Transportation and
Storage of Hydrogen
Hydrogen Transmission in Pipelines
Three different modes:
1) pipelines and tube trailers for gaseous hydrogen or a
mixture of hydrogen and natural gas transportation
2) trucks, rails, barges, and ships with cryogenic tanks for
liquefied hydrogen delivery
3) ) high energy- density carriers such as ethanol, methanol,
and other liquids derived from renewable biomass that can
be transported and reformed to hydrogen at the end point
of use
Illustration of hydrogen delivery methods by
(a) pipeline, (b) gas tube trailer, and
(c) cryogenic liquid tank truck.
Hydrogen Compression
Compression is an integral aspect of gaseous hydrogen delivery via
pipelines
piston (or reciprocating) and rotary compressors are used to compress
hydrogen that are similar to those used for natural gas, with
modifications of design and materials.
Three available options for hydrogen storage :
1) compressed hydrogen gas at 5000-10000 psi
(Gaseous high pressure storage, with which the fuel
stored under high pressure in a storage cylinder
at ambient temperature )
2) liquid hydrogen-cryogenic liquid
Liquefied storage, in which the hydrogen is liquefied to cryogenic temperatures
(-411F) at which point the hydrogen becomes a liquid
3) solid
fuel as adsorbed hydrogen as metal hydrides, MH, and
carbon materials
There are several hazards associated with hydrogen, ranging from respiratory ailment,
component failure, ignition, and burning.
The primary hazard with hydrogen is the production of a flammable mixture, which can
lead to a fire or explosion. Because its minimum ignition energy in air at atmospheric
pressure is about 0.2 mJ, so hydrogen is easily ignited.
l
Hydrogen can produce mechanical failures of containment vessels, piping, and other
components due to hydrogen embrittlement.
l
Upon long term exposure to the gas, many metals and plastics can lose ductility and
strength, which leads to the formation of cracks and can eventually cause ruptures.
l
A form of hydrogen embrittlement takes place by chemical reaction. At high temperatures,
for instance, hydrogen reacts with one or more components of metal walls to form hydrides,
which weaken the lattice structure of the material.
Hydrogen leaks are typically caused by defective seals or gaskets, valve misalignment, or
failures of flanges or other equipment.
There are four major issues for gaseous hydrogen
delivery via pipelines
High initial capital investment costs : new pipeline design and
construction imply high initial capital costs, Transporting gaseous
hydrogen via the existing pipelines is the low-cost option for delivering
large volumes of hydrogen. Converting natural gas pipelines to carry a
blend of natural gas and hydrogen (up to about 20% hydrogen) may
require only modest modifications to the pipeline; however, more
substantial modifications may be required for delivering pure hydrogen
Material challengehydrogen embrittlement of steel pipelines
and alternatives : Hydrogen delivery via pipelines would require the
gaseous hydrogen to be transmitted under very high pressure levels (up
to 3000 psi) and the use of economically viable materials such as pipeline
steels. This mechanism is not well understood.
eals, valves and fittings, and equipment design to avoid leakage. Low-cost leak det
ession of hydrogen as compared with four to five stages for natural gas.
All types of structural materials will be exposed to hydrogen at elevated
pressures and expected to perform their function. For example:
Steels-transmission pipelines, compressors, storage containers,
dispensers
Al Alloys-containers, tube trucks, on-board storage
Polymers and PMCs-distribution pipelines, storage containers
Stainless Steels-fuel cell containers and components, on-board tubing
and storage
Ni Based Alloys-compressors, valves, bearing surfaces
Others-Cu alloys, Ti Alloys,
Goal for optimum hydrogen Storage Materials
High hydrogen capacity per unit mass and unit volume (which determine
the available energy)
Low dissociation temperature
Moderate dissociation pressure
Low heat of formation to minimize the energy necessary for hydrogen
release and low heat dissipation during the exothermic hydride formation
Reversibility for limited energy loss during charge and discharge of
hydrogen
Fast kinetics
High stability against O2 and moisture for a long cycle life
Cycleability
Low cost of recycling and charging infrastructures
High safety
solid fuel as adsorbed hydrogen as metal hydrides, MH, and
carbon materials
Types of Metal Hydrides
safe, volume-efficient storage method for on-board vehicle
applications
Metal hydrides have higher hydrogen-storage density (6.5Hatoms/cm3 for
MgH2) than hydrogen gas (0.99Hatoms/cm3) or liquid hydrogen
(4.2Hatoms/cm3)
Metals can combine with hydrogen to form metal hydrides by three
different bond types:
(1) ionic, (2) covalent, and (3) metallic
Based on the strength of the bonds, metal hydrides are broadly
classified into two categories: (1) reversible and (2) irreversible
There are two possible ways of hydriding a metal, direct dissociative
chemisorption and electrochemical splitting of water.
