing material. The radiation shield
material is usually very thin aluminum sheets or thin plastic sheets (mylar or kapton) that
have been coated by a thin vapor-deposited layer of aluminum, gold, or some other high
reflectivity material. Spacer materials are usually silk, nylon, or dacron netting. The
insulation volume is evacuated to a near-vacuum to minimize gas convective thermal
transfer. Consequently, radiation is the primary heat transfer mode.
As seen in the insulation listing, insulation conductivity varies dramatically between
insulation types. Heat leakage and insulation thickness vary linearly with insulation
conductivity, so accurate estimation of the conductivity factor is critical to an accurate system
performance estimate. An insulation conductivity k of 0.000052 W/mK (3 x 10-5
BTU/hr/ft/°R) has been selected for the tank design discussed in the next section. This
corresponds to non-load bearing SI-62 and agrees well with a semi-empirical relationship
used by Lockheed to predict the performance of MLI systems. Los Alamos National Labs,
however, has observed nearly a doubling in the conductivity of MLI LH2 storage systems
after vibration testing.35 Automotive LH2 systems would also suffer this performance
degradation due to vibration induced movement of the insulation and tank. Consequently, the
tanks should be designed for this higher level of conductivity or, as is assumed in this report,
designed to prevent the deterioration.

Advanced Lh2 Tank Options

 Several design advances can be envisioned to make the LH2 system lighter. The first
option is to replace the inner and outer aluminum tanks described above with lined carbon
composite tanks as used in the pressurized gas system. This requires the inner carbon tank to
function at LH2 temperature. To investigate the effects of cryogenic temperature on the inner
carbon composite tank under 20.7 MPa (3,000 psi) pressure, A.D. Little hydrostatically tested
an aluminum lined, full carbon wrapped tank with LN2.39 Seventeen pressure cycles were
performed at 80K over a 0-20.7 MPa (0-3,000 psi) pressure range. Ten temperature cycles
were also performed between 80K and 300K. No burst, leakage or anomalous behaviour was
reported. After testing, the tank was returned to its manufacturer, Structural Composites
Industries (SCI), for burst testing. The tank burst at 77.57 MPa (11,242 psig): a 12%
reduction from its design burst pressure of 87.49 MPa (12,680 psig). This may be within
normal statistical limits on burst pressure or may indicate strength degradation due to
pressure/temperature cycling. Regardless, the test indicates operation of the tanks at
cryogenic temperatures is feasible but suggests more investigation is required to determine
the full temperature effects over time at 20K temperature and to determine the characteristics
of thin-wall tanks at the 345-690 kPa (50-100 psi) LH2 operating pressure.
The outer tank that maintains the insulation vacuum can also be constructed of carbon
but this creates two challenges. First, the composite tank's performance under compression is
more complex and less predictable. Second, the composite tank's joints for assembly disrupt
the carbon wrapping, so packaging of the inner tank and its insulation inside the vacuum shell
could prove difficult.
Dormancy, Boil-Off, And Lock-Up
One of the perceived major disadvantages of cryogenic systems is their poor
dormancy characteristics. Due to the large temperature gradient between the cryogen and
ambient air, heat leaks into the tank causing the LH2 to vaporize or boil-off. Pressure builds
up within the tank until tank pressure limits are exceeded at which time pressure valves vent
the H2 gas. The amount of time the pressure is able to build-up from fill pressure before
venting is necessary is called the lock-up time. It is a function of heat leak (insulation
effectiveness), pressure capacity of the LH2 tank, and empty volume available in the LH2 for
gas accumulation. A lock-up time calculation has not been conducted for the LH2 design
concept but is estimated to be approximately 15 hrs based on similar Los Alamos LH2 tank
designs. Insulation thickness has been sized to achieve a boil-off rate of approximately 1.8%
per day, or a maximum of 56 days before all tank LH2 vaporizes.
 Boil-off losses are a potential problem for three reasons. First, the H2 is lost and
therefore boil-off represents an expense. Second, vented boil-off losses may accumulate
causing safety concerns. Third, long term unattended LH2 vehicles may lose all stored H2.
This is the classic airport scenario, wherein a traveler leaves his car at the airport during his
2-3 week vacation only to find his car devoid of fuel and therefore undrivable upon his
return. The only way to extend the useful life of the LH2 is by thicker or better insulation or
by increasing the pressure capability of the LH2 tank. Thicker insulation is impractical since
it increases system volume and does not reduce the heat input through the feed lines, fill
lines, and supports. Higher tank pressure capacity is discussed in section 5.2 as part of the
cryo-pressure vessel system.
However, Hynek and Moore40 conclude that LH2 boil-off is not a significant
problem for two reasons. First, LH2 boil-off rates of 1%-2% cause the amount of H2 lost to
boil-off to be economically insignificant and eliminate the "airport scenario" except for the
longest trips (2+ months). Secondly, vented H2 can be run through the fuel cell or
catalytically converted, thus eliminating accumulation of vented H2 in a garage. Furthermore,
they estimate that if the vehicle is run every other day, pressure will not build up within the
tank and no H2 will ever leave through the pressure vent. Overall, they do not see any
significant vehicle dormancy issues with LH2. Two cautionary comments on the LH2
dormancy issue are warranted. First, if boil-off loss cannot be maintained at less than a
couple of percent per day, boil-off losses become a big issue. As stated earlier, normal
automobile vibrations may significantly degrade the MLI effectiveness potentially tripling (or
more) the boil-off rate. Vapour cooling may alleviate some of this but only at the expense of
complexity and manufacturing cost. Routing the boil-off to the fuel cell adds complexity and
may impact vehicle battery sizing. Secondly, dormancy is also an issue for the hydrogen
infrastructure and losses (or re-liquefaction) must be considered for production plant storage,
bulk transport, and dispensing site storage. Overall, these factors add to the delivered price of
LH2 potentially causing LH2 to be economically uncompetitive.

Liquid Hydrogen Safety

Liquid hydrogen has potential hazards, including the risk of cold burns, and the
increased duration of leaked liquid cryogenic fuel in the event of a collision. Liquid hydrogen
will initially condense air in the vicinity, and must warm up before the rapid dispersal
characteristics of gaseous hydrogen come into play. In this regard, a large spill of liquid
hydrogen has some of the characteristics of a gasoline spill. However, a liquid hydrogen spill
will dissipate much faster than a gasoline spill. Liquefaction of air represents a safety issue
due to the propensity for liquified air to combust with even stable materials such as asphaltic
Pavement. Thus, large LH2 spills could ignite due to the probable presence of liquified air.
Liquid hydrogen presents another set of safety issues that must be addressed in the context of
the hydrogen infrastructure. Since H2 liquefaction appears to be uneconomical at small scale,
hydrogen would be liquefied at a large central plant and transported by truck to distant
refueling stations. Industry has extensive experience with the safe bulk production of LH2
and the safety record of commercial LH2 truck transport is also excellent. No significant LH2
safety issues are currently linked to production or distribution, but Ford and its infrastructure
team members are continuing to examine the issue. Safe LH2 refueling by untrained
personnel remains an unresolved issue. Future LH2 stations would presumably operate as
current gasoline stations allowing users a "self-serve" option. Consequently LH2 pumps
would need to have redundant, fool proof safety features to allow safe refueling even by
inattentive, untrained drivers. Such systems are not difficult to conceptualize but more
detailed design work is needed. Ford and its infrastructure team members are exploring such
LH2 refueling facilities.

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