These reactions are:
M + x /2H2 MHx , (1)
M + x/2H2O + x/2e MHx + x/2OH, (2)
where M represents the metal.
host lattice of
the metal
-phase at which only some hydrogen is absorbed and -phase at which hydride is fully
formed.
The main disadvantages of MgH2 as a hydrogen store
high temperature of hydrogen discharge,
slow desorption kinetics
a high reactivity toward air and oxygen
high operating temperature which is too high for practical on-board
applications due to the high thermodynamic stability of MgH2 results in a
relatively high desorption enthalpy, which corresponds to an unfavorable
desorption temperature of 300 C at 1bar H2
Sodium Alanates (NaAlH4 )
theoretical reversible storage capacity of about 5.5 wt%.
The 200 meV AlH4 Breathing Modes
It is one of the known complex hydride with favorable thermodynamics and an acceptable
gravimetric storage capacity for use in conjunction with a polymer electrolyte membrane (PEM)
fuel cell system, which operates at about 90C.
Hydrogen is released from NaAlH4 in two steps:
3NaAlH4 Na3AlH6 + 2Al + 3H2 (3.7 wt% hydrogen released)
(thermodynamically favorable ambient pressure and above 33C)
Na3AlH6 3NaH + Al + 1.5H2 (1.8 wt% hydrogen released)
(above 110C )
NaH Na + 1/2H2
NaAlH4 first decomposes to evolve molecular hydrogen and forms an intermediate compound Na3AlH6 , which further decomposes to NaH with
the formation of additional metallic aluminum and hydrogen
Rehydrogenation is preferably done at 10 MPa and slightly above 100C.
Boron Hydrides
All the elements of the boron group form polymeric hydrides (MH3)x because
the MH3 monomers are strong Lewis acids and are unstable.
Borane (BH3) achieves electronic saturation by dimerization to form diborane
(B2H6).
Lithium tetrahydroborate, LiBH4, has a hydrogen storage capacity of 18.4 wt
%, which is the highest gravimetric storage capacity among the complex
hydrides . Its decomposition reaction to produce hydrogen is as follows:
Li(BH4) LiBH2 + H2 LiH + B + 3/ 2 H2
or
Li(BH4) LiB + 2H2
Disadvantages of Boron Hydrides
The thermodynamic properties of complex boron hydrides are unfavorable
for use in mobile hydrogen storage applications except in hydrolytic storage,
where other hydrides are much more stable than the corresponding alanates.
Small amounts of volatile boranes can form that are toxic and can damage
subsequent aggregates in a fuel cell system, which over time would lead to a
loss of storage capacity.
Magnesium Hydride
Magnesium hydride (MgH2) is inexpensive and has a potential storage capacity
of 7.6 wt% H2
Disadvantages of Magnesium Hydride
For hydrogenation, Mg needs to be exposed to a high temperature and pressure
of hydrogen. Dehydrogenation, at ambient temperature gives a low pressure of
about 0.1 Pa, mainly due to the very high dissociation enthalpy of 74.5 kJ/mol
MgH2. Thus, dehydrogenation needs to be carried out at 300C to achieve a
hydrogen pressure of more than 0.1 MPa .
Another difficulty is that MgH2 , similar to other light metal hydrides, has slow hydrogen absorption/ desorption
kinetics. A fast absorption/desorption kinetics is important especially for vehicular application to have a short refueling time and a
sufficient rate of hydrogen release to fulfill the power requirement while driving
Mg-11.3 atomic% Ni alloy that has been studied for hydrogen storage
Most of the hydrogen is
stored in the low-density
magnesium phase. The
small Mg2Ni inclusions
catalyze the decomposition
of the molecular hydrogen,
increasing the
hydrogen
absorption/desorption
kinetics significantly.
Catalysts are also finely
divided. And intimate
contact with pure Mg phase
two-phase mixture of pure magnesium and
Mg2Ni
Thermodynamics
An important feature in hydrogen storage by metal hydrides is the pressure
plateau, which is a pressure at which the material reversibly absorbs/desorbs
large quantities of hydrogen.
pressureconcentration isotherms (PCI) are generally utilized for assessing the ability
of metal hydrides to reversibly store hydrogen
For many applications, the plateau pressure should be close to ambient pressure,
which allows the use of lightweight storage containers
Hydrogen Detection
and Safety
Physical Properties
Hydrogen has the second lowest boiling point and melting points of all substances, second
only to helium. Hydrogen is a liquid below its boiling point of 20 K (423 F; 253 C) and
a solid below its melting point of 14 K (434 F; 259 C) and atmospheric pressure.
Pure hydrogen is odorless, colorless and tasteless. A stream of hydrogen from a leak is
almost invisible in daylight.
Hydrogen is non-toxic but can act as a simple asphyxiant by displacing the oxygen in the
air.
Inhaled hydrogen can result in a flammable mixture within the body. Inhaling hydrogen
can lead to uncon-sciousness and asphyxiation.
Hydrogen leaks are dangerous in that they pose a risk of fire where they mix with air. However,
the small molecule size that increases the likelihood of a leak also results in very high buoyancy
and diffusivity, so leaked hydrogen rises and becomes diluted quickly, especially out-doors.
Although hydrogen has many useful properties, some have serious safety
implications:
[Link] and odourless
[Link] reactive with oxygen and other oxidizers
[Link] ignition energy
[Link] flame temperature
[Link] flame in daylight conditions
[Link] Joule-Thomson coefficient; leaking gas warms and may
spontaneously ignite
[Link] molecular size promotes leaks and diffusion
[Link] wide flammability limits in air mixtures
[Link] diffuse into or react with certain metals, embrittling them
[Link] cryogenic liquid at 20K is even colder than frozen nitrogen,
oxygen or argon
Hydrogen codes and standards
Guidelines
The current ANSI/AIAA standard for hydrogen safety guidelines is AIAA G-095-
2004, Guide to Safety of Hydrogen and Hydrogen Systems. As NASA has been
one of the world's largest users of hydrogen, this evolved from NASA's earlier
guidelines, NSS 1740.16 (8719.16). These documents cover both the risks posed
by hydrogen in its different forms and how to deal with them.
Ignition
"Hydrogen-air mixtures can ignite with very low energy input, 1/10 that required
igniting a gasoline-air mixture. For reference, an invisible spark or a static spark
from a person can cause ignition.
"Although the autoignition temperature of hydrogen is higher than those for most
hydrocarbons, hydrogen's lower ignition energy makes the ignition of hydrogen
air mixtures more likely. The minimum energy for spark ignition at atmospheric
pressure is about 0.02 millijoules."
Leaks
Leakage, diffusion, and buoyancy: These hazards result from the difficulty
in containing hydrogen. Hydrogen diffuses extensively, and when a liquid
spill or large gas release occurs, a combustible mixture can form over a
considerable distance from the spill location.
Hydrogen, in both the liquid and gaseous states, is particularly subject to
leakage because of its low viscosity and low molecular weight (leakage is
inversely proportional to viscosity). Because of its low viscosity alone, the
leakage rate of liquid hydrogen is roughly 100 times that of JP-4 fuel, 50
times that of water, and 10 times that of liquid nitrogen.
Hydrogen leaks can support combustion at very low flow rates, as low as 4
micrograms/s.
Prevention
Hydrogen collects under roofs and overhangs, where it forms an explosion
hazard; any building that contains a potential source of hydrogen should
have good ventillation, strong ignition suppression systems for all electric
devices, and preferably be designed to have a roof that can be safely blown
away from the rest of the structure in an explosion.
It also enters pipes and can follow them to their destinations. Hydrogen
pipes should be located above other pipes to prevent this occurrence.
Hydrogen sensors allow for rapid detection of hydrogen leaks to ensure that
the hydrogen can be vented and the source of the leak tracked down.
As in natural gas, an odorant can be added to hydrogen sources to enable
leaks to be detected by smell. While hydrogen flames can be hard to see
with the naked eye, they show up readily on UV/IR flame detectors.
Accidents
There are reports of explosions of compressed hydrogen during delivery at
the Muskingum River Coal Plant (owned and operated by AEP) caused
significant damage and killed one person.
During the 2011 Fukushima nuclear emergency, four reactor buildings were
damaged by hydrogen explosions. Exposed Zircaloy cladded fuel rods
became very hot and react with steam, releasing hydrogen. Safety devices
that normally burn the generated hydrogen failed due loss of electric power.
To prevent further explosions, vent holes were opened on the top of
remaining reactor buildings.
Detection
The detection layers themselves encompass different detection techniques that either
improve scenario coverage or increase the likelihood that a specific type of hazard is
detected.
Such fire and gas detection layers can consist of catalytic sensors, ultrasonic gas
leak monitors, and fire detectors .
Ultrasonic gas leak detectors can respond to high pressure releases of hydrogen,
such as those that may occur in hydrocracking reactors or hydrogen separators.
In turn, continuous hydrogen monitors like catalytic detectors can contribute to
detecting small leaks, for example, due to a flange slowly deformed by use or
failure of a vessel maintained at close to atmospheric pressure.
To further protect a plant against fires, hydrogen-specific flame detectors can
supervise entire process areas. Such wide coverage is necessary: Because of
hydrogen cloud movement, a fire may be ignited at a considerable distance from the
leak source.
Pipeline Integrity Monitoring
nine major potential integrity threats present in the natural gas
pipelines
internal and external corrosion,
Sensor ,
third-party damage,
soil movements,
manufacture and construction-related threats,
incorrect operation, weather,
and outside force threats
the highest integrity risk is from third-party damage
construction and excavation
